Die approbierte Originalversion dieser Dissertation ist an der Hauptbibliothek

der Technischen Universität Wien aufgestellt (http://www.ub.tuwien.ac.at).

The approved original version of this thesis is available at the main library of
the Vienna University of Technology (http://www.ub.tuwien.ac.at/englweb/).

TECHNISCHE

IlJ
UNIVERSITÄT
WIEN

VIENNA
UNIVERSITY OF
WIE N TECHNOLOGY

DISSERTATION

ANNUAL CYCLES OF MAJOR IONS, LEVOGLUCOSAN AND

CELLULOSE IN ATMOSPHERIC AEROSOL SAMPLES

•
ausgefùhrt zum Zwecke der Erlangung des Akademischen Grades eines Doktors der
technischen Wissenschaften/der Naturwissenschaften

unter der Leitung von

A.o. Univ. Prof. Dipl. Ing. Dr. Anne Kasper-Giebl
am

Institut für Chemische Technologien und Analytik (164)

•
Eingereicht an der Technischen Universität Wien
Fakultät für Technische Naturwissenschaften und Informatik

von

Mag. Asuncion Sanchez Ochoa

Matr. Nr. 327271
Schelleingasse 36-605
A- 1040 Wien

Wien, Juli 2005

"
 Kurzfassung

KURZFASSUNG

Diese Arbeit beruht auf Ergebnissen, die im Rahmen der Projekte ,Sackgroundmessungen
Sonnblick' und ,CARBOSOL' gewonnen wurden. Seide Forschungsprojekte befaßten sich
mit der Untersuchung des atmosphärischen Aerosols.
Im Projekt ,Sackgroundmessungen Sonnblick' wurden am Sonnblick Observatorium (3106 m
Seehöhe) die Aerosolkomponenten Sulfat, Nitrat, Oxalat, Chlorid, Ammonium, Kalzium,
Magnesium, Natrium und Kalium sowie die Spurengase Schwefeldioxid, Salpetersäure und
Ammoniak mit zwei parallel installierten In-Line Filterpacks gemessen. Im Zeitraum von
Dezember 2002 bis Oktober 2004 wurden täglich Proben genommen. Das Projekt

• ,CARBOSOL' wurde an sechs Meßstellen durchgeführt.

Herbst 2004 wurden Hi-Vol Wochenproben aufQuarzfaserfiltern
wurden nur die Messungen von Cellulose und Levoglucosan
In der Zeit von Sommer 2002 bis
gesammelt. Für diese Arbeit
ausgewertet. Die Meßstellen
können in Bodenstationen und Bergstationen eingeteilt werden. Bodenstationen sind auf den
Azoren (maritime Hintergrundstation, 50 m Seehöhe), in Aveiro (Portugal, ländliche Station
in Küstennähe, 40 m Seehöhe) und K-Puszta (Ungarn, ländliche Station 136 m Seehöhe).
Bergstationen sind Schauinsland (Deutschland, ländliche Station 1205 m Seehöhe), Puy de
Dome (Frankreich, kontinentale Hintergrundmeßstelle 1405 m Seehöhe) und Sonnblick
(kontinentale Hintergrundmeßstelle, Einfluß der freien Troposphäre, 3106 m Seehöhe).

Die im Rahmen der ,Backgroundmessungen Sonnblick' bestimmten Aerosolkomponenten

• sowie Ammoniak und Salpetersäure zeigten ausgeprägte Jahresgänge mit höheren Meßwerten
im Sommer und geringeren Werten im Winter. Das ist charakteristisch
wie das Sonnblick Observatorium. Die Konzentrationswerte
für eine Bergstation
für Oxalat sind etwa eine
Größenordnung geringer als für die anorganischen Hauptkomponenten, zeigen aber auch den
charakteristischen Jahresgang. Für Schwefeldioxid wurden keine deutlichen Unterschiede
zwischen den Winter- und Sommerwerten bestimmt. Die Jahresmittelwerte der
Aerosolkomponenten Nitrat, Sulfat und Ammonium lagen bei 5,5 bis 15 nmollm3, die
Jahresmittelwerte der Spurengase bei 2,9 bis 19 nmollm3•

Die im Rahmen von ,CARBOSOL' gemessenen mittleren Konzentrationswerte lagen an den

sechs Meßplätzen bei 14 bis 273 nglm3 für Levoglucosan und bei 13,5 bis 133 nglm3 fur
Cellulose. Die höchsten Werte für Levoglucosan wurden an den Bodenstationen Aveiro und
K-Puszta bestimmt. Besonders in Aveiro weist in den Wintermonaten sehr hohe
 Kurzfassung

KURZFASSUNG

Diese Arbeit beruht auf Ergebnissen, die im Rahmen der Projekte ,Backgroundmessungen
Sonnblick' und ,CARBOSOL' gewonnen wurden. Beide Forschungsprojekte befaßten sich
mit der Untersuchung des atmosphärischen Aerosols.
Im Projekt ,Backgroundmessungen Sonnblick' wurden am Sonnblick Observatorium (3106 m
Seehöhe) die Aerosolkomponenten Sulfat, Nitrat, Oxalat, Chlorid, Ammonium, Kalzium,
Magnesium, Natrium und Kalium sowie die Spurengase Schwefeldioxid, Salpetersäure und
Ammoniak mit zwei parallel installierten ln-Line Filterpacks gemessen. Im Zeitraum von
Dezember 2002 bis Oktober 2004 wurden täglich Proben genommen. Das Projekt
• ,CARBOSOL' wurde an sechs Meßstellen durchgeführt. ln der Zeit von Sommer 2002 bis
Herbst 2004 wurden Hi-Vol Wochenproben auf Quarzfaserfiltem gesammelt. Für diese Arbeit
wurden nur die Messungen von Cellulose und Levoglucosan ausgewertet. Die Meßstellen
können in Bodenstationen und Bergstationen eingeteilt werden. Bodenstationen sind auf den
Azoren (maritime Hintergrundstation, 50 m Seehöhe), in Aveiro (Portugal, ländliche Station
in Küstennähe, 40 m Seehöhe) und K-Puszta (Ungarn, ländliche Station 136 m Seehöhe).
Bergstationen sind Schauinsland (Deutschland, ländliche Station 1205 m Seehöhe), Puy de
Dome (Frankreich, kontinentale Hintergrundmeßstelle 1405 m Seehöhe) und Sonnblick
(kontinentale Hintergrundmeßstelle, Einfluß der freien Troposphäre, 3106 m Seehöhe).

Die im Rahmen der ,Backgroundmessungen Sonnblick' bestimmten Aerosolkomponenten

• sowie Ammoniak und Salpetersäure zeigten ausgeprägte Jahresgänge mit höheren Meßwerten
im Sommer und geringeren Werten im Winter. Das ist charakteristisch fill eine Bergstation
wie das Sonnblick Observatorium. Die Konzentrationswerte für Oxalat sind etwa eine
Größenordnung geringer als fiir die anorganischen Hauptkomponenten, zeigen aber auch den
charakteristischen Jahresgang. Für Schwefeldioxid wurden keine deutlichen Unterschiede
zwischen den Winter- und Sommerwerten bestimmt. Die lahresmittelwerte der
Aerosolkomponenten Nitrat, Sulfat und Ammonium lagen bei 5,5 bis 15 nmoVm3, die
JahresmitteIwerte der Spurengase bei 2,9 bis 19 nmoVm3•

Die im Rahmen von ,CARBOSOL' gemessenen mittleren Konzentrationswerte lagen an den

sechs Meßplätzen bei 14 bis 273 ng/m3 für Levoglucosan und bei 13,5 bis 133 ng/m3 für
Cellulose. Die höchsten Werte für Levoglucosan wurden an den Bodenstationen Aveiro und
K-Puszta bestimmt. Besonders in Aveiro weist in den Wintermonaten sehr hohe
 Kllrzfassung

Konzentrationswerte auf. Die höchsten Konzentrationswerte für Cellulose wurden an den

ländlichen Meßstationen Schauinsland und K-Puszta gemessen. In K-Puszta wurden die
höchsten Konzentrationen gemessen und es sind kaum jahreszeitliche Änderungen zu sehen.
Der mittlere Beitrag von Levoglucosan-C und Cellulose-C zu OC (Organischer Kohlenstoff)
lag bei 1,2 bis 2,3 % für Levoglucosan und 0,5 bis 2,7 % für Cellulose. Für Levoglucosan
wurde der höchste Beitrag auf den Azoren gemessen, obwohl dort die absolut geringsten
Konzentrationswerte bestimmt wurden. Die Luft an der maritimen Hintergrundmeßstelle ist
sehr sauber. Daher wirkt sich ein möglicher Einfluß einer Holzverbrennung besonders stark
aus. Für Cellulose wurde der höchste Beitrag an der kontinentalen Hintergrundmeßstelle
Sonnblick gemessen.
Verwendet man Levoglucosan und Cellulose als ,Makro-Tracer', so kann der Beitrag der
Holzverbrennung und Pflanzenabbrieb am Organischen Material einer Aerosolprobe
bestimmt werden. Der Beitrag der Holzverbrennung liegt bei 21 bis 39 %, während der
Einfluß des Pflanzenabrieb geringer ist und im Bereich von 3 bis 16 % liegt. Wie bereits oben
erwähnt wird der stärkste Einfluß der Holzverbrennung auf den Azoren und der des
Pflanzanabriebs am Sonnblick bestimmt. In Summe liegt der Beitrag beider Quellen am
Organischen Material bei 37 bis 50 %.
Die Bestimmung der Größenverteilung von Cellulose und Levoglucosan wurde an
Impaktorproben aus Aveiro vorgenommen und zeigte, daß bei der Mehrheit der Proben der
Hauptanteil von Levoglucosan und Cellulose im Größenbereich unter 3 ~m a.d. lag .

•
 Abstract

ABSTRACT

This work contains input from two projects: "Backgroundmeasurements Sonnblick" and
"CARBOSOL". Atmospheric aerosol samples were collected for both projects. In
"Backgroundmeasurements Sonnblick" the aerosol compounds sulphate, nitrate,
oxalate, chloride, ammonium, calcium, magnesium, sodium and potassium as well as
the trace gases sulphur dioxide, nitric acid and ammonia were collected with two
parallel in-line system filter packs at Sonnblick Observatory (3106 m a.s.l.). Daily
samples were collected during the period between December 2002 and October 2004.
The "CARBOSOL" project was carried out in six sampling sites across Europe. With a
High-Volume sampler, weekly aerosol samples were collected during two years (2002-
2004) on quartz fiber filters. Here the determination ofthe organic compounds cellulose
and levoglucosan for all the six sampling sites was carried out. The sites can be
classified into low elevation and high elevation sampling sites. Low level sampling sites
are at Azores (Portugal), maritime background site 50 m a.s.l., at Aveiro (Portugal),
rural coastal site with maritime influence at 40 m a.s.l. and K-Puszta (Hungary), rural
continental site at 136 m a.s.l. High elevation sampling sites are at Schauinsland
(Germany), rural mountain site at 1205m a.s.l., at Puy de Dôme (France), continental
background mountain site 1405m a.s.l. and at Sonnblick (Austria), continental
background / free tropospheric site at 3106m a.s.l.

Aerosol compounds as well as ammoma and acid nitric (collected within

• "Backgroundmeasuraments Sonnblick") show pronounced annual cycles with high

values in summer and low in winter. That is typical for a high mountain sampling site
such as Sonnblick. For sulphur dioxide the situation was different and no variation was
observed comparing summer and winter values. The concentration values for oxalate
are much lower (approx. one order of magnitude) than the major inorganic aerosol
compounds, but they still show a very pronounced annual cycle.
For aerosol compounds as nitrate, sulphate and ammonia the average concentration
values of the whole period range between 5,5 and 15 nmoVm3 and for the trace gases
nitric acid, sulphur dioxide and ammonium 2,9 and 19 nmollm3•

Concerning "CARBOSOL" the average concentrations of the whole period for the six
sampling sites in Europe range between 14 and 273 nglm3 for levoglucosan and between
 Abstract

13,5 and 133 nglm3 for cellulose. The highest values for levoglucosan were obtained at
the low elevation sites, Aveiro and K-Puszta. Especially Aveiro presents very high
concentrations during the winter seasons. The highest values for cellulose were
determined at the rural sampling sites, Schauinsland and K-Puszta. K-Puszta, presents
the highest concentrations without very high differences between summer and winter.
The average contribution values of levoglucosan-C and cellulose-C to OC (Organic
Carbon) range between 1,2 and 2,3 % for levoglucosan and 0,5 and 2,7 % for cellulose.
For levoglucosan the highest contribution corresponds for Azores, where the lowest
concentration values were determined. As here the air is very clean and there is no
influence of other sources of pollutes. For cellulose the highest contribution was
obtained at Sonnblick, the other background site.
Using levoglucosan and cellulose as macrotracers for "wood smoke" and "plant debris"
it is possible to calculate the contribution to OM. The contribution of wood smoke to
OM ranges between 21 and 39 %, while the contribution ofplant debris to OM is
between 3 and 16 %. The highest percentage for wood smoke is obtained at Azores due
to the same reasons as mentioned before; for plant debris it is Sonnblick. The
contribution ofboth ofthese sources to OM range between 37 and 50 %.
Furthermore the size distributions (10-7,2 ~m, 7,2-3,0~m, 3,0-1,5J..lm, 1,5-0,95~m,
0,95-0,49~m, <0,49~m) of cellulose, levoglucosan were determined with a cascade
impactor at AVE. In most ofthe samples, the major fraction oflevoglucosan and
cellulose was associated with the fine particle fraction (< 3~m a.d.) .

•
 Index

INDEX

1. Introduction

2. Experimental 7
2.1. Sites 7

2.2. Sampling systems 13

2.2.1. Filter packs 13

2.2.2. High-Volume 15
2.3. Analytical method 17

• 2.3.1. Inorganic

2.3.2. Levoglucosan

2.3.3. Cellulose
ions 17

21

22

3. Results 25

3.1. Filter packs

Major inorganic aerosol constituents and trace gases 25
3.1.1. Detection limit 25
3.1.2. Intercomparison ofthe filter packs 27
3.1.2.1. Intercomparison of in-line system "A" &"B" 28
3.1.2.2. Intercomparison of in-line system "A" &"B"
with the open-face "C" 31
3.1.3. Annual cycles ofSO/', NO]' and NH/

• as well as S02, HNO] and NH]

Seasonal cycles
Comparison between summer and winter
39
39
46
3.1.4. Neutralization ratio 47
3.1.5. Aerosol fraction 48

3.1.6. Annual cycles of minor inorganic and organic

aerosol constituents 51

Seasonal cycles 51

Comparison of oxalate and sulphate concentrations 55

3.1.7. Comparison ofthe measurement series 2002-2004 with
the measurement series 1991-1993 57

Page 1
 Index

3.1.8. Comparison of aerosol data and gas phase concentrations

and precipitation data 61
3.2. High-Volume- Levoglucosan and cellulose 67
3.2.1. Literature comparison for levoglucosan 67
3.2.2. Literature comparison for cellulose 72
3.2.3. Detection limit 73
3.2.4. Average concentrations for levoglucosan and cellulose 75
Levoglucosan 75
Cellulose 77
3.2.5. Annual cycles oflevoglucosan and cellulose 78
Levoglucosan 79
Cellulose 83
Comparison of levoglucosan versus cellulose 87
3.2.6. Comparison oflevoglucosan and Organic Carbon (DC) 91
3.2.6.1. Annual cycles of levoglucosan-C and DC 91
3.2.6.2. Contribution of levoglucosan-C to OC 95
3.2.6.3. Contribution ofwood smoke to Organic Matter (OM) 98
3.2.7. Comparison oflevoglucosan and potassium 101
3.2.8. Comparison of cellulose and Organic Carbon (OC) 106
3.2.8.1. Annual cycles of cellulose-C and OC 106
3.2.8.2. Contribution of Cellulose-C to OC 110
3.2.8.3. Contribution ofplant debris to Organic Matter (OM) 114
3.2.9. Mass balance of OM using levoglucosan and cellulose as macrotracers 117
3.3. Size classified measurements of levoglucosan and cellulose 118
4. Summary 126

Literature

Annex

Page 2
 lntrodllccion

1. INTRODUCClON

The seasonal concentrations and the vertical distribution of atmospheric aerosols and
trace gases depend on the strength and variability of their emission sources, their air
chemistry behaviour and meteorological conditions. To get information about the vertical
distribution of air constituents sampling sites at higher elevations are needed in addition
to ground based measeurements. These sampling platforms can either be airborne (e.g.
airplane measurements) or they can be situated at mountain slopes or even mountain tops.
The Sonnblick Observatory is located in the Austrian Alps at an elevation of 3106 m and
provides such a sampling platform. During the last three years two projects called
'Backgroundmeasurements Sonnblick' and 'CARBOSOL' investigated the seasonalities
of inorganic and organic air constituents at Sonnblick.

Sampling within 'Backgroundmeasurements Sonn blick' was carried out at the

Sonnblick only and comprised the aerosol compounds sulphate, nitrate, oxalate, chloride,
ammonium, calcium, magnesium, sodium and potassium as well as the trace gases
sulphur dioxide, nitric acids and ammonia.

Large quantities of sulphur dioxide enter the atmosphere each year from anthropogenic
sources, mainly the combustion of fossil fuels and the smelting of metals. Sulphur

•
dioxide indisputably ranks as a prominent pollutant, although emissions have been
reduced drastically during the last decades. Research of the past years dealing with
atmospheric sulphur has concentrated on problems such as the dispersal of sulphur
dioxide from industrial emission sources (e.g. power stations) and urban centres, its
conversion to sulphuric acid, the formation of sulphate aerosols, and the deposition of
sulphate and sulphur dioxide at the ground surface. Natural sources of atmospheric
sulphur include volcanic emissions of sulphur dioxide and reduced sulphur compounds
such as H2S), aeolian generation of particulate sulphate (e.g. in the form of sea salt), and
the emanation of reduced sulphur compounds from the biosphere.

Page 1
 Introdllccion

Atmospheric nitric acid is the oxidation product of NOx and is therefore found in areas
with influence of high emissions of NOx• The main sources of NOx are combustion
processes which transform nitrogen from air and fuel into nitrogen oxides. A natural
source for the formation of nitric oxides is lightning (sparkle discharges). By this process
nitrogen oxides and nitric acid are not only fonned at ground level, but also in the free
troposphere. Gaseous nitric acid is in equilibrium with particulate nitrate. The
equilibrium between particulate nitrate and nitric acid depends on the composition of the
gas phase and aerosols, as well as aerosol water content and the temperature. Aerosol
nitrate is formed from nitric acid, which can dissolve directly in an aqueous aerosol
solution or react with ammonia to form particulate ammonium nitrate

Ammonia is the most abundant alkaline gas in the atmosphere. The significant sources of
NH3 are animal waste, ammonification of humus followed by emissions from soils, losses
of NH3-based fertilizers from soils and industrial emissions. The trace gas ammonia
reacts to particulate ammonium with nitric acid and sulphur dioxide. The ammonium ion
is an important component of the continental troposphere aerosols. Because ammonia is
readily absorbed by surfaces such as water and soil, its residence time in the lower
atmosphere is quite short. Wet and dry depositions of NH3 are the main atmospheric
removal mechanisms for NH3. In fact the deposition of atmospheric NH3 and NH4 + may
represent an important nutrient to the biosphere in some areas .

• While nitrate, sulphate and ammonium were generated predominantly in the atmosphere
by gas-particle reaction, the other named aerosol compounds, aside from oxalate, were
primarly emitted. They can be formed by erosion processes from stones and ground
material (mineral aerosol), but also by combustion process. Oxalate and oxalic acid can
be formed by both pathways, by atmospheric reaction from organic precursors or be
direct emission during combustion processes.

Page2
 Introduecion

The project had its main focus on the determination ofthese compounds since:
~ they are precursor substances of "acid rain"
~ they are cloud condensation nuclei, which influence cloud formation
~ the big part of inorganic and soluble in water aerosols is collected with the
determination of nitrate, sulphate and ammonium.

The experimental work for the project 'CARBOSOL: Present and retrospective state of
organics versus inorganic aerosol over Europe, implications for climate' was not only
performed at Sonnblick, but at six different sites across Europe. The sites can be
classified into low level and high level sampling sites. Low level sampling sites are at
Azores (Portugal), maritime background site 50 m a.s.l., at Aveiro (Portugal), rural
coastal site with maritime influence at 40 m a.s.l. and K-Pusta (Hungary), rural
continental site at 136 m a.s.l. High level sampling sites are at Schauinsland (Germany),
rural mountain site at 1205m a.s.l., at Puy de Dôme (France), continental background
mountain site 1405m a.s.l. and at Sonnblick (Austria), continental background / free
tropospheric site at 3106m a.s.l. Here the determination of the organic compounds
cellulose and levoglucosan is described for all the six sampling sites over Europe.

Several studies have been conducted to identify and quantify individual organic species
in atmospheric aerosols. Generally these studies concentrated on the soluble fraction of
the organic aerosol. Rogge et al. (1993a) have shown that about 30-50% of the organic
fraction of fine particulate urban aerosol comprises insoluble. organic species. Likely
candidates for this group are polymeric substances either primary or secondary and of
anthropogenic or biogenic origin. The most frequently occurring biopolymer in terrestrial
environments is cellulose, as green plants contain around 50% of dry weight cellulose in
leaves (Butler and Baily, 1973). Due to the seasonal cycles of the canopies of decidous
trees in temperate regions and the decay processes of the leaf litter, large fluxes of the
decay products to the atmosphere are likely to occur (Brimlecombe, 1986).
Cellulose in green plants occurs as a macromolecule with a polymerisation degree
generally in the range of 300-3000; in some cases, e.g. in fibres of cotton seeds up to
15,000 (Kürschner, 1966). The cellulose molecules are formed from D-glucose units in ß-

Page 3
 Introduccion

(1,4)-glucosidic bonding. The linear macromolecules form micelles vIa hydrogen

bonding, which then associate to micro fibrils (Denffer, 1978). In many plant seeds the
visible white fibres are pure cellulose. This type of cellulose is referred to as "free
cellulose", as it is directly accessible to saccharification. The cellulose micelles in leaves
and wooden material are to a certain extent encapsulated by lignin and in bark also by
suberin. Lignin, a mixed polymer of phenylpropane, adds pressure strength of the fibrous
cellulose (Kirk and Obst, 1988). Green leaves and wooden parts of plants contain free as
well as encapsulated cellulose.
In leaves of terrestrial plants the content of cellulose is around 50%, while lignin amounts
to <20% and hemicelluloses 20-30% (Butler and Bailey, 1973). As we assume that the
major fraction of cellulose in continental aerosol originates from decomposition
processes of leaves, the portion of plant debris in aerosols has been proposed (Kunit and
Puxbaum, 1996) to be estimated according to the concentration of cellulose by:
"plant debris" = 2. cellulose

Plant debris appears to be an important contributor to OC in atmospheric aerosols (Kunit

and Puxbaum, 1996).

Traditionally, fossil charcoal and black (soot) carbon, which are carbonaceous residues
derived from the incomplete combustion of plant tissues, are the indicators used most
frequently to trace forest fires over geological time (e.g., Schmidt and Noack, 2000).
However, Elias and Simoneit, 2000 report that levoglucosan (1,6-anhydro- ß-D-
glucopyranose) can also be used as a specific molecular indicator to trace biomass
combustion in sediments.
Levoglucosan is a dehydrated glucose containing an intramolecular glycoside bond. This
monosaccharide derivative is formed from the thermal breakdown of cellulose during
combustion (pyrolysis). It is emitted in fine smoke particulate matter and can
consequently be utilized as a specific and general tracer for the presence of emissions
from this source in atmospheric particulate matter (Simoneit et aI., 1999).
Cellulose decomposes on heating or on exposures to an ignition source by two alternative
pathways. The first, which dominates at temperatures < 300°C, involves
depolymerization, water elimination, fragmentation and oxidation leading finally to char

Page 4
 lntrodllccion

formation. The second pathway occurs at temperatures> 300°C and involves bond
cleavage by transglycosylation, fission and disproportionation reactions yielding tarry
anhydrosugars and volatile products. This pathway (summarized in Fig. I) gives rise to
the source specific molecular traces, i.e., mainly the 1,6-anhydride of glucose called
levoglucosan and minor amounts of other monosaccharide dehydration derivatives (e.g.
galactosan, mannosan).
v. o. Elias el al.

Cellulose, n = 7-12x103 D-glucose monomers

OH

o OH

HO~
Co~ _0

OH

Other Decomposition
Products

OH
1,4-Anhydride
OH
1.6-Anhydr*D-gluoo-
pyranose (levoglucosan)
OH
- HO

»
HO""-

OH
1,2-Anhydride
0

Other Minor Decomposition Products

HoMOH
1,6-Anhydro-jl-DllaJacto-
HoMOH
1,6-Anhydro-ß-D-manno-
pyranose (galactosan) pyranose (mannosan)

Fig 1,#: Schematic showing the major decomposition products during the pyrolisis (T > 300°C)
of cellulose and hemicellulose (adapted from shafizadeh, 1984).

Levoglucosan is accompanied by other minor stereoisomeric monosaccharide anhydrides

in atmospheric aerosols, with mannosan and galactosan. These compounds results from
the pyrolisis of hemicellulose, although the emitted amounts are substantially lower than
those of levoglucosan. This is consistent with the lower content of hemicellulose in wood

Page 5
 Introdllccion

as well as with the lower content of mannose and galactose as compared with glucose
residues in hemicelluloses (Shafizadek et al. 1984)

The determination of the concentration values of cellulose and levoglucosan in

combination with the overall sampling programm of the EU-project 'CARBOSOL' had
its main focus on:
~ the investigation ofthe seasonal cycles at different sampling sites across Europe
~ the determination of the contribution of the macro-tracers cellulose and
levoglucosan to the organic matter of atmospheric aerosols and their temporal and
spatial variations
~ to provide a basis for further evaluations relating aerosol concentrations to
concentrations in precipitation samples

Page 6
 Exoerimental: Samolini!svstem

2. EXPERIMENTAL

2.1 Sites

The experimental work for the project "Backgroundmessungen Sonnblick" was

performed at the Sonnblick Observatory (SBO). The experimental work for the project
"CARBOSOL" was performed in six sampling sites across Europe. Ones was Sonnblick,
already described, and the other sites were at Azores (Portugal), Background Oceanic
50m a.s.l., at Aveiro (Portugal), Rural Coastal Maritime 40m a.s.l., and K-Pusta
(Hungary), Continental Rural 136m a.s.l., at Shauinsland (Germany), Rural Mountain
1205m a.s.l. and at Puy de Dôme (France), Continental Background Mountain 1405m
a.s.l.

Fig. 2.1. Situation of the six sampling sites over Europe

Page 7
 EXDerimenta/: SamDlinJ!svstem

Austrian site
The SBO is located at the summit of Mt. Sonnblick at an altitude of 3106 m. Mt.
Sonnblick is situated in the main ridge ofthe Austrian Alps (Hohe Tauern, 12°57'E,
47°03 'N). As Mt. Sonnblick is among the highest peaks in the area, it is exposed to air
masses from all directions. The Observatory is surrounded by large glacier fields.
Towards the northeast, a steep wall descends over 800 m down to a sparsely populated
valley. There are no noticeable local emission sources. Since the Observatory is supplied
with electricity, it has no local sources of exhaust fumes. Hence the Observatory has the
ideal characteristics of a high alpine background station for air chemistry measurements.
The SBO is situated in the centre of Europe, surrounded by regions with large emission
densities at distances of a few hundred kilometres. The site was operated by ZAMG and
TU Vienna.

';,:::; .-.",,~~,..:r.:"::~~'::;.;"{~'\~;i~:;:)<..,:. >;"\" ...'. .:,"'.:. .'."

~.. .
~,~:~<~.~~'
','..::'::.:;~~':~
. . -.-
'~;~-~*r-:~:~~=.'
.~.
-,

,. ':-~,:'
.',.:'.:~:f'~,~;,
T~ •

Fig. 2.2. Sonnblick Observatory (Austria)

Page 8
 Experimental: Samplinf!svstem

Fig. 2.3. Situation of sampling site Sonnblick (Austria)

Portugal sites
The experimental work for the CARBOSOL PROJECT was preformed at Moitinhos -
iIhavo (40° 34'37"N; 8°39'29"W) and at Terceira Island Azores (38° 38'N;27°02'W),
Portugal. These sites were prepared specially for this project. They represent a rural
coastal maritime atmosphere (Moitinhos) and a background oceanic atmosphere
(Azores).
The sampling site at Moitinhos (AVE) was located, near a small village and was
surrounded by agricultural fields (mainly maize culture) and forested area (mainly pine
and eucalyptus). The area is influenced by local sources (eg. wood- burning for heating
purposes, agricultural activities, vehicular exhaust) and distant sources (eg. Aveiro is
located 11 km North ofthe sampling site).
The sampling site at Azores (AZO) was located near a high cliff and was surrounded by
grass fields. The area has limited human activity and has a great ocean influence.
The sites were operated at Aveiro and Azores by University of Aveiro and University of
Azores, respectively.

Page 9
 Exoerimenta/: SamolinJ!svstem

--- .-

Terceira

(/(','a/W Ar/û"rh-n

Figures 2.5. Terceira Island Site

France site
Puy de Dome (POD) is situated in the Massif central in france (450 75' N, 30 E). Its

height is 1450m a.s.l. The station is an Observatory which is attached to the "Observatoir
du Physique du Globe de Clermont Ferrand".

The Puy de Dom is the highest moutain in the Massif Central. Since the Observatory is
supplied with electricity it has no local sources of exhaust fumes. The surrounding of

POD is rural aerea with forest; the biggest city is Clermont Ferrans at a distance of about

20 km east to the side. Meteorological conditions consist often in westerly flows

especially in winter.

The site was operated by "Laboratoire de Glaciologie et Géophysique de l'Environnement

in Grenoble.

Page 10
 Exoerimental: SamolinJ!system

Germany site

The German sampling site (SIL) is a mountain sampling site located at the Schauinsland
(470 55' N, 70 55' E) at 1205 m above sea level. The station is operated aH year round by
the German Umweltbundesamt (htto://www.umweltbundesamt.deD.
The station is located on the highest most westerly mountain of the Schwarzwald. The
surroundings of the station consist of forest (mostly coniferous forest), pastures and
farmland. The station is located approximately 1a km southeast of Freiburg (approx.
200.000 inhabitants) and the Oberreihngraben (300 m above sea level). During stationary
temperature inversions quite often prevail, around the site with fog and low temperatures
in the Oberrheingraben and Freiburg and sun at the mountain site. Thus boundary layer
air from the urban regions is not transported to the site by convection as usual in summer.

The High Volume Sampler operated within this Projekt by the University of Heidelberg
is located close to the main building (distance approx. la m). The sampling height is at
3,7 m, the immediate vincinity of the sampler is grassland. Quarz fiber filters were
changed every Thursday, wrapped in aluminium foil and stored in the refrigerator until
they were sent to Heidelberg. In Heidelberg they were stored in the deep freezer.

Hungary site
K-Puszta (KPZ) sampling site is situated in a mixed forest clearing on the Great Hungary
Plain (460 58' N, 19033' E) about 80 Km SE ofBudapest. Its height is 136 m a.s.1.
Because ofthe lack ofnearby anthropogenic pollution sources, the location is
representative of a continental, rural background air. The site was operated by University
of Veszprem.

Page J J
 Exoerimenta/: Samolim!svstem

Background Rural
Oceanic Mountain
SOmasi 1205masl

..•r

Rural Free
coastal troposphere
maritime 3106masl
40masl

Continental
Rural
136masl

Fig. 2.5. The six sampling sites of"Carbosol" Project

Page 12
 Exoerimenta/: SamolinJ!svstem

2.2 Sampling system

2.2.1 Filter pack

The filter pack sampling within the project "Background measurements Sonnblick"
comprised sulphate, ammonium, nitrate, oxalate, calcium, sodium, potassium, chloride,
dioxide sulphur, nitric acid and ammonia. Two parallel In-Line filter packs (A & B) were
used. Filter holders were made from polycarbonate and were supplied by NILU
(Norwegian Institute for Air Research). Filter pack "A" contains a teflon filter and an
oxalic acid filter. Filter pack "B" contains a teflon filter, a nylon filter and a potassium
hydroxide filter. Table 2.1 gives a summary description about the used filters as well as
the compounds determinate and analysis method. All filters had a diameter of 47 mm.

Table 2.1: Summary description of In-Line filter-packs

Filter manufacturer, Coating Compounds Elution Analysis
details solution
Teflon Pall Aerosol Ethanol, IC: CI,N03, 504•
Zeflour 1J.lm H20 des!. Na, NH4, K, Ca,
Oxalat

Nylon Pall H202, IC: N03, S04

Nylasorb 1J.lm Na2C03/NaHC03

KOH Schleicher&Schüll KOH

Schwarzband

Oxalic Schleicher&Schüll Oxalicacid

acid Schwarzband Glycerin
IC: Ion Chromatography

The filter pack method used was based on the system described by Kasper (1994). It is a
version of the method by Fellinger (1991). They used a filter pack consisting of a PTFE
front filter, a nylon filter and a potassium carbonate impregnated filter. In addition, there
was a fourth filter, which was coated with oxalic acid/glycerine for the collection of
gaseous ammonia (Wiebe et al. 1990, Williams et al. 1992). The addition of glycerine to
the coating solution prevented the total drying up of filters and produced reactive

Page 13
 Exoerimenta/: Samolinrzsyslem

superficies. Thus the collection efficiency of ammonia could be improved (Kasper,

1994). Furthermore, a potassium hydroxide impregnated filter was used instead ofthe
potassium carbonate impregnated filter. Since potassium hydroxide converts to potassium
carbonate during contact with air, the potassium hydroxide filters are replacement
equivalents for the potassium carbonate filters.
The sampling with two filter packs was necessary to determine particulate oxalate. As the
filter pack "A" had an impregnated oxalic acid filter to determine ammonia, the front
teflon filter could not be used to determine particulate oxalate because ofhigh blank
readings. The filter pack "B" did not contain oxalic acid, thus the teflon front filter could
be used to determine particulate oxalate.

Assembling and shipping of filter packs

The coating, assembling and extraction of the filters were performed in the laboratory in
Vienna. Usually the filter packs were shipped to the SBO in sets of 15 filters holder (15
"A" and 15 "B") in aluminium box. From these 15 filters, 3 were used like blanks to
control the contamination during the shipping and the storage ifthe filters at the site.

Sampling
At the Sonnblick Observatory, the sampling time of a filter pack was 24 hours. The daily
exchange of samples was carried out by the observatory staff every day in the morning
approx. at 8 a.m.
Until February 2003 the air flow was approximately 35 l/min (at 1013mbar and 273K).
After the installation of new tubing, the air flow was reduced to 25 I/min (at 1013mbar
and 273K).
In the last sampling months the sampling volume was further decreasing, to
approximately 20 l/min (at 1013mbar and 273K), most probably due to membrane pump
wear.
The sample volume was determined with a gas meter. Pump, gas meter and manometer
reside in the pump house.
The sampling equipment is installed of the upper platform of the Observatory (see figure
2.1).

Page /4
 Exoerimenta/: Samolin£svstem

Fig. 2.1: Filter pack- sampling ofthe upper platform ofthe Sonnblick Observatorium.

2.2.2 High-Volume Sampler

In the "CARBOSOL" project the following parameters were determined: PM2,5 mass,
Total-, Organic-, and Black Carbon, HUllS, Water Soluble Organic Carbon (WSOC),
Cellulose, Anhydro sugars, Inorganic ions, Water Soluble Organic Acids (WSOAC),210Pb
and 7Be. To determine these compounds, every sampling site was equipped with a High-
Volume sampler PM 2,5 with quartz fiber filters weekly aerosol samples were collected.
The sampling sites were operated by different groups from Portugal, France, Germany,
Austria and Hungary. Concerning analyses every group was in charge for only one or a
group ofparameters as listed below. Table 2.2 (compiled by Pio et al. 2004) gives the
information about the analysis conducted in every laboratory.

Table 2.2: Distribution ofthe different parameters and their respectively analytical
methods in the different laboratories.
Parameters Analytical method Laboratory
PM 2,5 mass Weighting at 50% RH University of Aveiro,
Univesity of Azores
TC/OC/BC Thermalprogramming/Optical University of Aveiro
Control by transmittance
HUllS SPO Extraction! Micro University ofVezsprem
combustion
WSOC Water extraction; water analysis University ofVezsprem
Cellulose Enzymatic conversion; UV Tech. University of Vienna
detection of D-glucose
Anhydrosugars HPLC with electrochemical Tech. University ofVienna

Page /5
 Exoerimenta/: Samolinf!svstem

detection
Inorganic Ions Ion chromatography Lab. Environ. G1aciol. and
Géophysique.
Water sol. Organic Ion chromatography Lab. Environ. Glaciol. and
Acids. Géophysique.
210Pb 7Be
, Radioactive emission / detection Karls-University of
Heidelberg

Sampling at SBO
At the Sonnblick Observatory weekly aerosol samples were collected with a High-
Volume Sampler PM 2,5 (DH-77) on quartz fiber glass filters (Pallflex ™ 2500QAT-UP-
150, 150 mm diameter). The filters were mounted in filter holders in Vienna and
subsequently transported to Sonnblick Observatory in air tight stainless steel containers.
Every Thursday morning the observatory staff changed the filters. Since we had problems
with the software of the High-Volume sampler, the sampler volume varied quite a lot and
sometimes we did not receive the sampling protocol properly. In this case we had to
calculate an estimated volume for these samples. Generally these problems were caused
by humidity (rain, snow cloud water) entering the sampling line and clogging the filter.
The resulting high pressure drop stopped the sampler and occasionally led to a reset of
the controIIing software. The average sampling volume for the whole period was 3151 m3
(at 1013 mbar and 273 K). The sampling head ofthe High-Vol sampler is instaIled at the
upper platform ofthe Observatorium. The filter holder unit as weIl as the control unit (see
figure 2.2) is located below in the pump house.
\ .. ,

\\
\
\
\
\\
\
\
Fig. 2.2: High-Volume sampler at the SHO.

Page 16
 Experimental: Samplin£svstem

2.3 Analytical Method

2.3.1 Inorganic ions & organic acids

Now the description ofthe preparation and analyses of each filter follows. Extraction of
the filters was performed in 5ml polyethylene vials in an ultrasonic bath (30min).

Teflon filter
For sampling of aerosol compounds, teflon filters were used to avoid the possible
sorption of reactive gases (e.g. nitric acid). The collection of nitric acid on the teflon filter

• would result in an overestimation ofparticulate nitrate (positive artifact) and,

consequently, lead to an underestimation of nitric acid concentrations determined with
the nylon filter. For extraction PTFE (Pall "Zefluor", l!lm pore size) filters were soaked
with acetone (O,2ml). Then Milli-Q water (3,4ml) was added. The extracts were analyzed
for anions (chloride, nitrate, sulphate and the organic acids acetate, formiate, malate,
malonate, maleate and oxalate) and cations (sodium, potassium, ammonium, magnesium
and calcium) with ion chromatography.

Nylon filter
Nylon filters collect nitric acid and sulphur dioxide (Anlauf et al. 1985, Chan et al. 1986,
Cadle 1987). The collection of nitric acid is quantitative. Unfortunately this is not the

• case for sulphur dioxide. No relationship could be found between the collection
efficiencyand either the relative humidity, the air temperature or the absolute
concentration of nitric acid or sulphur dioxide (Hicks et al. 1993) in the ambient air.
Nylon filters (Pall ''Nylasorb'', l!lm pore size) were extracted in 1% H202 (O,2ml) and
carbonate buffer solution (3,4ml) (2,6mM Na2C03-3,3mM NaHC03). This buffer
soluti~n was later on used as on elute for ion chromatography. Addition of H202 was
necessary as nylon filters retain S02 as SO{ and sol- ions. H202 oxidizes SO{
quantitatively. Thus, the extracts ofthe nylon filters were analyzed for N03- and sol-
with ion chromatography.

Page 17 -
 ExverimentaJ: Samvlin£svstem

KOH-fiIter
Cellulose filters coated with potassium hydroxide were used for the quantitative
collection of sulphur dioxide. The total sulphur dioxide concentration was calculated as
the sum of sulphate recovered from the potassium hydroxide and nylon filters.
Impregnation ofthe filter paper (Schleicher & Schüll, Schwarzband, 47mm diameter)
with potassium hydroxide solution was performed at the laboratory with an aqueous of
1% w/v potassium hydroxide (KOH-pellets p.a. Merck Nr 5033).
The filters were covered with Milli-Q water in a glass, which was placed in an ultrasonic
bath (10 min). Afterwards the water was decanted. The filters were washed three times

• with Milli-Q water, then washed three times with a 1:5 diluted coating solution. Finally,
they were washed three times with a concentrated l% potassium hydroxide solution.
Several filters could be impregnated at the same time, without a deterioration of the
blanks. At the end, the filters were put in petri dishes above (Polystyrol, Fa. Nunc) and
dried in a dessicator over silica gel. If the dried filter showed blank readings of sulphate,
then the whole procedure of washing and coating solution was repeated with a new
coating solution. The filter can be kept in a box in the refrigerator for several weeks, with
an increase of the blank readings.
The extraction of the potassium hydroxide coated filters was performed with 1% H202
(0,2ml) and Milli-Q water (3,4ml). Again addition ofH202 was necessary to oxidize
SO/- to solo. The extracts were analyzed for sol- with ion chromatography .

• Oxalic acid filter

For sampling of ammonia, cellulose filters (Schleicher & Schüll, Schwarzband, 47mm
diameter) coated with oxalic acid and glycerine were used. As coating solution on
aqueous solution of an oxalic acid (containing 3% w/w oxalic acid in 5%w/w glycerine)
was used.
The procedure of washing and impregnation was the same as for potassium hydroxide
filters. Afterwards the filters were dried in the dessicator, and the filters were checked for
ammonium blanks.
The filters were extracted with Milli-Q water (3,6ml). Extracts were analysed for NH4 +
with ion chromatography.

Page 18
 Experimental: Samplin$!svstem

Ion chromatography
The determination ofinorganic anions, cr, N03-, solo, and the cations, Na+, NH/, K+,
Mg2+ and Ca2+ was carried out with an isocratic ion chromatography system from
Dionex.
The tables 2.3 to 2.6 show the analytical parameters as well as the detection limit ofthis
ion chromatography system (IC).

Table 2.3: Analytical parameters of inorganic anions

Column and guard column AS 12A-4mm und AG 12A

• Eluent
Flow
Suppressor
Detector
2,6 mM Na2C03/3,3
2,3 ml Imin
ASRS-UL TRA 4 mm
Sensitivity 30 ilS
mM NaHC03

Injection volume 50 ,.tl

Table 2.4: Detection limit IC (inorganic anions)

[Ilg/I]
Chloride 25
Nitrate 17
Sulphate 22

• Table 2.5: Analytical parameters of cations

Column and guard column CS 12A-4mm und CG 12A
Eluent 12 mM Methan sulfonic acid
Flow 1,1 ml Imin
Suppressor CSRS-ULTRA 4 mm
Detector Sensitivity 30 ilS
Injection volume 90 III

Table 2.6: Detection limit IC (cations)

[Ilg/I]
Sodium 10

Page 19
 Exoerimenta/: SamolinJ!system

Ammonium 5
Potassium 7
Magnesium 4
Calcium 15

The determination of organic amons (oxalate, malate, malonate, maleate, formiate,

acetate and pyruvate) was carried out with gradient ion chromatography (KOH-Gradient).

Tables 2.7 and 2.8 summarize the IC system and the detection limit of the gradient ion

chromatography system .

• Table 2.7: IC-Gradient analysis (organic anions)

Column and guard column
Eluent
AS 17 und AG 17 sowie A TC-l
KOH Gradient
Flow 1,8 ml Imin
Suppressor ASRS-ULTRA 4 mm
Detector Sensitivity
Injection volume 100 III

Table 2.8: Detection limit IC (organic anions)

[llgl1]

Acetate 3
Formiate 3
Pyruvate 4
Chloride 23
Nitrate 4
Malate 7
Malonate 4
Maleate 4
Sulphate 6
Oxalate 6

Page 20
 Exoerimenta/: Samolinf!svstem

2.3.2 Levoglucosan
The filters were put in 5 ml polyethylene vials and wereeluted with 3ml Milli-Q water.
The extraction took place in an ultrasonic bath (20m in). The determination of
levoglucosan was carried out with a HPLC with electrochemical detection (ED40,
Dionex). Gradient elution was performed with deionized water as solvent D and sodium
hydroxide (250mM) as solvent C. The binary gradient had a flow rate of 1 mL min'l. It
started with 30mM sodium hidroxide (88% D (water) and 12% C (NaOH)). For the
detection (amperometry) we used a gold working electrode. The column was a CarboPac
PA 10, and the eluent was a NaOH gradient from 30 to 40 mM for each sample. Eluent
flow was 1 ml/min. For cleaning the analytical system is rinsed with 250 mM NaOH
during 5 min. after every sample. To prevent contamination from carbonate an Ionpac
ATC guard column is installed which has to be cleaned regularly. Before the analysis the
eluent is purged with a helium degassing system for approx. 10min.
For determining Levoglucosan a Bio LC from Dionex was used with a NaOH-Gradient
from 30mM to 40mM. In table 2.9 are the analytical parameters.

Table 2.9: Analytical parameters Bio LC (anhydrosugars )

Column and guard column Carbopac PA 10 and AmminopacC)
Eluent NaOH Gradient
Flow 1,0 ml/min
Electrodes Ag! AgCI reference electrode and Au
• working electrode
Detector Amperometry
Injection volume 100,.L1

Table 2.10: Detection limit Bio LC (anhydrosugars)

[~g!l]
Levoglucosan 10
Galactosan 10
Mannosan 10
Glucose 10
Fructose 10

Page 2/
 EXDerimental: SamDlinJ!svstem

2.3.3 Cellulose
To determine atmospheric cellulose we used the method of Kunit and Puxbaum 1996.
The authors mentione three steps for the cellulose determination: In the first step, samples
are subjected to a delignification treatment to liberate cellulose associated with lignin and
hemicellulose. In the second step, the "free" cellulose is enzimatically hydrolysed to 0-

glucose (saccharification). In the third step, D-glucose is determined with a test-

combination by Boehringer Mannheim GmbH with a UV-VIS spectrophotometer.
We determined the "free cellulose" from the aerosol samples only, thus we did not use
the delignification step. "Free cellulose" is a fraction of "total cellulose", thus the amount
of"total cellulose" can be estimated by applying the conversion factor from previous
work ofPuxbaum et al. 2003.
a) Reagents
• Citric acid buffer (0,05 M pH 4.8): 210 g citric acid monohydrate (Merk extra
pure) was dissolved in 750 ml ultrapure water, NaOH was added to obtain pH 4.3,
and filled to 1000 ml ( stock solution, 1M citrate buffer pH 4,5). The buffer was
diluted to 0,05 M prior to use, and Thymol (Merk cryst. Puriss.) was added to
obtain a 0,05% solution for conserving and sterilising the incubate.
• D-Glueose test kit (Boehringer-Mannheim). Cellulose Hydrolysing enzymes:
Celluc1ast 1,5L and Novozym 188 fom Novo Nordisk. Celluc1ast 1,5L is a
Thrieoderma reesei cellulose for technical use (e.g. saccharification of straw).

• The optimum enzyme activity is reported to be 50-60°C, and a pH of 4,5-6,0 .

Novozym 188 is a cellobiase suspension obtained from Aspergillus niger. The
optimum enzyme activity is around 50°C, at pH 4,8. Hydrolysis of cellulose with
cellulose yields D-glucose and cellobiose. The cellobiase then hydrolyses the
cellobiose and increases the total yield of D-glucose in the assay. The producer
recommends the followingamounts of enzymes relative to cellulose: 1-2%
Celluc1ast 1,5L; 0,2% Novozym 188. The enzyme suspensions are stored frozen
as obtained. For analytical use the suspensions are diluted (1: 10 for Celluc1ast
1,5L and 1:100 forNovozym 188). Cellulase and Cellubiase enzymes may
contain o-glucose from the production process and for stabilisation. Enzymes

Page 22
 Exverimental: Samv/inJ!system

from several suppliers were tested (kunit and Puxbaum 2003) and above
mentioned products showed the lowest blank value of D-glucose.
• Enzymes preparation: As the enzymes contain glucose they have to be precleaned
by dialysis. For the dialysis a solution of 22.6 g of Citric acid monohydrate and
38.9 g of Tri-Sodium Citrate in 5L of Milli-Q water were prepared. The dialysis
tubes pieces (length as needed) were cut and placed in Milli-Q water for 1 hour.
One end was closed with a knot; the tubes were filled with enzymes. Then the
other end was closed with a knot as well. The dialysis tubes filled with enzymes
were put in the Citric acid/Tn-Sodium Citrate solution, which was previously

• placed in an ice bath (the solution temperature must then be lower than lOOC),
with agitation. After about 12 hours (all day long), the bucket was put in the
refrigerator at 2-6°C for about 15 hours (overnight). Finally, it was one end ofthe
dialysis tube was cut open and small aliquots of the enzymes (about 300 ilL for
Cellulase and 100 ilL for Cellobiase) were transferred to plastic sample vials; 5%
(viv) ofGlycerin were added and the solutions were stored in the freezer.

b) Analytical method
• Saccharification of cellulose: The filters were put in one-way 5 ml polyethylene
vials. They were mixed with a solution of 3ml 0,05 M citric acid containing
0.05% thymol at pH 4,8. These samples were incubated with 100111of cellulase
and 100111of cellobiase. As mentioned before the enzyme suspensions had to be
diluted before use (1: 10 for Celluclast 1,5L and 1:100 for Novozym 188), which
resulted in an actual addition of I,.tl cellobiase and 10111cellulose. The extraction
took place in an ultrasonic bath (20min).The aerosol samples were incubated for
24h at 45°C.The enzymatic saccharification reaction was stopped by heating the
vial to 80°C then cooling during 10 min and centrifuging for 15 min. After 10 min
of centrifugation the supernatant fluid was taken for glucose determination.
• Determination of D-glucose: The Boehringer-Mannheim (BM) test kit contains
two "solutions" and a glucose standard. Solution 1 contains a triethanolamin
buffer pH 7.6, NADP, ATP and magnesium sulphate; Solution 2 contains an
enzyme suspension of hexokinase and glucose-6-phosphate-dehydrogenase. The

Page 23
 Exoerimental: Samolingsvstem

prescribed assay was modified with regard to the volumes of sample and
solutions. The pipetting scheme is indicated in table 2.11. Reagent blank and
samples were prepared according to the pipetting scheme. The components were
mixed in a disposable cuvette (l em). For each of these vials the absorbance
before the reaction (Absorvance() was determined at 340 nm, 3 min after the last
addition. Then the solution 2 was added, and after lOmin the developed colour of
NADH at 340nm was determined (Absorbance2). To check that the reaction is
complete, another measurement of the absorbance was performed after 15 min. If
the result was the same as after 10min, the reaction was finished. If it did not
remain constant, the absorbance was measured again every 5min until a constant
value was reached. Results were derived from the differences between the
Absorbance2 and Absorbance( readings for each measured vial.

Table 2.11: Pipetting scheme for o-glucose determination

Blank Sample
BM solution 1 O,5ml a,s ml
Samle solution a,5ml
bidest. water 1,0 ml a,5ml
Determination of Absorbance 1
BM solution 2 0,01 ml 0,01 ml
After 15 min Determination of Absorbance 2

To determine Cellulose, an UV-Vis spectrophotometer (Unicam 5625 ) was used. The

absorption (340 Ânm) of the samples inside disposable cuvettes (Plastibrand, 1,5ml semi
micro), was measured. At the beginning of each batch, the zero absorbance was set with
bi-distilled water and checked during the measuring session.

Page 24
 Results: Filter /Jacks

3. RESULTS

3.1 Filter packs

3.1.1 Detection limit

To determine the detection limits and to regularly check the samples for impurities, field
blanks were included in every series of filter. A blank was analyzed every six samples.
The preparation, storage, and analysis were the same for samples as well as for blanks. At
SBO, the samples were collected during 24 hours, while blanks were installed for a few
minutes only. Therefore it is possible to control the sample contamination, which took
place during the storage, shipping, sampling, assembling or disassembling of the filter
holders.

The variation of the field blanks limits the detection limit of the measurement procedure.
The detection limit was determined by calculating three times the blank standard
deviation and relating this number to the mean of the sampled volumes. To avoid outliers
the field blanks were controlled using the "Nalimov-test". In the time period from
December 2002 until July 2003, the sampling had a mean volume of 17,4 m3 (1013 mbar
and 273 K). Due to the decreased sampling volume (as previously noted) since January
2004 an average sample volume of 13 m3 (with 1013 mbar and 273 K), has to be used.
Hence different detection limits have to be reported from January 2004. In addition
elevated field blanks were observed for nitrate and nitric acid, as well as for ammonium
and ammonia starting with April 2004. This led to the definition of a third set of detection
limits. As an alternative the highest detection limit could have been used for the whole
sampling period (December 2002 - December 2003). However in this case a lot of
information would have been lost for the winter periods, when several of the daily
averages were close to the limits of detection.

The detection limit for trace gases, nitric acid, sulphur dioxide and ammonia, as well as
aerosol components, nitrate, sulphate, ammonium, calcium, chloride, sodium, potassium

Page 25
 Results: Filter /Jacks

and oxalate are listed in Tables 3.1, 3.2 and 3.3. In addition the number of field blanks
(FB) which were used to determinate the detection limit are given. Because filter pack
"A" and filter pack "B" have a teflon filter, the amount of field blanks is higher for
aerosol compounds than for gases. The exception is for oxalate. Here we cannot use filter
pack "A" because the installation of the ammonia impregnate oxalic acid paper filter
produced notable blank readings (0,31 - 0,54 Jlg/ml) on the teflon filter.

The detection limits of nitric acid, sulphur dioxide, nitrate, sulphate and ammonium are
also low enough for the extremely small air concentrations at Sonnblick.

Problems occured mainly with the determination of ammonia during the winter months,
when most ambient concentration values were below the detection limit of 2,1 nmol/m3,
This relatively high detection limit for ammonia is due to the elevated variation of the
blanks observed in every filter series. This contamination is most likely because of
shipping and storage. The determination of ammonia is very sensitive to errors as the
ammonia concentration values inside the room, are clearly much higher than ambient air
concentrations at Sonnblick.

Table 3.1: Detection limits determined from the field blanks (from December 02 to December 03)
cr NOJ' 5042• c20/' Na+ NH/ K+ Mg2+ Ca2+ HNOJ 502 NHJ
DL (nmol m'o) 0,6 0,8 0,3 0,2 1,1 0,6 0,5 0,2 0,9 0,9 1,6 2,1
Ammount of FB 84 79 79 39 86 79 85 55 75 35 79 37

Table 3.2: Detection limits determined from the field blanks (from January 04 to March 04)
cr NOJ' sot C2042• Na+ NH/ K+ Mg2+ Ca2+ HNOJ 502 NHJ
DL (nmol m'J) 0,3 1,3 0,6 0,6 1,2 0,4 0,2 0,5 0,9 0,4 0,7 1,7

Ammount of FB 18 14 19 7 18 16 20 20 15 9 21 9

Table 3.3: Detection limits determined from the field blanks (from April 04 to September 04)
cr NOJ' 5042' C2042• Na + NH4 + K+ Mg2+ Ca2+ HNOJ 502 NHJ

DL (nmol m'J) 0,3 3,6 0,5 0,7 1,0 0,9 0,2 0,6 1,3 3,0 2,0 2,1
Ammount of FB 66 57 64 24 64 61 65 64 55 34 67 30

Page 26
 Results: Filter oacks

For compounds like chloride, potassium, and magnesium, most of the winter day values
were below the detection limit. In summer a quantitative measurement is possible.
Similar problems occurred for oxalate. Also calcium often cannot be quantified. In
summer we observed a marked increase of the concentration values for calcium. An
influence due to building activity which took place at SBO during the summer months in
2003 and 2004 could not be eliminated, although the measurements were carried out only
during the night.

For the compounds chloride, sodium, potassium, calcium and magnesium, most of the
daily values were determined close to or below the calculated detection limit. (Table 3.4)

Table 3.4: Percent orcr, Na+,K+,Mg2+and Ca2+values below the detection limit (DL)
cr Na+ K+ Ca2+ Mg2+

Value< DL 98% 85% 59% 35% 62%

Ambient air concentrations below the detection limit were replaced with half the
detection limit to allow for the calculations with these numbers. All compounds at least
showed a limited number of these readings, especially during winter months. (Annex
Tables)

Page 27
 Results: Fi/ter packs

3.1.2 Intercomparison of the filter packs

In the period from 10.12.2002 to 23.12.2003 (13 sampling days), from 16.05.2003 to
27.05.2003 (12 sampling days) and from 3.07.2004 to 17.07.2004 (10 sampling days),
intercomparisons between the In-line filter packs (A&B) and the Open- face filter pack
(C) were carried out. The intercomparisons were carried out in the cold as well as in the
warm seasons. As it is expected, the winter concentration values were smaller than the
concentrations in May and July. The small values in summer mostly occurred during days
with snowfall or rainfall.
Generally, measurements with the filter packs could be influenced by "filter errors".
"Positive" errors are all the effects which cause an overestimation of the aerosol fraction
- e.g. gases were collected on the particulate filters and therefore attributed to the
particulate phase. "Negative" errors include all the effects which cause an
underestimation in the aerosol sampling -e.g. the evaporation of semivolatile compounds
from the teflon filter. The filter errors are determined by the composition of the air
sample and parameters such as air temperature and humidity or their changes during the
sampling. Also, the filter material used and the construction of the sampling line are
important. The use of an in-line filter pack with a heated inlet is different compared to an
open-face filter pack. The heated inlet and sampling line will shift the occurrence of
semivolatile compounds to the gas phase.
During a previous project (Kasper and Puxbaum, 1998) an open-face filter pack has been
used. At times when the sampling site was within clouds, rime or snow deposits could
occur on the front filter. Usually these deposits ("snow caps") were removed during filter
change. Trace amounts of rime or snow were allowed to remain on the filters. Although
the "snow-caps" observed at the Sonnblick did not cover and block the whole front filter,
they may act as a prefilter and scavenge gaseous components as well as aerosols. To
estimate their influence the ionic concentrations of several deposits were determined and
compared with data from snow and cloud water samples. No enrichment of ionic
constituents were observed in the "snow-caps" compared with average snow samples.
However artifacts, especially for reactive and highly soluble gases are likely.
To avoid these influences in this work in-line measurement have been performed.

Page 28
 Results: Filter oacks

3.1.2.1. Intercomparison of in-line system liA" and liB"

To start the intercomparison we compare the results of the in-line system. Both systems
comprise a teflon filter as a front filter. Thus the aerosol concentrations can be compared.
Regarding trace gases no comparison is possible as either ammonia or sulphur dioxide
and nitric acid are collected by systems "A" and "B" respectively. The illustrations 3.1 to
3.4 show the comparison of daily aerosol concentrations and systems "A" and "B".

For particulate sulphate and ammonium, the seasonal trends determined by filter packs A

• and B show good agreement. Also the direct comparison of data shows the good
agreement of system A and B. In case of sulphate one sample was excluded because of an
extremely high concentration value pointing to a contamination of one filter. Without this
measurement (25.05.2003) the linear regression of sulphate gives the relationship of A =
1,1448 * B (r = 0,9155). The calculated regression with all the measurement values is A
= 1,2426* B (r = 0,8551). For ammonium, the linear regressions has a relationship of A
= 1,11741 * B (r = 0,6452), if the measurement of 5.07.2004 is eliminated. Under
consideration of all samples, A = 1,3329 * B (r = 0,7711) is obtained. The large
deviation determined on 24.05 and 25.05.2003 cause the rather low value for r.

On basis of these comparisons we can assume, that the systems A and B, which are

• operated in parallel deliver comparable data .

Page 29
 Results: Filter packs

A,B (S04)-Datum

3,500

3,000

1:1
2,500 ~
ii

,:
Il

E
a. 2,000
I I

,
-=0., ID

!!!.
CD 1,500
.{

•
1,000

0,500

-II-

Fig. 3.1: Comparison of In-line filter packs "A" and "B" determined concentration values
ofparticulate sulphate during seasonal variation,

A,B(S04)

4,000

3,500

3,000

• ~
VI
;r
2,500

-=g 2,000
y=l,1448x
R2 = 0,9155
1,500
• A,B(S04)
-Linear (A,B(S04))
1,000

0,500 •

0,000 '
0,000 0,500 1,000 1,500 2,000 2,500 3,000 3,500 4,000
B(S04) (jlg/m']

Fig. 3.2: Comparison of data for particulate sulphate.

Page 30
 Results: Filter packs

A,B (NH4)

1,600

III
"
1,400 /'

,I
," '
: I
1,200

1,000
Ë
a
2;
~ 0,800
è
III a
< 0,600 .' ----..,--

•
Fig. 3.3: Comparison ofIn-line filter packs "A" and "B" determined concentration values
of particulate ammonium during seasonal variation.

A,B (NH4)

1,000

•
0,800

•
~ 0,600
a •
.-
2;
J:
è y = l,1174x
et 0,400
• •
R2 = 0,6452
• A,B(NH4)
-Unear(A,B (NH4))

• •
0,200

•
•
0,000
0,000 0,200 0,400 0,600 0,800 1,000
B (NH4)(llg/m')

Fig. 3.4: Comparison of data for particulate ammonium.

Page 31
 Results: Filter Dacks

3.1.2.2. Intercomparison of in-line system HA" and "E" with the open-face
filter pack "C"

The best agreement between in-line and open-face sampling filters was determined for
sulphate.
A,C (SQ4).Oate

3.000

2.500

2.000

• Ë
13>
:>.
g
Ul
(.)
..{
1.500

1.000

0,500

--0
0.000

..~ ..~ ..~I"~I;I:I,~..<f>~~"~#;ll~I,

..~ ..~ ..~#;,..<f>:#;,
..<f>:~.,
..~1': ..~#;,1':..~ ~ ..~ ~ ..~ ~ ~~ ..~ ..~ ~
~~~~~~~~~~~~~~~~~~#~~~~~#~~~~~~~~~~~
Fig. 3.5: Comparison ofIn-line filter packs "A" and the Open-face filter pack "C" determined
concentration values of particulate sulphate during seasonal variation.
A,C (504)

3,500

•
3,000

•
2,500 ----- ...

ï"
~ 2,000

~
;t. 1500
y= 0.9553x
• R2 = 0.9055
1.000
• • A,C(S04)
-linear (A.C (504))

0.500
•
0,000
0,000 0,500 1,000 1.500 2.000 2.500 3,000 3.500
C (504) liJglm')

Fig. 3.6: Comparison of data for particulate sulphate.

Page 32
 Results: Filter packs

For ammOnIum and nitrate the differences were greater because of the semI volatile

behaviour of ammoniumnitrate.

A,C (NH4)

1,600

1,400
~
'I
/1
il
1,200
II -

--rr----- I I
I I

•
I .
I \
, I
I I

0,400

0,200

Fig. 3.7: Comparison of ln-line filter packs "A" and the Open-face filter pack "C" determined
concentration values ofparticulate ammonium during seasonal variation.
A,C (NH4)

1,600

•
1,400 -- ------ ,---

• 1,200

1,000
------.------.

-
y=
• R2
O,9397x
= 0.6227
0,400

• • • A.C (NH4)

0,200 • • -Unear (A,C (NH4»)

0,000
0,000 0,200 0,400 0,600 0,600 1,000 1,200 1,400 1,600

C (NH4) [~g1Nm')

Fig. 3.8: Comparison of data for particulate ammonium.

Page 33
 Results: Filter oacks

B,e (N03)-Oate

1,400

1,200

1,000

"\
\
Ë 0,800
a. \
.=
0:;-
o
z
U 0.600 --. --.--- ..
ai

0,400

0,200

Fig. 3.9: Comparison of In-line filter packs "B" and the Open-face filter pack "C" determined
concentration values of particulate nitrate during seasonal variation.
B,e (N03)

1,400

1,200 •

1,000

• ..
~ 0,800
.=
0:;-
0
~ 0,600
III

••
0,400
•
0,200 • •

0,000
0,000

Fig. 3.10: Comparison of data for particulate nitrate.

Page 34
 Results: Fi/ter DOcks

In winter a very good agreement of the measurement systems was obtained for sulphur
dioxide. Unfortunately in summer 2003, the results were clearly worse. That was the
main reason to repeat the intercomparison in summer 2004. The repetition of the
comparison yielded improved results; however, 2 out of the 10 measurements again
showed large deviations. At present, a methodical explanation for this behaviour cannot
be given. A humidity film in the heated inlet line of the in-line filters could be the reason
for the small concentration values of the in-line system, but this effect would be
independent of the season and, should give even stronger deviations for the others gases
since both nitric acid and ammonia are more reactive and better water soluble than
sulphur dioxide. However this effect is not found for ammonia and nitric acid.

For ammonia, the concentration values were below the detection limit during the winter
months. In spring 2003 a quite good agreement was obtained, although certain
fluctuations are visible. During this period the in-line system "A" constantly showed
higher concentration values than the Open-face filters "C". The linear regression result
shows a relationship of A = 1,4928 * C and r2 = 0,8668. This trend is the opposite of the
behaviour for ammonium, and is most likely caused by the heated inlet line. The results
of sum ammonium and ammonia determination agree well. Unfortunately the good
agreement of systems A and C was not confirmed in July 2004. Here the measurement
systems showed clear difference in both directions .

• In December 2002 and May 2003 the intercomparison for nitric acid gives reasonable
results. In July 2004, in-line filter measurement values are clearly above the values of
Open-face filters. During this period elevated field blanks were observed. Therefore we
expected some contamination and do not discuss the differences further. Generally the
measurement system for nitric acid showed the highest deviation. Days with elevated
results of nitric acid in the In-line system "B" (predominantly during the summer
measurements) corresponds to the above mentioned effect (see ammonia/ammonium) of
semivolatile compounds in heated inlet lines. In this case, it is useful to compare the sum
of particulate nitrate and gas phase nitric acid (Figure 3.16). Here the agreement of both
filter packs is clearly better. The linear regression of L(N03-+HN03) for December 2002

Page 35
 Results: Filter /Jacks

and May 2003 is B = 1,0806 * C ( r = 0,546). The small value for r shows that even for
the sum or nitric acid and nitrate marked differences of the measurement systems are
determined. Nitric acid is an especially reactive and very good water soluble compound,
thus show - ice deposits on the open-face filter- can have a strong influence on the
results.

Basically, the agreement of filter measurements for the gases IS not as good as for
particulate matter.

B,C(S02)

0,900

0,800 --

0,700

0,600

Ë
~ 0,500
N
o
!!!. 0400
U '
ai
0,300

0,200

0,100

• Fig. 3.11: Comparison of Filter pack "B" and Filter pack "C" for S02 during the same time
period

Page 36
 Results: Filter /Jacks

A,C (NH3)

0,700

0,600
A-
I \

1\, ,---+-
i
~
I
0,500
;--r- I '
...
E I \!
I t
! \
I

~ 0,400
ILL, I

~
:r
~
:

I
\;

I I ! \
I I

o
.{ 0,300
!
I
\!
--,-,----,-
I.
J \I
\
\1 ~ ~
0,200
" :

<NWG
0,100

Fig.3.12: Comparison ofFilterpack ,A' and Filterpack ,C' for NH3 during the same time
period.

B,C(HN03)

1,400

1,200
..

• Ë
'al
2:
~
1,000

0,800 !

~
j
i
I
,

0
z
e- 0,600 !
!
u
ai
}
/ \
\ :
'
0,400 aV--L-L-
\i
\, It
I I
I
0,200

Fig. 3.13: Comparison of Filter pack "B" and Filter pack "C" for HN03 during the same time
period

Page 37
 Results: Fi/ter /Jacks

B,C (rN03)

40.000

Il
35.000
,,
,,

30.000
~
I
!
;
I
"è 25.000
'"Eo ,i
I
c
9
;:;: 20.000
o If,
!\ '*
z
w I /1
0' I \
tti 15.000
i
10.000
/
5.000

Fig. 3.14: Comparison ofthe ln-line Filter pack "B" and the "Open-face" Filter pack "C"
determined concentration values for the sum of particulate nitrate and
gaseous nitric acid during the same time period.

Dezember 02-Mai 03

20,000
•
18,000

16,000

• ~
.ê
Ö
E
oS
M
14,000

12,000

10.000 •
• •
•

0
z 8.000
•
t!-
al •
6.000
y =
1,0806x
4.000 • R2 = 0,546
• B-C(SN03)
2.000
• Linear (B-C(SN03))

0.000
0,000 2,000 4,000 6,000 8,000 10,000 12,000 14,000 16,000 18,000 20,000
C[rN03][nmol/m")

Fig. 3. IS: Comparison of data for the sum of particulate nitrate and gaseous nitric acid.

Page 38
 Results: Fi/ter lJacks

Abb.3.16: Comparison ofthe In-line Filter pack "B" and the "Open-face" Filter pack "C"
determined concentration values for the sum of particulate ammonium and
gaseous ammonia during the same time period.
B,C (ENH.)

90

80
•
70

• Ë
::.

~
~
~ 50
60

40
----------

•
!:!
III •
30 •
y= 1,1289x

20
R2 = 0,7447
• B,e SNH4
-Linear (B.e SNH4)
10

10 20 30 40 50 60 70
C (l:NH.)[nmoUm')

Abb.3.17: Comparison of data for the sum ofparticulate ammonium and gaseous ammonia.

Page 39
 Results: Filter oacks

3.1.3. Annual cycles of solo, NO]- and NH/ as well as S02, HNO] and NH]

The filter measurements began in December 2002 and continued until October 2004.
During the entire period of this project daily samples were taken. Some day are missing
because of filter packs shipping delays, i.e. problems to reach the Observatory in time.
Regarding individual months 20 % (October 2004) to 93 % (February 2003) of the days
could be evaluated. The amount of day samples per month is given in table 3.5. Overall
472 samples (i.e. 70 %) and 91 field blanks have been evaluated.

Seasonal cycles
The trace gases nitric acid and ammonia as well as the aerosol components nitrate,
sulphate, and ammonium, showed lower concentration values in the winter months
(November till January), than during the summer months (June till August). In
comparison with previous measurements at Sonnblick (Kasper and Puxbaum, 1993), the
increase of nitric acid concentrations occurred slightly later and is less pronounced. The
concentration values for sulphur dioxide do not show marked difference between winter
and summer. Except for these differences, the results of the recent measurements
correspond widely with the trends of the years 1991 till 1993. In chapter (3.1.7) the time
series will be compared. In the Figures 3.18 and 3.19, the seasonal trend (monthly
average) of major inorganic compounds in trace gases and the soluble aerosols,
respectively, are represented.

In table 3.5, concentrations ofnitric acid, sulphur dioxide, ammonia, nitrate, sulphate and
ammonium are summarized according to the monthly averages, as calculated from the
single days (arithmetic average). Furthermore medians, maximum and minimum
concentrations, standard deviations and the number of samples (n) taken per month are
given. Figures 3.20 to 3.25 give a visual layout of the concentration values in each
month, the median, and the minimum and maximum values. In the winter only very small
concentration values were determined while in the summer both, very small as well as
very high individual measurement values were possible.
All daily average values are listed in the appendix.

Page 40
 Results: Filter /Jacks

Table 3.5: Monthly averages,median concentrations, minimum (min) and maximum (max) values,
standar deviation (s) and number of sample taken per month (n), in (nmol/m')
(nmol m.3) N0 ' 3 50/' NH/ HN0 3 502 NH3
Dec.02 Average 0,5 0,9 1,9 0,9 1,6 7,1
=
n 20 Median 0,3 0,7 1,6 0,4 1,3 6,1
65% min. 0,2 0,03 0,3 0,1 0,3 2,0
max. 1,7 2,8 6,2 3,4 3,8 16,1
s(:!:) 0,4 0,9 1,6 1,0 1,4 4,7

Jan.03 Average 1,2 1,7 2,5 0,7 1,8 2,6

n = 13 Median 0,5 1,9 1,8 0,7 0,5 2,0
42% min. 0,4 0,3 0,8 0,1 0,3 2,0
max. 10,0 3,3 6,8 0,7 9,9 10,2
s(:!:) 2,6 0,9 1,7 3,2 2,9 2,3

Feb.03 Average 0,6 4,6 5,7 1,6 2,1 3,1

=
n 26 Median 0,2 4,3 5,1 1,2 0,7 2,6
93% min. 0,2 0,05 0,4 0,2 0,5 2,6
max. 2,3 18,6 18,5 7,3 8,7 13,5
s(:!:) 0,6 4,4 4,3 1,5 2,4 2,1

March 03 Average 2,5 3,3 6,3 1,9 1,8 17,7

n = 16 Median 1,3 2,2 5,4 1,2 1,2 15,7
52% min. 0,2 0,05 0,4 0,2 0,5 2,6
max. 13,4 19,6 17,6 5,4 5,5 53,0
s(:!:) 3,7 4,7 5,3 1,7 1,7 16,2

Apr.03 Average 13,3 10,8 28,6 3,4 3,7 28,8

=
n 27 Median 8,0 9,2 23,7 2,2 2,3 22,0
90% min. 0,2 0,7 1,5 0,5 0,5 2,6
max. 44,3 27,4 80,0 15,4 15,8 83,S
s(:!:) 13,9 8,9 24,4 3,5 3,8 22,1

May 03 Average 8,1 9,6 16,9 2,3 1,2 24,6

n= 14 Median 7,3 9,2 19,4 2,5 0,8 22,3
45% min. 0,2 0,3 0,4 0,5 0,5 2,4
max. 27,9 30,4 32,1 4,2 3,2 55,1
s(:!:) 7,3 7,8 10,7 1,4 0,9 15,3

June 03 Average 8,7 13,7 25,6 5,6 3,0 40,7

=
n 19 Median 5,7 11,5 20,7 5,2 2,5 37,1
63% min. 0,8 2,0 1,1 0,2 0,5 21,3
max. 27,7 42,7 61,9 10,8 10,2 68,9
s(:!:) 7,1 9,8 17,2 3,0 2,0 13,2

July 03 Average 3,2 10,8 19,7 16,6 3,9 40,6

=
n 25 Median 2,4 8,0 15,4 12,1 3,8 36,9
81% min. 0,2 0,05 0,5 0,2 1,2 17,7
max. 11,7 31,3 59,5 49,2 13,4 96,3
s (+) 3,0 9,2 16,8 14,8 2,5 16,2

Page 41
Page 42
Page 43
 Results: Filter Dacks

70,0

60,0
- ..... HN03
~S02 ~
I \
50.0 -.- NH3
I I
I \

~
Ë
40,0
I
r-.... " I \

,\ \
I. ~
;,.,,
/ I ;/ II

1
~ 30.0 ,,,
I
/ \
I
\ ,I
t
.1 I.
II
\
I'" I, ~ .
'~I \ TO, _ ~ \
I .. I "-. \

.
I I I ~ ~
20,0 I ~, ~ /~. I'
I ~ , I 1'1

/
/' I
'. \ ~ \
/" /¥
.t
'~
•
I I '\.\ ,/
10,0
....,' I .~ ~~ ..../
... I ji ~._~.
_ ..... -Il...... _;¥"';-.t~~
~ . .... .J. .~~.
..::!:::::';-~_______.~ ~---~.::-:::: ' ::.
.... - -.........-_0:>--_ ...............-.0-.--..
0,0
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~F~~~~'~~'&~~F~~~"~~, Monaten
.~

Fig.3.18: Annual cycle ofthe measured values oftrace gases.

70,0

60,0
- ..... N03 ""
-""-S04 I,"
I,
-.- NH4 I ,
50.0 I \
I I
I I
I I
I ,
.. 40.0
" I I
E
:. 1\ I I
o " I I
~ / \ I I
- 30.0
~ I
/ \\ I
'R' ;' I

'1\' /
I I A I \ '/\' \
,\ /',,' '. /4 ! \~
20,0

I"
II IIl I \
\ .. "," 6. ii
Ii'
\l' I
J ~.. /', _& I \,

10,0
I
' .'.",.v-' _...
I '. - _. ,lit.
\~\
\ /
.. " ~
.',
'll- ""'(f"/"'4\..
',,-'- '\.
\l I

_-4 ;. '. ,,' '. '.-- .. , / ~~- .~

,., ' .. _-ßt ~/ "
_ ~ --:" '<1. --~A'
~=- ~ -. .- .- - ..... -. - .... - +-
0,0

~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~F~~~"~~~~~~F~~~"~~' .~

Monaten

Fig. 3.19: Annual cycle of the measured values of particulate aerosols.

Page 44
 Results: Filter /Jacks

140.0

120,0

100,0

.,I
80.0

60,0
fil
Median
40.0
Average

20.0
/'
.-- '--~.
0,0
1
~",~"~~,~/~,,,~#,~~,~
~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~

140.0

120.0

100,0

i 80.0

~ 60.0

40.0

20.0

--
Average
....... Median

-----

140.0

120.0

100.0

I
'f
80.0

60.0

Average
40.0

"~------
!,\
.' ...•.. / ,/
,
20.0

Median

Fig. 3.20 - 22: Average-, median-, maximum- and minimum values for sot, N0 3' and NH/

Page 45
 Results: Filter packs

90.0

80.0

70.0

80.0.

1 50 0
.

1 40 0
.

30.0

Average
20.0

10.0
~l ..~.. --" /'
Median

35.0

30.0

25.0

~ 20.0

I
sf 15.0

10.0 Average

5.0

......
0.0

~,,~~,,~~,~#~,,~~,~~~,~
~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~

160,0

140.0

120.0

100.0

I
f
80.0

---
Average
60.0.

40.0

1~---- ---
20.0

0.0
~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~
~., ~.~.~.~.~. ~~# if~~ ,~.~.~.~.~. ~~# if

Fig. 3.23-25: Average-, median-, maximum- and minimum values for HNO), S02 and NH)

Page 46
 Results: Filter /Jacks

Comparison between summer and winter averages

The period of November, December, and January was averaged as winter, while the

months of June, July, and August were summarized as summer period. The calculation of

a summer / winter ratio represents the seasonal changes of the concentration values of the

individual compounds at the background site Hoher Sonnblick. These data are

summarized in Tables 3.6 and 3.7.

Table 3.6: Arithmetic average (x) and Standard deviation (s) for the summer and winter periods
and the entire sampling period (December 02 to October 04)
NO)- SO/- NH/ HNO) S02 NH)
[nmol/m ]3
x(s) x(s) x(s) x(s) X (s) x (s)
Dec. 02 - Oct. 04 5,5(10) 7,9(10) 15(20) 9,6(12) 2,9 (4) 19 (21)
Winter (Dec.-Jan.) 1,1 (1) 2,7 (3) 4,4 (4) 3 (3) 2,5 (3) 3,6 (4)
Summer (Juny - Aug) 8,4 (12) 15 (14) 28 (27) 20 (16) 3,4 (3) 38 (22)

Table 3.7: Summer / winter ratios calculated from monthly average

NO)- SO/- . NH/ HNO) NH)
Summer / Winter 8 5 6 7 Il

Summer and winter average values can also be calculated based on median values of the
single months. Summer/winter ratios based on these data are given in table 3.8.

Table 3.8: Summer / winter ratios calculated from the median

NO)- SO/- NH/
Summer / Winter 7 6 8

Page 47
 Results: Filler packs

3.1.4. Neutralization ratio

The compounds sulphate and ammonium show, as expected, very similar annual cycles.
Since the SBO is a background measurement site both compounds appear mainly in the
form of ammonium sulphate. Normally, it can be expected that at a background site the
aerosols are totally neutralized. At a background site at an elevation of 3 km, this is not
always the case. In free tropospheric air masses more there is a sulphate source but no
source for ammonia and/or ammonium. Thus aerosol gets more acidic. Regarding
monthly averages at Sonnblick, the aerosol neutralization ratio (calculated as NHl+
[nmol/m3] / 2*SO/- [nmol/m3]) is always below 1. The ratio of 1 represents a completely

neutralized aerosol. Values above 1 show an excess of ammonium and therefore point to
the existence of other ammonium salts like ammonium nitrate.

Considering the daily averages, it is possible to note that low neutralization ratio are
mainly determined in winter and during days with a lower aerosol concentrations. If the
measurement site is influenced less from ground level air masses, the influence of
ammonia is smaller and, consequently, also the aerosol neutralization ratio. Aerosols
collected within the free troposphere show low neutralization ratios (Georgii 1978,
Galasyn et al. 1987, Huebert and Lazrus 1980). At SBO during the months November
2003 till January 2004 the neutralization ratio is 0,8 on average.

During summer maximum aerosol concentrations were determined. The neutralization

ratio is generally about l, while during individual summer months the monthly average
increases to a value of 1,2.

During the winter months some days show ammOnIum concentrations below the
detection limit. As the detection limit for ammonium is higher than for sulphate, is the
neutralization ratio gets overestimated during these days. Furthermore the presence of
other ammonium salts (such as ammonium nitrate) would give a neutralization ratio
above 1. The scale in figure 3.26 was arbitrarily defined with a neutralization grade of 2.
There are other sporadic data points, which are above this value.

Page 48
 Results: Filter oach

Neutralization ratio

2,0
EI EI
•
•
1,8
...• a
B
t.
1,6
Œ'"
1.4 • •
• •
Il GI

II
•
Ii • •
• x • • •• • ..
•• • II
• • te
•
'" • •• • •
• •
• •
0,6
.. .. • a • EI
• Winter

0.4
• • a Spring

0,2
x • • Summer

x autumm
••
0.0
0.00 10.00 20.00 30.00 40.00 50,00 60,00

SO.[nmol/m')

Fig.3.26: Comparison ofneutralization grades (NH42+(nmol/mJ]/2*S042Tnmol/mJ])

and sulphate concentrations (daily samples).

3.1.5. Aerosol fraction

Table 3.9 shows, based on monthly averages, the relative contribution of the particle
phase fraction to the sum of aerosol compounds and trace gas. The calculations were
performed only for sulphate and nitrate. For ammonium it is not reasonable to calculate
this fraction, as the detection limit for ammonia is clearly above the detection limit for
ammonium. As ammonia concentrations were frequently below the detection limit in
winter, the relationship would give a systematic error.
Figure 3.27 shows the aerosol fraction for sulphate and nitrate compared to the aerosol
concentration. Based on daily values, the aerosol fraction for sulphate (SOl- / (SOl- +
S02» has an annual average of about 64%. In summer this value is about 71% and in
winter about 52%. These points to the special conditions prevailing at Sonnblick. In
summer, the measurement site is influenced by the mixing layer. Being not directly
influenced by emission sources the boundary layer below the sites contains more

Page 49
 Results: Filter {Jacks

particulate sulphate, a secondary polluted, than the precursor substance sulphur dioxide.
In winter the influence of the mix layer decreases. Therefore, the sulphate concentration
decreases more than the sulphur dioxide concentration.

For nitrate no big difference between winter (33%) and summer (3 I%) was determined.
The annual average is about 35%. The concentration of particulate nitrate in comparison
with the reactive gas nitric acid is controlled mainly by the semivolatile behavior of
ammonium nitrate both in the mix layer and the free troposphere.

_ Table 3.9: Monthly averge of Aerosol fraction for sulphate and nitrate
Months 80/"Œ(80z+804 z") N03'Œ(HN03+N03')
December02 0,3 0,4
January 03 0,6 0,5
Februayr 03 0,7 0,3
March 03 0,5 0,6
April 03 0,7 0,7
May03 0,8 0,7
June 03 0,8 0,6
July 03 0,6 0,2
August 03 0,7 0,3
September 03 0,6 0,1
October 03 0,5 0,1
November 03 0,7 0,2
December03 0,5 0,3
January 04 0,5 0,3
Februayr 04 0,4 0,3
March 04 0,6 0,5
April 04 0,7 0,3
May04 0,7 0,4
June 04 0,8 0,3
July 04 0,7 0,3
August 04 0,8 0,2
September 04 0,6 0,3
October 04 1,0 0,1

Page 50
 Results: Filter packs

1,0
• •••• • • • •
a
t a
•
0,9 ~ •• •
I) •• ~
..•g> .a
..•
II

0,8 • • •
•
• II
D
• •
III
0,7 I!I a

I\, •.. • II

c 0,6 • III
D
g El
u
ca ....
~ 0,5 III
Ö
..
I!! Il a
D il .. l:l
co

~ 0,4 a D

il
• III

0,3
[! •
iii
II
Il
0,2 II
~
lia
~
0,1

0,0
0,0000 10,0000 20,0000 30,0000 40,0000 50,0000 60,0000 70,0000
Aerosol contration [nmoUm']

Fig.3.27: Comparison ofthe "Aerosol Fraction" versus the aerosol concentration determined
at SBO.

Page 5/
 Results: Filter /Jacks

3.1.6. Annual cycles of minor inorganic and organic aerosol constituents

Seasonal cycles
The concentrations of chloride, oxalate, sodium, potassium, calcium and magnesium are
clearly lower than the values for sulphate, nitrate and ammonium. Table 3.10 summarizes
the monthly arithmetic averages, medians, minimum and maximum concentrations,
standard deviations, and the number of samples taken per month (n).
In Figure 3.28, the seasonal cycles of the aerosol compounds chloride, oxalate, sodium,
potassium, calcium and magnesium are given based on monthly averages (arithmetic
average ofthe daily samples).

12,0

--+-CI
-Oxalat
10,0 _.~. Na
- -)(-. K
-Mg
8,0 -Ca

:ê'0 6,0
E
.=.
4,0
•

2,0

D,a
~ ~ ~ ~ ~.~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~-~ ~ ~ ~ ~
~f~$'~"'~~#'~~~f~-$'~"'~~#'
Monaten

Fig 3.28: Seasonal cycle of concentration values for chloride, oxalic, sodium, potassium,
magnesium and calcium.

Page 52
 Results: Filter /Jacks

Table 3.10: Monthly averages,median concentrations, minimum (min) and maximum (max) values,
standar deviation (s) and number of sample laken per month (n), in (nmol/m')
cr K+ - Mg2+ Ca2+
(nmol m.J) c 0/"
2
Na+
Cec.02 Average 0,3 D,OS 0,9 0,2 0,1 0,7
n = 20 Median 0,3 0,02 0,8 0,2 0,1 0,4
65% min. 0,3 0,02 0,8 0,2 0,1 0,2
max. 0,3 0,1 3,1 0,2 0,7 3,3
slt) 0,0 0,04 D,S 0,0 0,1 0,7

Jan.03 Average 0,3 0,1 0,8 0,2 0,1 0,4

n = 13 Median 0,3 0,02 0,8 0,2 0,1 0,2
42% min. 0,3 0,02 0,8 0,2 0,1 0,2
max. 0,3 0,1 0,8 1,1 0,4 1,1
slt) 0,0 0,04 0,0 0,0 0,0 0,3

Feb.03 Average 0,6 0,2 1,2 0,3 0,1 1,0

n =26 Median 0,4 0,1 1,0 0,2 0,1 0,3
93% min. 0,4 0,03 1,0 0,2 0,1 0,3
max. 6,5 D,S 2,3 0,9 0,4 4,6
s (:t) 1,2 0,1 0,4 0,2 0,1 1,1

March 03 Average 0,4 0,2 1,3 0,3 0,1 0,9

n = 16 Median 0,4 0,1 1,0 0,2 0,1 0,7
52% min. 0,4 0,03 1,0 0,2 0,1 0,3
max. 0,8 1,6 3,4 0,7 0,1 2,1
s ~) 0,1 0,4 0,8 0,2 0,0 0,6

Apr.03 Average 0,4 D,S 1.3 0,9 0,3 1,4

n =27 Median 0,4 0,4 1,0 0,8 0,1 1,0
90% min. 0,4 0,03 1,0 0,2 0,1 0,3
max. 2,0 1,4 6,4 2,3 1,9 5,1
slt) 0,3 0,5 0,6 0,7 0,4 1,5

May03 Average 0,6 0,3 1,3 0,6 0,3 1,4

n = 14 Median 0,4 0,3 1,0 0,7 0,1 0,7
45% min. 0,4 0,03 1,0 0,2 0,1 0,3

•
max. 1,7 1,1 4,4 1,5 3,2 5,8
s ~) D,S 0,3 0,9 0,4 0,2 1,5

June 03 Average 0,9 1,2 1,6 0,6 0,7 4,2

n = 19 Median 0,4 1,1 1,0 D,S 0,6 3,5
63% min. 0,4 0,4 1,0 0,2 0,1 0,7
max. 3,2 3,0 4,1 1,3 1,7 8,9
slt) 0,8 0,8 1,1 0,4 D,S 2,8

July 03 Average 1,1 0,8 1,5 D,S 0,4 3,5

n =25 Median 0,4 0,5 1,0 0,2 0,3 2,9
81% min. 0,4 0,03 1,0 0,2 0,1 0,3
max. 5,6 2,1 4,6 1,8 2,3 10,5
s (:t) 1,5 1,1 2.2 0,8 0,9 4,0

Page 53
 Results: Filter packs

Continued table 3.10

(nmol m-3) cr c20/' Na+ K+ Mg2+ Ca2+
Aug.03 Average 0,3 1,7 1,6 1,6 1,4 10,3
n =26 Median 0,3 1,5 0,9 1,0 1,0 8,4
84% min. 0,4 0,0 0,9 0,2 0,3 0,3
max. 0,4 6,1 4,7 6,3 4.7 25,1
s(:!:) 0,0 1,6 1,2 1,6 1,2 8,8

Sep.03 Average 0,3 0,3 0,8 0,4 0,3 1,7

n = 16 Median 0,3 0,3 0,8 0,2 0,3 1,3
53% min. 0,3 0,04 0,8 0,2 0,3 0,4
max. 0,3 0,9 0,8 1,7 0,3 4,9
s(:!:) 0,0 0,3 0,0 0,5 0,0 1,4

Oct. 03 Average 0,3 0,1 0,9 0,2 0,2 1,3

n =26 Median 0,3 0,1 0,9 0,2 0,1 0,9
84% min. 0,3 0,0 0,8 0,2 0,1 0,4
max. 0,7 0,3 1,8 0,8 0,4 4,1
s(:!:) 0,1 0,1 0,2 0,1 0,1 2,8

Nov.03 Average 0,4 0,2 0,9 0,5 0,4 2,9

n =26 Median 0,3 0,2 0,9 0,2 0,1 1,7
84% min. 0,3 0,0 0,9 0,2 0,1 0,4
max. 1,2 1,7 0,9 4,1 3,1 10,6
s(:!:) 0,2 0,4 0,0 0,8 0,6 3,0

Dec.03 Average 0,4 0,1 1,1 0,4 0,3 1,3

n =23 Median 0,3 0,1 0,9 0,2 0,1 0,4
74% min. 0,3 0,0 0,9 0,2 0,1 0,4
max. 1,9 0,5 2,8 1,8 1,2 7,9
s(:!:) 0,3 0,1 0,5 0,4 0,3 1.7

Jan.04 Average 0,2 0,3 1,9 0,2 0,3 1,8

n =22 Median 0,2 0,1 0,9 0,1 0,1 1,2
71% min. 0,2 0,1 0,9 0,0 0,1 0,3
max. 0,5 1,8 7,4 0,5 1,0 6,3

• Feb.04
n = 15
52%
s(:!:)

Average
Median
min.
max.
0,2

0,4
0,2
0,2
1,7
0,5

0,4
0,1
0,1
1,6
1,6

3,7
0,9
0,9
29,2
0,1

0,3
0,2
0,0
1,2
0,3

0,4
0,1
0,1
1,8
1,8

2,2
1,8
0,3
9,5
s(:!:) 0,5 0,5 7,3 0,4 0,5 2,3

March 04 Average 0,3 0,5 1,6 0,2 1,0 4,0

n = 25 Median 0,2 0,5 0,9 0,2 0,4 3,2
83% min. 0,2 0,1 0,9 0,1 0,4 0,4
max. 1,9 1,8 13,9 1,1 3,1 10,5
5 (:!:) 0,4 0,4 2,6 0,3 0,8 2,8

Apr.04 Average 0,3 0,9 0,8 0,2 0,7 2,8

n = 27 Median 0,3 0,6 0,8 0,1 0,4 2,7
90% min. 0,2 0,2 0,8 0,1 0,4 0,6
max. 0,9 3,8 0,8 0,5 2,2 13,0
s(:!:) 0,2 0,9 0,0 0,1 0,5 2,4

Page 54
 Results: Fi/ter oacks

Continued table 3.10

(nmol m.3) cr c20/' Mg2+
May 04 Average 0,4 1,0 0,9 0,2 0,5 1,9
n =24 Median 0,2 0,8 0,8 0,1 0,4 1,8
77% min. 0,2 0,2 0,8 0,1 0,4 0,6
max. 2,6 2,5 3,7 0,8 1,0 5,2
s(:t) 0,5 0,8 0,6 0,2 0,2 1,4

June 04 Average 0,4 1,5 2,7 0,1 1,7 4,8

n = 20 Median 0,2 1,3 0,8 0,1 0,4 0,6
65% min. 0,2 0,2 0,8 0,1 0,4 0,6
max. 4,1 6,9 38,8 0,3 14,5 39,5
s(:t) 0,9 1,4 8,5 0,1 3,1 8,8

•
July 04 Average 0,2 1,3 1,0 0,4 0,9 4,2
n = 16 Median 0,2 1,2 0,8 0,2 0,4 2,5
53% min. 0,2 0,2 0,8 0,1 0,4 0,6
max. 0,5 2,5 3,4 1,7 2,0 18,1
s(:t) 0,1 0,8 0,6 0,5 0,6 4,8

Aug.04 Average 0,2 1,7 0,8 0,9 n.a n.a

n 10= Median 0,2 1,8 0,8 0,8 n.a n.a
32% min. 0,2 0,2 0,8 0,4 n.a n.a
max. 0,2 2,6 0,8 1,7 n.a n.a
s(:t) 0,0 0,8 0,0 D,S n.a n.a

Sep.04 Average 0,2 0,7 0,9 0,2 0,7 3,7

n =27 Median 0,2 0,4 0,8 0,1 0,4 0,6
90% min. 0,2 0,2 0,8 0,1 0,4 0,6
max. 0,8 3,1 1,7 0,9 1,5 15,9
s(:t) 0,2 0,7 0,2 0,2 0,8 4,7

Oct.04 Average 0,2 0,7 0,8 0,5 0,4 2,8

n=6 Median 0,2 0,7 0,8 0,4 0,4 0,9
20% min. 0,2 0,2 0,8 0,1 0,4 0,6
max. 0,2 1,2 0,8 1,1 0,4 9,2
s(:t) 0,0 0,4 0,0 0,4 0,0 3,5

n.a. = not analized

As for the major aerosol compounds chloride, oxalate, sodium, potassium, magnesium
and calcium, show some annual cycles, although they are less pronounced. At the same
time, it is important to point to the small concentration values and that, especially in the
cold season, a clear portion of the measurement values are below or in the range of the
detection limit. To determine monthly average and median values, the measurement
values below the detection limit were replaced with half ofthe detection limit. Especially
noticeable IS the pronounced seasonal cycle for calcium. Here the influence of
construction activity for renovation at the top of Sonnblick cannot be neglected.

Page 55
 Results: Filter [Jacks

Comparison oj oxalate and sulphate concentrations

In attempting to characterize an aerosol sample with the individual substances contained
in organic carbon, organic acids represent a significant contribution, in the range of 10%
(Limbeck and Puxbaum 2000). Oxalic acid, a dicarboxilic acid (C2) that is very water
soluble, is most frequently found in aerosol samples and often shows elevated
concentration values (Löflund et al. 2002). With respect to oxalic acid formation in the
atmosphere, different mechanisms were discussed in the literature. The biomass
combustion represents an emission source, whereas both the direct emission and the
photochemical formation of this acid in an exhaust-gas plume are possible. Also

• anthropogenic sources are considered for the oxalic acid emission, whereas here the
photochemical formation from hydrocarbon of antecedence is important. Because of its
relatively high concentration values and good determinability (the sampling and analysis
of teflon filter are possible), oxalate was taken as a tracer for the determination of organic
acids and consequently organic carbon in aerosol samples.
Figure 3.29 compares the seasonal cycle of sulphate and oxalate at SBO. The annual
cycles of both compounds show good agreement, although oxalate concentrations are
generally more than one order of magnitude lower than sulphate concentrations.

Page 56
 Results: Filter Dacks

35,0 2,00

1,80
30,0

I 1,60

25,0
J\ /
\7 i
\
1,40

/ \j \,
~ 1,20
~ 20,0 ,
,:.£
è
Ö
\ 1,00

N - 15,0
0,80
è
II)

10,0 0,60

0,40
5,0
0,20

0,0 D,DO

Fig.3.29: Seasonal cycle of concentration values for sulphate and oxalate.

Analysis also included the determination of the organic acids acetate, formate, pyruvate,
malate, malonate and maleate. For these compounds daily average values over the
detection limit could be scarcely quantified. Hence the detection limit can be given only

(see table 3.11) as on "upper concentration range" usually not reached at the site .

• Table 3.11: Detection limit of the determination of organic acids

Acetate Formiate Pyruvate Malate Malonate Maleate
3] 0,1
DL [nmol/m 0,4 0,1 0,1 0,1 0,1

Page 57
 Results: Fi/ter /Jacks

3.3.7. Comparison orthe measurement series 2002-2004 with the measurement

series 1991-199

Figures from 3.30 to 3.35 show a comparison between the measurement series described
here and the measurements at the beginning the 1990's (Kasper and Puxbaum, 1998). So
the seasonal cycles of the measurement series were overlaid with each other. Of course,
an optimal agreement of the values was not expected. The comparison shows similarities
in the concentration range and general temporal trends but also differences of the annual
cycles.

•
Basically, both the measured concentration range and the annual cycle are very similar,
especially in the winter months. That is the time when Sonnblick is influenced by the free
troposphere. The maximum monthly average values in the summer months show some
differences. In summer 2003 and especially in early summer 2004, the concentration
values of aerosol compounds ammonium and sulphate are clearly below the results of the
previous measurements. For nitrate this effect does not appear.
The summer period in 2003 was rather hot, while in 2004 winterly conditions were
prevailing ofthe site until middle of July.

35,0

30,0

•
25,0

~ 20,0
!
i,...
c !
ä !
,
'" 15,0
,
/ ,"
10,0

5,0 -
-+-504 (1991-93)
--- 504 (2002-04)
0,0

Fig. 3.30: Comparison of the filter measurement in 1991-1993 with the measuremet in series
2002-2004 for sulphate

Page 58
 Results: Filter oacks

70,0

60,0

50,0

"è 40,0

'"oE
F-
i 30,0

•
20,0

10,0

0,0
----
Fig. 3.31: Comparison of the filter measurement in 1991-1993 with the measurement series in
2002-2004 for ammonium.

16,0

14,0 -----------

~
1\ 1\
12,0 -----
1\
"
il
!\ \l. /
/\ ,
I \ 1\ / \

•
10,0
I \"
I
,I 'ri \,
~o I I
! 6,0 ----+---
Ô \
z
~
6.0

4,0

2,0

0,0

Fig.3.32: Comparison ofthe filter measurement in 1991-1993 with the measurement series in
2002-2004 for nitrate.

Page 59
 Results: Filter !Jacks

The evaluation of trace gases showed major differences, although the basic trends
remained. Sulphur dioxide showed during both sampling periods only a weakly
pronounced seasonal cycle. The maximum monthly average values are not driven by the
air status at the site (like it is the case for the aerosol compounds). Sulphur dioxide
concentrations are apparently determined by long-distance transport and cloud events
(Tscherwenka et al. 1998). Ammonia concentrations are higher in the 2002-2004 period
than at the beginning of the 1990's. Here a methodic effect (adjustment the equilibrium
ammonium / ammonia) by the heating of the suction line can not be eliminated. This is
valid also for the clearly higher concentration values for nitric acid, which were measured
in summer months 2003 and 2004.

25

20

15
Ë
::.
o
e -+-S02 (1991-93)
.!:.
-e- S02 (2002.Q4)
Ö
CIl
10

• 5

Fig.3.33: Comparison ofthe filter measurement in 1991-1993 with the measurement series in
2002-2004 for Sulphur dioxide

Page 60
 Results: Filter oacks

60

/
1:
I
50 i \

--+- NH3 (1991-93)

/ \
I
.I ,
\
---- NH3 (2002-04) I

I \
I:I---d ~
40
\
\

"e
::.
o
\,
I

I
/~\ i
e
oS
30
\ I
/-t-
£ "'- ~ \
z \ I ~- \

20 --

I
f--
I
\ \
il
;
10

Fig.3.34: Comparison ofthe filter measurement in 1991-1993 with the measurement series in
2002-2004 for ammonia

50

45

~
{,
40
--+- HN03 (1991-93) I \.
-a- HN03 (2002-04) i \
l--I_
35
I
, 'I
I \
,I ,
,
-.----.--;--j
... 30
,g
, ,
j \
o I
125
I

Ô
z
:z: 20
) \
15
(
___
/
1
10
£

--
5 /I

:--o---~
o

Fig.3.35: Comparison ofthe filter measurement in 1991-1993 with the measurement series in
2002-2004 for nitric acid

Page 61
 Results: Filter /Jacks

3.1.8. Comparison of aerosol data and gas phase concentrations and

precipitation data

During the filter measurements snow samples were collected with a W ADOS (Wet and

Dry Only Sampler). These measurements are continually carried out since 1987 in

cooperation with the Local Authority of Salzburg. The precipitation samples are collected

daily at 8 a.m. Thus it is possible to compare precipitation and filter pack data.

Table 3.12 lists the monthly average values of precipitation measurements. Table 3.13

•
contains the annual average values and average values for the summer and winter periods

of snow measurements at Sonnblick.

Table 3.12: Monthly average ofprecipitations [!lg/I]

SO/, NO)' NH4+
Dec.02 375 508 50
Jan. 03 125 247 31
Feb.03 32 81 37
Mar.03 305 717 153
Apr.03 1261 1265 614
May03 1131 1261 616
Jun.03 1052 1156 658
Ju1.03 1050 1208 575
Aug.03 1107 1096 553
Sep.03 1026 1408 436
Okt.03 184 227 60
Nov.03 170 166 10

•
May04 749 1420 458
Joo.04 720 1184 441
Ju1.04 775 998 384
Aug.04 879 1051 382
Sep.04 459 820 301

Table 3.13: Annual and period average ofprecipitations [!lg/I]

SO/, NO)' NH/
Summer period 931 1116 499
Winter period 223 307 31
Annual average 671 871 339

Page 62
 Results: Filter Dacks

The concept of scavenging ratios IS based on the simplified assumption that the
concentration of a component in precipitation is related to the concentration of the
respective compound in the air (Engelmann, 1971).

roi = Cp,i / Ca,i

roI Scavenging Ratio of compound i

Cp,i Concentration of compound i in snow
Ca,i Concentration of compound i the gas phase (or in aerosol)

Thus scavenging ratios can be calculated on a volume basis:

• roi = (Cp,i [Ilequ/l] / Ca,i [nequ/m3]) * 106

Using this approach it has to be held in mind that the transfer ofairbome compounds into
the liquid phase and further to snow or rain is extremely complex (Slinn, 1984). Aerosol
particles can act primarily as condensation nuclei. Thus they are already included in the
cloud water drops when they form. Furthermore aerosol particles can be collected by the
existing droplets via both, impaction and diffusion processes. Trace gases can also be
dissolved in droplets. Especially nitric acid is very well soluble and reactive. In case of
sulphur dioxide the uptake in the liquid phase does not depend only on the compound
concentration in the gas and liquid phase, but also on another reaction partners (e.g.

• oxidation of sulphite to sulphate by hydrogen peroxide) .

Sulphate, nitrate and ammonium determined in precipitation samples can be related to

aerosol phase sulphur, nitrate and ammonium (aerosol scavenging) and to the trace gases
sulphur dioxide, nitric acid and ammonia (gas phase scavenging).

Due to the air concentrations of particulate matter and trace gases at Sonnblick and the
different reactivity ofthe trace gases following scavenging ratios were calculated:

Û)S04 = Cpo 504 / Ca. 504

Page 63
 Results: Filter /Jacks

Scavenging ratios represent a summarizing parameter, which contains all the different
processes of scavenging. Nevertheless average scavenging ratios have proven to be an
useful tool to relate airborne concentrations to concentrations in precipitation and they are
used in large-scale models of wet depositions. Another field of application is the use of
scavenging ratios to calculate concentrations of past atmospheres based on liquid phase
concentrations from ice cores. The results of scavenging ratios determined at different
locations and from different viewpoints (e.g. Harrison and Allen 1991, Davidson et a\.
1985, Davidson et al. 1987, Barrie 1985, Chan and Chung 1986, Baltensberger et al.
1993) show the usability of this strong simplified approach .

• The calculation of concentration values in snow from aerosol phase measurements gives
data for wet deposition for sampling sites where only gas and aerosol measures are
available.

The figures from 3.36 to 3.38 show the annual cycle of concentrations in gas phase and in
snow. Unfortunately, between November 2003 and May 2004 there was a longer loss of
snow measurements because of a failure of the WADOS instrument. Even so, the regular
trend of the concentration values for the single compounds in Aerosol as well as in snow
is possible to recognize.

2000

1800 -----

• ....E
1600

1400

1200
----

il>
.5. 1000
~
a.
800

600

400 --

--+- S04-aerosol
200 -
-0- S04.precipitation

~,~~-~~,~~,~/~,~~~~,~~,
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~

Fig.3.36: Annual cycle for sulphate in aerosol and in precipitation

Page 64
 Results: Filter packs

700

600 ~-/\
I ~
I
I
i
500

.. 400
E
Q
E.
~
':300

200

100 -+- NH4-aerosol

-0- NH4-predpdation

Fig.3.3?: Annual cycle for ammonium in aerosol and in precipitation

2500

2000

500
-+- N03+HN03-aerosol & gas phase

-lI- N03-predpitation

~,~~~~,~~~&~~,~~~~,~~,
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~

Fig.3.38: Annual cycle for nitrate in sum of aerosol & gas phase and in precipitation

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Table 3.14 summarizes the monthly average values of the calculated scavenging ratios.
As previous measurements showed the tendency to high scavenging rations during the
cold annual cycles, additionally to the yearly averages the average for the summer (June-
August) and winter period (November- January) are given. Also here it is possible to
compare the results with the calculation of scavenging ratios for the measurements in the
beginning 1990' s. For the measure period from 1991 to 1993 the annual average values
of scavenging ratios are 2,6 * 106 for the sum nitrate, 1,4 * 106 for sulphate and 1,8 * 106

for ammonium.

Table 3.14: Annual and period average orthe scavenging ratios

sot NO)'+HNO) NH/
6
(10 ) (106) (106)
Summer period 0,8 1,3 1,2
Winter period 1,8 5,0 0,8
Annual average 1,0 2,9 1,1

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3.2 High-Volume - Levoglucosan and cellulose

3.2.1. Literature comparison for levoglucosan

The major organic components of smoke particles from biomass burning are
monosaccharide derivates from the breakdown of cellulose, accompanied by generally
lesser amounts of straight-chain, aliphatic and oxygenated compounds and terpenoids
from vegetation waxes, resins/gums, and other biopolymers. Levoglucosan and the
related degradation products from cellulose can be utilized as specific and general
indicator compounds for the presence of emissions from biomass burning in samples of
atmospheric fine particulate matter (Simoneit et al. 1999). Some previous works have
obtained the same conclusion about levoglucosan. It is emitted in large amounts, is
sufficiently stable and is specific to burning celIulose-containing substances. Thus, it
meets all important criteria to serve as an ideal molecular marker ofbiomass burning.
Table 3.15 shows a compilation of reported concentration ranges and contribution of
levoglucosan in wood burning to oe. All these works were performed using a quartz
fibber filter for sampling.
The highest concentration values of levoglucosan are observed in Kuala Lumpur
(Malaysia). The episode ofbiomass smoke pollution, 10caIly known as haze, which
struck Southeast Asia in 1997 has been claimed as one of the world' s worst ever
poIlution events in terms of its intensity, extent, duration, and the number of people

• affected (Nichol et al. 1998). In urban atmosphere like Kuala Lumpur, the particles
during a haze event are expected to be comprised of both input from biomass combustion
as we]] as vehicular emissions. In this work, Nichol and collaborators reported the results
of a study of the extractable organic components of air particles sampled during day- and
nighttimes (daytime from 07:31 to 19:30 local time, and nighttime from 19:31 to 07:30)
over a 5-day period (from 15 to 19 September) during the smoke-haze episode of 1997
(Simoneit et al. 2004). The dominant biomass burning component is comprised of
levoglucosan, the concentration value for daytime is 40240 ng/m3 and for nighttime is
33600 ng/m3• The difference between day and night is not very pronounced, that is
because of the stability during the haze episodes. The other sampling place in this work,

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used as background, presents also very high concentration values during the day as well
as during the night. The values are 3780 and 1400 ng/m3, respectively, but these values
are at least ro tünes lower than the urban place.
Zbynek and collaborators work was based on the analysis of aerosol samples were
analyzed from two different regions ofthe globe, a Brazilian tropical rainforest and a
Belgian urban site (Zbynek et al. 2000). Samples were collected during episodes that
were characterized by a different biomass combustion activity (winter vs. summer in
Belgium, dry vs. wet season in Brazil). The highest concentrations are observed in
Rondônia (Brasil) during the dry period (2006 ng/m3, ranging between 446 and 4106
ng/m3). This is almost 400 times higher than during the wet (nonburning) season (4,40
n/m3, ranging between 0,4 and 13,2 ng/m3). Urban total aerosols collected in Gent
(Belgium) present an average atmospheric concentration of levoglucosan of 477 ng/m3,
with a range of 121-1133 ng/m3, for the winter season, which is a factor of20 higher than
for the summer season (19,4 ng/m3, with a range of 4,1-34,6 ng/m3).
Table 3.15 contains a workfrom James et al. 2000. The sampling was performed in USA
for two urban sites, Fresno and Backersfield, and one background site, Kern Wildlife
Refuge, during the periods: December 26-28, 1995, and January 4-6, 1996. In the first
sampling period (26-28 December 1995) should be noted the very high average
concentration of levoglucosan in Fresno (7590 ng/m3), indicating the significant influence
of wood combustion at that time. In the same sampling period the average concentration
in Bakersfield was 1100 ng/m3, and for the background sampling site 25,3 ng/m3• For
Bakersfield and Kern Wildlife the difference between both sampling periods were very
small in comparison with Fresno. In the second sampling period the average
concentration of levoglucosan was 2130 ng/m3, less than in the first sampling period by
almost a factor of four.
Atmospheric particulate matter from three sites in the city of Campos dos Goytacazes
(Brasil) were analyzed for biomass burning emissions (Santos et al. 2002). Levoglucosan
has been detected at three sites (LC, CB and UENF), analyzed during a one-year
bimonthly investigation (six times). From May to November (1997), sugarcane and
bagasse burnings (used as fuel by the sugar mills) were observed all around the city. On
the other hand, from December 1996 to March 1997, only sporadic burnings occurred.

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Concentrations oflevoglucosan ranged from 0,15 to 1,65 ng/m3, 0,36 to 6,83 nglm3 and
0,19 to 28,42 ng/m3 for CB, UENF and LC, respectively. The LC site, surrounded by
sugarcane plantations is at face value a non-polluted countryside area, scarcely impacted
by vehicular pollution. The greatest concentrations of levoglucosan were detected at this
site, considered as an ideal ecological area.
In the work done by Simoneit et al. 2004, aerosol samples were collected during the
ACE-Asia campaign in 2001 spring to autumn at island sites: Gosan on Cheju (Jeju)
Island (Korea), and Sapporo on Hokkaido Island. Aerosol samples from Chichi-jima
(Japan) were collected over the western North Pacific, the East ofChina Sea and the Sea
of Japan during the cruise of the R/V Ronald H. Brown in the same time period. Ground
stations were located in Gosan, Sapporo and Chijima. Levoglucosan was determine in all
the samples, for Gosan the conce~tration values ranged from 8,0 to 74,0 nglm3 and in
Sapporo from 6,4 to 54 nglm3• Chimi-jima is located to the southeast ofthe major dust
outflow trajectories from Asia, but is still impacted. Ten years before (1990-1991) the
concentration values ranged from 0,5 to 1,4 nglrn3• Marine aerosols over the North
Pacific collected during the cruise of the R/V Ronald H. Brown from Hawaii to the East
Asia region changed from solely marine to dominantly terrestrial sources. Levoglucosan
is detectable in all the samples (0,2-40 nglm3), indicating biomass burning smoke is
spread over the western North Pacific.
During the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia),
samples of carbonaceous aerosols were collected on board the Center for
Interdisciplinary Remotely Piloted Aircraft Studies (CIRPAS) De Havilland DHC-6
Twin Otter aircraft (Mader et al. 2004). A total of 19 Research Flights (RFs) were
conducted between 31 March and 1 May 2001. The center of aircraft operations was
located at the Marine Corps Air Station (MCAS) Iwakuni, Japan, and the sampling area
included portions of the Sea between China, Japan and Korea, and the Philippine Sea
south of Japan. The different Flights collected the filter between several altitudes. The
minimum altitude registered was 25 meter and the maximum 3826m. Levoglucosan was
determined in all the samples (7,0 - 78,5 nglm3).
In the present work atmospheric aerosol samples were collected from six remote places
over Europe: Azores and Averio (Portugal), Puy de Dôme (France), Schauinsland

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(Germany), Sonnblick (Austria), and K-Puszta (Hungary). The sampling period was
between July I October 2002 and June I September 2004. Levoglucosan has been detected
in all this sampling sites and concentration values, depending the site showed different
results; the lower concentration values were determined in both background sampling
sites, AZO and SBO with average concentration of 13,9 and 19 ng/m3, respectively.
These results are followed for PDD (48 nglm3) and SIL (57 nglm3). The highest
concentration of levoglucosan were determined in AVE (273 nglm3) and KPZ (239
nglm3), the two low levels and with more influence ofbiomass burning.

All these recent studies over the world manifest that levoglucosan is generally present in
atmospheric aerosol samples in major or minor quantities. These studies collected
samples in rural, urban, suburban areas as well as Background, marine and aircraft
measurements. Levoglucosan was always present in these different samplings, indicating
the influence ofbiomass burning in the atmosphere and confirming that levoglucosan is a
good tracer for wood smoke.

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Table 3.15 Recent studies of levoglucosan determination in atmospheric samples

Levoglucosan/OC
Levoglucosan in wood buming
Sampling site [nglm'] emissions Date Reference
%C

RondÔnia, Brazil Rural 4,4 (0,4 - 13,2) 0,34 (0.02 -1,30) 10 April - 21 May 1999 Zbynek Z. et al. 2002
110m asl
2006 (446 - 4106) 4.79 (2,10 - 7) 3 Sept- 31 Oct 1999

Gent, Belgium Urban 19,4 (4,1 - 34,6) 0,22 (0,8 - 2) 10 June - 21 Aug. 1998 Zbynek Z. et al. 2002

477 (121-1133) l,52 (0,05 - 0,37) 12 Jan. -11 March 1998

Lake de Cima (LC). Brazil Rural 0,19 - 28.42 Dec. 1996 - Nov. 1997 Santos et al. 2002

"Corpo do Bombeiros" (CB) Urban 0,15 -1,65 Dec. 1996 - Nov. 1997 Santos et al. 2002

Universidade Estadual do suburban 0,36 - 6,83 Dec. 1996 - Nov. 1997 Santos et al. 2002
Norte Fluminense (UENF) area

Fresno (USA) rural-urban 7590 26-28 December 1995 James et al. 2000
2130 4-6 January 1996

Bakersfield (USA) Urban 1100 26-28 December 1995 James et al. 2000
1370 4-6 January 1996

Kem Wildlife (USA) Background 25,3 26-28 December 1995 James et al. 2000
22.5 4-6 January 1996

Gosan, Jeju Island (Korea) Ground marine 8,0 - 74,0 0,29 (0,14 - 0.49) 8 April- 17 May 2001 Simoneit et al. 2004

Sapporo Island, (Japan) Ground marine 6.4 - 54 0,44 (0,07 - 0,78) 8 April- 12 Jan. 2002 Simoneit et al. 2004

Chichi-jima Island. (Japan) Ground marine D,S -1,4 0,06 (0,04 - 0,08) 9 April 1990 - 20 Sept 1991 Simoneit et al. 2004

Western North Pacific Board marine 0.2-40 0,18 (0,003 - 0,37) 16 March - 20 April2001 Simoneit et al. 2004

Sea of Japan south Aircraft 31.4 (7,0 - 78,S) 2,0 - 10 31 March- 1 May 2001 Mader et al. 2004
east of the Korea Peninsula measurements
east china sea

Kuala Lumpur, Malaysia

UMGday Urban, Haze 40240 15-19 Sept 1997 (7:31-19'30) Simoneit et al. 2004
UMG night Urban, Haze 33600 15-19 Sept 1997 (19:31-7.30)

SPday Suburban 3780 15-19 Sept 1997 (7:31-19'30) Simoneit et al. 2004
SPnight Suburban 1400 15-19 Sept 1997 (19:31-7 30)

Azores. Portugal Oceanic 13,9 «0,1 - 79,6) 1,02 (0,1 - 5.8) 8 July 2002 - 2 July 2004 this work
Background

Aveiro, Portugal Rural coastal 273 (1.8 - 1478) 20.06 (0.1 - 108,6) 1 July 2002 - 17 June 2004 this work
maritime

Puy de DÔme, France Continental 48 «0,1 - 321) 3.5 (0,2 - 23,6 ) 25 Sept 2002- 15 Sept 2004 this work
Background

Schauinsland, Germany Rural mountain 57 «0,1 - 470) 4.2 (0,5 - 34,S) 19 Sept, 2002 - 16 Sept. 2004 this work

Sonnblick. Austria Free Troposphere 19 «0.1 - 166) 1,42 (0.1 -12,2) 3 Oct 2002 - 7 Oct 2004 this work

K-Puszta, Hungary Continental rural 239 (2 -684) 17.56 (0,1 - 50.2) 4 July 2002 - 23 May 2004 this work

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3.2.2. Literature comparison for cellulose

Atmospheric cellulose is a mam constituent of the insoluble orgamc aerosol and a

"macrotracer" for plant debris. The method to determine cellulose in atmospheric aerosol
samples is relative new, only two papers (Kunit and Puxbaum, et al. 1996, and Puxbaum
and Kunit, et al. 2003) have presented results about cellulose determination. Kunit and
Puxbaum developed a new analytical method for the quantitave determination of
cellulose in aerosols. The first results of cellulose determination were obtained from
samples acquired during autumn and winter of 1994 in Vienna. The values range between
0,10 J.lg/m3 and 0,94 J.lg/m3•

The second work was carried out also in Vienna. The aerosol samples were collected in
downtown Vienna during 9 months (September 1994 to June 1995). The grand average of
the monthly data is 0,374 J.lg/m3 total cellulose. The highest monthly average of the
atmospheric cellulose concentration was observed in September (0,63 J.lg/m3). The
occurrence of higher values during autumn is consistent with the production of leaf litter
during fall.

Thus "Carbosol" project is the first work where during a long time of sampling (2 years)
cellulose concentrations were determined. After two years of sampling it is possible to
describe an annual cycle for atmospheric cellulose. The publications mentioned above
give information about cellulose concentration values at an urban site (Vienna), but with
this work it is possible to know more about the distribution of atmospheric cellulose
concentrations over Europe at remote sites. As we described before the sampling sites
(chapter 2.1) at different see levels can give us an idea about the distribution of "free
cellulose", in the atmosphere.

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3.2.3 Detection limit

To determine the detection limits and to check for contamination during the shipping,
storage, sampling and assembling of the filter holder, field blanks were sent with the
samples for every sampling site.

The detection limits were determined by dividing three times the standard deviation of
the field blanks by the average air volume collected for the weekly samples. This volume
varies with the sampling sites. The following Table 3.16 shows the average volume
sampled for every sampling site.

Table 3.16: Average sampled volumes orall the sampling sites

[Nm3] Azores Aveiro Puy de Sonnblick Schauinsland K-Pusta
Dome
Aver. Vol. 10081 10691 8025 3019 7380 4457
sampled

First the detection limits were calculated for all sites separately to check whether it is
possible to combine then to one detection limit for all the sites. The following table 3.17
summarizes the detection limit for cellulose and levoglucosan.

Table3.17: Detection limit for Cellulose and Levoglucosan

DL [ng/m3] Azores Aveiro Puy de Sonnblick Schauinsland K-Pusta
Dome
Cellulose 5,2 7,7 3,4 22,1 6,4 32,7
Levoglucosan 0,3 0,7 0,3 0,3 0,7 1

Concerning cellulose, the field blanks for AVE, KPZ and SBO showed strong variations,
and consequently the detection limits for these sites are higher than the others. As stated
before, these high field blanks can be attributed to the shipping, storage, sampling, etc,
during the sampling period. Regarding AZü, pnD and SIL conditions were much better
and quite similar. An overall detection limit calculated for those three sites is 5,6 ng/m3•
In a next step another calculation was made with all six sites, disregarding the extremely

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several high blanks. In this case the detection limit was 6,6 ng/m3• As an approximation
the overall detection limit was set to 5 ng/m3 for cellulose for the six sampling sites. This
approximation does not create problems for KPZ as only a limited number of samples
show concentrations between 5 and 33 ng/m3 (4 samples). However for SBO this
compromise does make a change and it has to be kept in mind that a number of samples
are close to the detection limit. As the detection limit is often calculated according to a Is
criteria (instead of "3 s- criteria") we nevertheless took the approach of one detection
limit of 5 ng/m3 for all six sites.

In case of levoglucosan generally no blank reading was obtained in the field blanks. Thus
the detection limit was calculated according to the detection limit ofthe analytical
method. As the sampled air volume and the filter aliquots areas used were different for
the six sites, the detection limits change as well. Just for simplicity, we decided to use
one detection limit, i.e. 1 ng/m3• Since concentration levels for levoglucosan were
generally high enough, this approximation does not lead to data loss compared to the
values given in Table 3.17. The following Table 3.18 shows the percentage of samples
below the detection limit for every site.

Table 3.18: Arnount ofsamples (%) below the detection limit

Levoglucosan Cellulose
Azores 3% 44%
Aveiro 0% 2%
'e Puyde Dome 2% 13%
K-Pusta 0% 0%
Sonnblick 7% 9%
Schauinsland 3% 0%

AZO shows a notable amount ofcellulose samples below the detection limit (44%); it is
followed by POD (13%) and SBO (9%). For levoglucosan, SBO shows several samples
below the detection limit (7%), but still this percentage is not very high. For the rest of
sampling sites hardly only samples were below the detection limit.

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3.2.4 Average concentrations for levoglucosan and cellulose

Levoglucosan
The impact from biomass combustion has been shown to affect atmospheric chemistry
after transport periods of several days and thousands ofkilometres (Swap et al. 1996),
meaning that the effect ofbiomass combustion can be seen also in great distances from
the source region. In order for a molecular marker to be useful in tracing long-range
transport from source region to receptor locations, the compounds must be conserved in
transport (Fraser et al. 2000). Previous work has shown that levoglucosan does not
undergo decomposition reactions when exposed to ambient levels of gaseous
photochemical oxidants such as ozone or nitrogen dioxide (Locke et al 1988). However,
if one reviews the chemistry of levoglucosan, one reaction pathway that might selectively
remove levoglucosan above and beyond the possible reactions of other molecular
markers in the acid-catalyzed hydrolysis of levoglucosan to form ß-D-glucose. Frasser et
al. 2000 presented a work with a test of levoglucosan stability. The simulations in this
test were designed to simulate the possible composition of atmospheric liquid droplets
that could catalyze the hydrolysis oflevoglucosan to produce ß-D-glucose. The
concentrations of levoglucosan during the time period of 10 days do not show
preferential degradation ofthe levoglucosan due to acid-catalyzed hydrolysis. This
suggests that levoglucosan does not undergo acid-catalyzed hydrolysis over the transport
time of several days. Another test from Simoneit et al. 2004 also confirmed this
experiment. They tested the hydrolysis of standard levoglucosan in water and in acid (pH
- 2) solutions and found recoveries after 1,3,5, and 15 days of99% for both cases.
Table 3.19 summarize the average, median, minimum and maximum values of all six
sampling sites.
The concentration values oflevoglucosan in the different sampling sites change
considerably. At the background sampling sites, AZO and SBO, as is expected, the
concentrations are very small in comparison with the other sites. At AZO the average
concentration is 13,9 nglm3 with a range of <1,0-79,6 nglm3• At SBO an average of 19
nglm3 was determined with a range of<I,0-166 nglm3• POD and SIL present very similar
average concentrations of 48 nglm3 with a range of< 1,0-321 nglm3 and 57 nglm3 with a

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range of<I,0-470 nglm3, respectively. KPZ presents a high average concentration of

levoglucosan, 239 nglm3 with a range of2,0-684 nglm3. The highest average
concentration is for AVE, 273 nglm3, with a range of 1,8-1478 nglm3•

Table 3.19: Average, median, minimum and maximum values of the six sampling sites
Levoglucosan Azores Aveiro Puy de Dome Schauinsland Sonnblick K-Pusta
[ng/m3]
Average 13,9 273 48 53 19 239
Median 9,2 171 31 48 9 226
Min <1.0 1,8 <1,0 <1,0 <1,0 2,0
Max 79,6 1478 321 142 166 684

Table 3.20 shows the average concentration of summer and winter periods and the ratio
between summer-winter periods. As in "Backgrounmessungen Sonnblick" project, the
summer period is defined as June, July and August and for winter period November,
December and January.

Table 3.21: Arithmetic average and ratio between summer and winter periods
Levoglucosan Azores Aveiro Puy de Dome SchauinsJand Sonnblick K-Puzta
[ng/m3]
Summer 13,4 40,1 115 55,1 20,2 147
Winter 17,0 525 20,6 44,7 19,0 362
Summerlwinter 1 0,08 6 1 1 0,4

As was expected, at the background sampling sites there are no differences between
summer and winter periods, therefore the ratio between both these periods was only I for
AZO as well as SBO. If we regard AZO and SBO as maritime and continental
background sites, we see that especially winter concentrations are quite similar. At PDD
and SIL, the average concentrations of summer period are higher than winter period. It is
observed that for PDD the difference is more pronounced. With a summer-winter ratio of
six, average concentrations in summer are six times higher than in winter. For SIL the
proportion is not so marked, the average concentration in summer is only two times
higher than in winter.

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A VE and KPZ, present opposite seasonal cycles with low levels during summer. This
ratio is obtained below O. Ifwe calculate the ratio ofwinter- summer periods we obtain at
AVE the ratio of 13 and for KPZ only 2. As it can be seen in figure 3.40, the difference
between summer and winter for AVE is very abruptly. For KPZ this difference is not
very pronounced.

Cellulose
Atmospheric cellulose is a main constituent of the insoluble organic aerosol and a
"macrotracer" for plant debris. The average concentration values of cellulose as well as
the median, minimum and maximum values for the six sampling sites are summarized in
Table 3.22 At AZa, a background sampling site, it was expected to find the lowest
average concentration values of cellulose (13,5 nglm3, with range of <5,0-68,6 nglm3).
SBa is a background mountain sampling site, but especially in winter representative for

the free troposphere. The observed concentration values of cellulose consequently might
be lower than POD and SIL. In this sampling site an average concentration value of 33
nglm3 was found with a range of<5,0-155 nglro3• At POD, an average concentration
value of 60 nglm3 is found with a range of <5,0-226 nglm3, SIL, a rural mountain
sampling site, presents also an average concentration values of cellulose of 60 nglm3,
with a range of 6,4-369 nglm3• AVE is a low level site, but the average concentration is
not as high as at KPZ. The difference is that AVE is close to the urban area and to the
coast maritime. This sampling site has an average concentration value of 52 nglm3, with a
range of <0,5-213 nglm3• The highest average value is for KPZ (133 nglm3, with a range
of 22,3-436 nglm3). At KPZ there are two factors to influence this high value. One is a
low level site, and it is more affected by other emission sources ofpollutants.
Furthermore it is a rural site and the contribution of cellulose in the air is higher than for
example in an urban site. Table 3.22 shows the results of average concentration values
and median as well as minimum and maximum values for the six sampling sites.

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Table 3.22:Average, median, minimum and maximum values orthe six sampling sites
Cellulose Azores Aveiro Puy de Dame Schauinsland Sonnblick K-Pusta
[ng/mJ]
Average 13,5 52 60 89 33 133
Median 8,9 44 56 62 25 114
Min <5.0 <5.0 <5.0 6,4 <5.0 22,3
Max 68,6 213 226 369 155 436

Table 3.23 presents the average of summer and winter periods and the ratio between both
seasons. For all the sampling sites the averages of summer were higher than winter
concentration values, except for AVE. Here, the average of winter concentration values is
higher.

Table 3.23: Arithmetic average and ratio between summer and winter period
Cellulose Azores Aveiro Puy de Dame Schauinsland Sonnblick K-Puzta
[ng/m3]
Summer 13,6 33,9 98,0 113,6 43,7 168,2
Winter 10,1 61,9 28,6 38,7 20,8 94,8
Summerlwinter 1 0,5 3 3 2 2

3.2.5. Annual cycles of levoglucosan and cellulose

• Within the framework of the "CARBOSOL" project aerosol samples were collected
during two years (2002-2004). At AVE and AZO the sampling began in July 2002 and
until July 2004. At KPZ sampling began in July 2002 but it is finalized continued already
at the end of May 2004. At POD, SIL and SBO the collection started in October 2002 and
continued until October 2004. At AVE, SIL and SBO more than 90 % ofthe overall
sampling period could be evaluated (AVE 98 %, SIL 97 % and SBO 91%). For POD,
KPZ and AZO the overall sampling period, which has been evaluated was 83 %, 73 %
and 72%, respectively. The Tables with the final results of all sampling sites are
summarized in annex.

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Levoglucosan
Levoglucosan is emitted in large amounts, is suffiently stable, is specific to burning of
cellulose containing substances, and thus meets all important criteria to serve as an ideal
molecular marker ofbiomass burning (Zbynek et al. 2002).
Levoglucosan is the most abundant sugar derivative emitted from wood combustion, and
was determined in all sampling sites.
As AZO is a maritime background site with hardly any emission sources, the
concentrations were low and no seasonality is observed in the annual cycles.
Nevertheless there are a considerable number of "spikes" throughout the year; which
most likely point to local effects.
For KPZ, the evaluation ofthe annual cycle is not straightforward, as there are values
only until May 2004. The highest concentration values for levoglucosan were found in
winter months, but unfortunately only one summer period was monitored.
At SIL hardly any seasonal cycle was observed for levoglucosan. For PDD low
concentrations were found during winter and elevated concentrations during summer.
This is typical for a mountain site because it might be above the mixing layer during
winter time and will be influenced more effectively by boundary layer air masses during
summer.
The annual cycle at SBO shows, what is expected for a mountain station and has been
discussed for PDD. In December 2002 very high concentrations were observed that were
not typical for this time season. We can hypothesize about a local effect from the valley
_ under Sonnblick Observatorium, where there are a few guest houses.
At AVE sampling site the highest concentration values of levoglucosan were determined.
AVE is a coastal maritime place, and the major concentration values were obtained in
winter. Here, the contribution of wood combustion is also observed for heating during
these winter months. The seasonal variation at AVE is very strong; the difference
between winter and summer months is really very pronounced.

The annual cycles oflevoglucosan at the different sites are represented in the following
Figures from 3.39 to 3.44.

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AZORES

200

180

160

140
.,...
e
a, 120
.:.
c:
:0
100
u
"
ä.
..
0
>
....
80

60

40

20

o
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
"
~~~#,#,#~##,~~~#~#~,#~~~#,#~##
'l: 0/ ...
'),C?f "C?f 'l: ~ '\'
C?f ,.,'" -V' ,,'\' ,,~ ~
'),'" ,.,'" -V' '),'" ,,'"
'),'" '),'" '),'Ii '),~ ...'Ö '),'Ö '" 'Ii '),C?f 'l: l'

Fig 3.39: Annual cycles for Levoglucosan at Azores

AVEIRO

1600

1400

1200

"e 1000
a,
.:.
..
c:
0
800
u

"
ä. ~
......
0
> 600 ,.
'.
., ( ', ..
400 \
=!
'! :
i. l'
200 !.
"
. ,,'
'1.
;."
'I'; ~I . : : ! : ;

Fig 3.40: Annual cycles for levoglucosan at Aveiro,

Page 80
 Resu/ts: Hif!h- Va/ume

K.PUZTA

1600

1400

1200

...
E 1000
e;,

..
oS
c
ln
0
800
u
:>
g
> 600
....
ID

400

200

o
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
,)~ )oS Yr-~<:f,cf'" ~o"" ""~ ~~. Yr-cf~",..;;
~",<: )~c:< Yr-~~ Yr-~~ ",et cf'" d''' ~o-¥ <;:l9,J1 )",c:< ",,01~~' ~~' Yr-<f
)~<f ~~ ~",... )~c:< )~o»~ ~eet ~eet
" -î-' ,\-'11 -î-' ,,~ '\' -î-' ,,'II ,,'l-' 'l-' ,\-'" ~ ,\-'1 ,,'1 'II -î-'~' 'II '\-<¥
,\-<::f QI '" ,\-'l-' ,,'l-' ",' ,\-<::f ,,<::f 'II.. 'l-' 1" "qj

Fig 3.41: Annual cycles for levoglucosan at K-Puzta,

SCHAUINSLAND

200

180 -. .. ----.

160 --- -----. _o. - .-.

140
...
E
a. 120 .---- -- ---- --
....
oS

•
c
!
0
100 , -- -
u
g" , ~ :
80 .---- --- ; ._- --- : -- - - -.-
>
....
ID :
: , ; I :

60
:
- ,- , -:- --- --- : - : --
: \ , I : : i :
; : , ,
: ! --- : !: - :
I
, : :
-.
40
, ;

,
:
,
:
i
:
I
;
: ;
! :, :

;, I : :
,: \
f! , : I i ::, > :
, , i :
, , :! , i: :
I
, : I
,! l
:1--
1[fi
20
j~ :
, !
;
, T: : , , iI ; , , ,, ; ; , i
,
.[ : . I i : , ,
IT
; !
!,, i
,
1: i ; ;
: " ;
I j
I
! ;
I
:
I
J , ! ! ! j
i : I
+rr

Fig 3.42: Annual cycles for levoglucosan at Schauinsland,

Page 8/
 Results: Hü!h- Volume

PUY DE DOME

400

350

300

..
e
a.
250
oS
c
il
0
200
u
:s
g. .-
> 150
"
...J

!
100 ------ I

.,
50 .'

Fig 3.43: Annual cycles for levoglucosan at Puy de Dôme.

SONNBLICK

200

180 -- --.--. .----

160

..
e
a.
140

120
oS
..
c
In
0
100
u
:s
ë;,
0
>
80
.3
60
j, .q
40 , .
.,
20

Fig 3.44: Annual cycle for levoglucosan at Sonnblick.

Page82
 Results: HiJ!h-Voillme

Cellulose
The seasonal variation of cellulose depends on the situation of the sampling sites. If the
sampling site is a background place like AZO, then small concentration values are
obtained and it is not really possible to observe a seasonal cycle. A significant number of
samples were below the detection limit. Thus it is not possible to define seasonality for
cellulose at AZO.
Thinking of "living biomass", i.e. plant debris, as the major source of cellulose, a typical
seasonal variation of cellulose would show high concentration values during the growing
season, especially during spring and fall. At SIL, KPZ, POD, and SBO, this variation can
be observed. Looking into more detail SIL and KPZ show similar patterns and POD and
SBO are comparable. As SIL is a rural mountain site and the difference between spring
and autumn in comparison with summer and winter is very pronounced. At KPZ, a rural
site, the concentration values during spring and autumn are also high but the difference
between seasons is not so pronounced as at SIL. POD and SBO are two mountain sites;
although the sea level ofthe observatories is still different. Especially the sampling site at
SBO is frequently located in the free troposphere during winter, and it can be used as a
background continental sampling site.
At POD the concentration values are lower than in SIL and KPZ and even lower
concentrations can be observed at SBO. As already explained for levoglucosan and
earlier for the inorganic aerosol constituents, mountain sites are influenced by boundary
layer air masses during summer, while in winter air masses are prevailing at the site are
decoupled from the mixing layer and can be representative for free troposphere
conditions. This effect even enhances the seasonal cycle which can be expected for
cellulose.
For AVE a different seasonal cycle was observed as expected. High concentrations of
cellulose are observed in the winter months, just like for levoglucosan. It could be
possible that this concentration of cellulose in the winter months is the part of wood that
does not undergo the pyrolisis of cellulose. However, first measurements of the emission
of cellulose during wood combustion do not point to marked emissions of cellulose
(Schmid, 2005).

Page 83
 Results: Hif!h- Va/ume

The annual cycles of cellulose at the different sampling sites are represented in the
following Figures from 3.45 to 3.50.

AZORES

200

180

160

..
140

E 120
a.
.:.
..
co
0
100

~
Gi 80
U

60

40 ----.

20

o
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
:~~ ')oS' '!l-v~ C:J0~ c:!'~ ~o-4 ')~«<,c~ ~'I>'"
~,,}. ~'I>.J( cF ~o-4' ~lJ')'1>«<,c~'
')v<:' .'>~ '!l-v~ ~~ c:!'q <,cO}) '!l-<f '!l-<t' ~'I>'" ')v«.;>~ ')oS' C:J0~ c:!'~
" '),Of "Of Of,.,<::1 '),<::1 ,.,<::1-'),<::1 '),<::1 'V '),'V ,,'V ~ '\' '),~ '),<:f ,,'0' -V' ,,'\' ~ ~ '),'<1 '" -V' '),<::1 ,,0,: '),Of 'V ~

Fig 3.45: Annual cycles for cellulose at Azores.

AVEIRO

500

450

400

..
350

E 300
a.
..
.:.
0
250 -----
~
Gi
U 200 -----

150

100 - .~
50

Fig 3.46: Annual cycles for cellulose at Aveiro.

Page84
 Results: Hif!h- Volume

K-PUZTA

500

450

400

350

Ë 300
a.
..
oS
co
0
2SO

:ä
Qi
U
200

ISO

100

SO

,I
o
"
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
"
~~~##&~~~~~####~~~~#&&#~~~~#####
,,'I: 'I:
'J,'t; ,,'I: 'I: ~
'J,"i' ,,":I ":I rf' '\' ~
~''J,-: l>' 'J,":I ,,":I ":I l>' 'J,":I
'J,<:Y ,,"i' ~ ~ '!; Qf 'J,"i' ,,"i' 'Ii '1,.Qf .v'

Fig 3.47: Annual cycles for cellulose at K-Puzta.

SCHAUINSLAND

400

350 -,
!,
;

300 -- ,'-
;-
, -'--
, ,

..
~
2SO ,,------,- --
,
-

;
i
:
.- ---
,

..
oS
co 200 ;
;
; ! :
I
I !, j - I ------
.
0 ;
:ä 1
0
; ; i ; ,!
Qi ; i ,
.,!
0
U 1 ; i0 I ----- -----
1SO
i
ii, ; I 1 r :
;

!I :, , Ii I, ;
i
f
!
.
I
I
i! l i
I
0

100 I i i:
1 0 , ~ I
I
i
.
;
I !!
I
!~ !, ,
.: ~
"
! : ~
Ii
0
i
! 1, !
i iI ; , l~ , ;
I, i
:I
~

~:blJ!~3!
, i ,f
il , ; "~:, ., ..i , , --
I
SO I i\ I

u1illli
I0

; ~ i j I
i, ,
.
0 1
! 1 ; tj
" I
0
I
~:~ i i ; ; ti , 1
• il:';'
l H.i ~ :
: I
!;
iI I
i
j, 1
,,
, i i! , ! 'I' i
1
I' ; i t ~ 0
!li1;;;1 i
:'t;
It •••
I .•
11.
,
I . ","",.q
,0
.0'
•
f
1 il ~1 !, 0
I i : I
; ;
~
!I:, "
: I l'l:i.~":
I

i I if ! ~i

Fig 3.48: Annual cycles for cellulose at Schauinsland.

Page85
 Results: Hif!h- Volwne

PUY DE DOME

400

350 ---

300

...
E
250 -.
C.
.:.
..
GI

0
200

:ä
Gi
(,)
150

100

50

Fig 3.49: Annual cycles for cellulose at Puy de Dôme.

SONNBLICK

200

160

160

140

....Ë 120

'"
.:.
..
GI
0
100

:2
~ Gi
(,) 60

60

Fig. 3.50: Annual cycles for cellulose at Sonnblick.

Page86
 Results: Hif!h- Volume

Comparison levoglucosan versus cellulose.

The comparison ofthe annual cycles (monthly average) oflevoglucosan and cellulose
show some differences between the different sampling sites (Fig. 3.51- 56). At AZü,
both levoglucosan and cellulose concentrations did not show a seasonality and had very
small concentration values. As this sampling site is a maritime background site, the
determined concentrations oflevoglucosan and cellulose most likely reflect background
conditions.
The annual cycles at SBO show higher monthly averages of cellulose compared to
levoglucosan for most ofthe monthly concentration values than for levoglucosan, with
maximum values during spring and summer. Only during two months (December 2002
and March 2004) levoglucosan average concentration levels exceed cellulose
concentrations.
The first year at POD, the monthly average concentrations of cellulose were slightly
predominating over levoglucosan, especially in April, May and June 2003. The second
year, the monthly average concentrations of cellulose in spring was higher than
levoglucosan, as it can be expected that concentrations of levoglucosan in summer at
ground level are lower.
During almost the entire annual cycle in SIL, the monthly average of cellulose and
levoglucosan are quite similar. Big differences can only be observed in spring months,
which the monthly averages for cellulose being almost a factor of 10 higher than the
monthly averages for levoglucosan. As SIL is a rural mountain place, these maximums in

• spring might originate from seed production and from repulsing of other cellulose
containing plant material.
In KPZ the monthly averages of levoglucosan are higher than cellulose, but they do not
show such pronounced differences as for AVE. As expected for cellulose in spring and
summer, the monthly average observed for cellulose is higher than levoglucosan.
At AVE both compounds show similar seasonal cycle with elevated concentrations
during winter. However the increase determined for levoglucosan is much more
pronounced (a factor of 9) compared to the concentration values of cellulose. During the
summer period the concentrations ofboth compounds were very similar.

Page 87
 Results: HiJ!h- Volume

AZORES

100

o Levoglucosan
OCellulose
80

60

40

20

~~,&~~,~,~,,~~,&~~,~,~,
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~

Fig. 3.51: Monthly average of annual cycles at Azores for levoglucosan and cellulose.

AVEIRO

1200

o Levoglucosan
OCellulose

800

• -;:
~
a 800 -- ..-- ..---- ... - ( -
.:. ';. .;

400

200

~~,&~~,~,~~,~~,&#~,#,~"
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~

Fig. 3.52: Monthly average ofannual cycles at Aveiro for levoglucosan and cellulose.

Page 88
 Resu/ts: HiJ!h- Va/ume

K.PUSZTA

1200
o Levoglucosan
OCeJlulose
1000

800

~ 600
.s

400

.\
.. .. I;

200

Fig. 3.53: Monthly average ofannual cycle at K-Puszta for levoglucosan and cellulose.

SCHAUINSLAND

300

o Levoglucosan
0CeJlulose
250

200
.... ~
,
~
~
.... f.

• ~ 150
.s ~
~
100

50

o
~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
&#"~~'#"~~#~#"~~~"~~#

Fig. 3.54: Monthly average of annual cycles at Schauinsland for levoglucosan and cellulose.

Page 89
 Resu/ts: Hif!h- Va/ume

PUY DE DOME

300
o Levoglucosan
mCellulose
250

200

..
E
a.
oS
150
,
Il

J---
100

j I j~--
~

•
I;l
q ;!
50 1:
~
I
i

'j
o
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
&~"~'~"~~~&~"F~'~"~~' -~ -~

Fig. 3.55: Monthly average of annual cycles at Puy de Dome for levoglucosan and cellulose.

SONNBLICK

100

o LevogJucosan
!3Cellulose

80

~
J

(I
~
~i

.
~
,;. u
2J
.~
g '.,;

~~
y
~
~,
~

Fig. 3.56: Monthly average of annual cycle at Sonnblick for levoglucosan and cellulose.

Page 90
 ReslIlts: Hü!ll- Voillme

3.2.6 Comparison of levoglucosan and Organic Carbon (OC)

Since the late 1990s levoglucosan has been found in atmospheric particulate matter over
the ocean (Simoneit and Elias et al. 2000), in sediments (Elias et al. 200 I), in samples
from the burning of specific plant species (Simoneit et al. 1999), in different types of
wood (Fine et al. 2001), and in particulate matter over urban areas.
As mentioned earlier levoglucosan (l,6-anydro-ß-D-glucopyranose) is an ideal molecular
marker ofbiomass burning [Zbynek et al. 2002; Frasser and Lakschaman et al. 2000]. It
is emitted at such high concentrations that it can be detected at considerable distances
from the original combustion source, and it is found as a major organic component in the
particulate matter of ambient aerosols (Simoneit et al. 1999). Thus it is straightforward to
compare concentration of levoglucosan and OC, the fraction this major organic
component belongs to.

3.2.6.1. Annual cycles oflevoglucosan-C and DC

The Figures from 3.57 to 3.62 represent the comparison ofannual cycles between
levoglucosan-C and organic carbon (monthly average) for each sampling site. The annual
cycle variation of organic carbon (OC) is very similar to the levoglucosan-C for most of
the sampling sites. Only some differences are observed in SIL, where in May and June
2003 low concentration values of levoglucosan-C were obtained and for OC a maximum

• was found. At SBO in December 2002 and May 2004 two maximum monthly average
concentrations for levoglucosan were observed that do not correspond with the
corresponding values of OC in these months.
As already listed in Table 2.2 the filters collected within CARBOSOL are analyzed for
organic carbon (OC) as well, this analysis was performed at the University of Aveiro.

Page 91
 Results: Hif!h- Volume

AZORES

20 1000

lB 900
Ea3levoglucosan-C
---OC
16 BOO

~ 14 700
"E
C.
c 12 .. "-.---.- 600
oè "E
:x 10 500
C.
o S
u u
~ 0
Öl B -. - 400
o
>
GI
...J 6 __
300

•
4 200

2 100

o 0

~~~~~,,~,.~,,~~,~~,,~,~,
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ -~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~

Fig. 3.57: Relation at Azores between levoglucosan-C and OC

AVEIRO

600 14000
G:E levoglucosan-C
---oc 12000
500

1‫סס‬oo
"E 400
C.
C
oè BOOO JO"
E

•
C.
:x 300 S
o
u U
~ 6000 0
Öl
o
>
3 200
4000

100
2000

o .. 0

~~,~~"~,~,,~~,~~~,~,.~,,
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~

Fig. 3.58: Relation at Aveiro between levoglucosan-C and OC

Page 92
 Results: Hüdl- Volume

K-PUSZTA

250 18000

E!!I Levoglucosan-G
16000
-+-oc
200
14000

"e 12000
Cl
c 150
tj 10000 "e
.....
c
III

o
Cl
.:.
u
8000
:)

8' 100 1- 0

>

/
G> 6000
...J

•
4000
50

2000

a a
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~
~~'&~~F~'~"~~'&#~F~#~'
Fig. 3.59: Relation at K-Puzta between levoglucosan-C and OC

SCHAUINSLAND

50 -. -
. .. - 5000

45
I - Cellulose-C I 4500
I ----oe
40 '" -'\
I
r ---\ 4000

35 -- • / / ..... -- \
!\j
3500
"e
a.
.:. 30 --_ . I 3000 ~
~c
I 1\ j Ë

•
25 --- --- .--- .-
8
u
..

.-1 v 2500 ~
u
"
g,
0
20 - -_._-- ....- 2000 0
>
co
-'
-
/ -
15 - ----- - - .. - 1500
t1
10
\
- -
1\
- -
[7
_. - - 1000
/
5 - - - 500

o -r -r -r -r -r T -r -r 0

~~-~~~,.~.,~~~,~~.~~~,~,~~
~~~~~~~~~~~~~~~~~~~.~~~~~

Fig. 3.60: Relation at Schauinsland between levoglucosan-C and OC

Page 93
 Results: HiJ!h- Volume

PUY DE DOME

120 4500

l!ZEI Levoglucosan-C
4000
-+-oc
100 .-
3500

Ë 80 3000
Cl
c:
U
c
::: 60
o
U
::I

8'>
~ 40- 1500

1000
20
500

~ ".
a ' a

&~"~#~"~~~'&~"~'~"~~'
~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~

Fig, 3.61: Relation at Puy de Dome between levoglucosan-C and OC

SONNBLICK

40 4500

4000
35

..
3500
30

E 3000
Cl 25
c:
'fi
c:
::: 20
o
U
::I

8'> 15
CI> 1500
..J

la
1000

5 500

a a

&~"~,~,,~~,&~,,~,~,,~,,
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~

Fig. 3.62: Relation at Sonnblick between levoglucosan-C and OC

Page 94
 Results: HiJ;!h-Volume

3.2.6.2. Contribution oflevoglucosan-C to OC

The average contribution (overall average across the whole sampling period) of
levoglucosan-C to OC for all the sampling sites varies between 1,2 and 2,3 %. The
highest contribution is observed at Ala, the maritime background site although the
lowest concentration values of levoglucosan were found at AlO. This contribution is 2,3
% and ranged between 0,1 and 16,5 % based on weekly averages. Therefore it is obvious

that OC levels at AlO are very low as well. Thus, here the air is very clean and there is
no influence of other sources of pollutes like road traffic, industry emissions, etc. It is
different for AVE; in this sampling site the highest concentration of levoglucosan were
found. The concentration values of levoglucosan were much higher in comparison with
the other sampling sites. Nevertheless the contribution of levoglucosan-C to OC in AVE
is not very high and very similar to the other sampling sites, especially in winter, where
the concentrations oflevoglucosan are very high. The contribution oflevoglucosan-C to
OC is 2,0 %, ranging between 0,04 and 6,8 %. Here, it can be assumed that AVE has a
strong influence on other sources of pollutes like road traffic, industry emissions, etc. At
KPl, the second site with elevated levels for levoglucosan contribution is high (2,1 %,
range between 0,01 and 16,4%) similar to AlD. It is a continental rural sampling site and
it is probable that the influences of other pollutes are lower in comparison of AVE, as it is
not a place close to the city or road traffic.
At the mountain sites, a very similar contribution of levoglucosan-C to ac was observed,

• especially in POO and SIL, where the averages were 1,8 % (ranging between 0,2 and
6,7%) in case ofPOO and 1,5 % (ranging between 0,1 and 5,1 %) in case ofSIL. At
SBO, the average contribution is similar to POO and SIL, 1,2%, but it shows much more
variation (with a range of 0,0 and 10,5 %). Thus the average contribution at the
continental background site SBO is only half as much as at the maritime background site
AlO.
The Table 3.24 summarizes the average contribution of levoglucosan to OC of the whole
sampling period for all the sampling sites. The Figures from 3.63 to 3.68 represent the
monthly average ofthis contribution for all the sampling sites.

Page 95
 Resu/ts: Hif!h- Volume

AZORES

10,00

...~ 9,00

8 8,00 ~;
S ",
"
;1-- )i
~
!f
7,00

~ .f.,~
6,00
c
1;.;
~,
5,00 'i':
_'J
~~ :~~
J'
'~~ ..-i.
,
;."

II
4,00 'Il:"
'~
"f - !~ :'
6 3,00 & ~I-
~ 2,00

~ 1,00

0,00

~~,&~~,~~~,,~~#&~~,~,~,
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ,~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~

AVEIRO

10,00

2! 9,00

8 8.00
S

1J
7,00

8,00

5.00
"
4.00 ..---
II
6 3,00
h1
~ 2,00

~ 1,00

K-PUSZTA

10,0

~ 9.0

8 8,0
s
7,0

1I 6,0

5,0
~.. -
n
15 4,0

6 3,0

~ 2,0

~ 1,0

Fig. 3.63 - 65 Contribution of levoglucosan-C to oe [%] at Azores, Aveiro, and K-Puszta

Page 96
 Results: HiJ!h- Volume

SCHAUINSLAND

10.00

...
~ 9,00

8 8,00
.9
7.00

1J 8.00

S,DO

4,00
'0
6 3.00

~ 2,00

~ 1.00

PUYDE DOME

10.0

2! 9.0

8 8.0
.9
7.0

1 6.0

J 5.0

4.0
'15
6 3.0

~ 2.0

~ 1.0

0.0

~/~,~,~"~~,~/~,,,~,~~~,
~ ~ ~ ~ ~ ~ ~ -~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~-~ ~ ~ ~ ~

SONNBLICK

10.00

2! 9.00

8 8.00
S
7.00

1I 8.00

5.00
------
---{ '.
4.00 ')
'15 "t-
,f,
é 3,00 '.J
t
"
~ 2.00

S 1.00

0.00

~/~",~,~~~,~/~,,~~.,~~~,
~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~

Fig. 3.66 - 68 Contribution oflevoglucosan-C to oe [%] at Schauinsland, Puy de Dôme and

Sonnblick

Page 97
 Results: Hizh- Volume

Table 3.25 Average, minimum and maximum values ofthe six sampling sites

Levoglucosan-C/OC Azores Aveiro Puyde Dome Schauinsland Sonnblick K-Pusta

[%]
Average 2,3 2,0 1,8 1,5 1,2 2,1
Min 0,1 0,04 0,2 0,1 0,04 0,01
Max 16 6,8 6,7 5 11 16

The Table 3.26 shows the average of summer and winter periods as well as the ratio

between these periods. For all the sampling sites the contribution in winter is higher than
in summer. The maximum winter/ summer ratio was calculated for AVE, where the

contribution in winter is 5 times higher than in summer, due to the elevated concentration

values of levoglucosan, as mentioned earlier (ratio between winter and summer

concentration values of levoglucosan is 13).

Table 3.26 Average of summer and winter period and ratio between summer and winter period

Levoglucosan-C/OC Azores Aveiro Puyde Dome Schauinsland Sonnblick K-Puzta

[%]
Summer 1,6 0,6 1,8 0,7 0,7 1,5
Winter 3,0 3,2 2,3 2,4 2,3 2,3
Winter/Summer 2 5 1 4 3 2

3.2.6.3 Contribution oJwood smoke to Organic matter

Concentrations of levoglucosan in fine particle (PM2.5) emissions from fireplace

combustion of wood in the northeastern and southern United States were reported by Fine

et al. (200 I a, 200 I b). The results of these papers are summarized in Table 3.27. If we

assume that the composition ofthe emission ofwood burning emissions in our sampling

sites are roughly similar to that from the fireplaces in the northeastern and southern
United States, we can derive a first, rough estimate for the contribution of wood

combustion to the Oe. Table 3.28 shows the results ofthis estimation for our sampling

sites in Europe.

Page 98
 ResulLç: Hif!h- Volume

Table 3.27: Resume ofresults in Fine et al. 2001 works

LevoglucosanlOe
Levoglucosan in wood burning
Sampling sile [mg/g OC) emissions Dale Reference
%e

Northeaslern Hardwoods 128,767 11-17

United Slales (108,509 - 168,254) Fine el al. 2001 a
Softwoods 76,40 5,2 - 9,5
(52,330 - 81.445)

Soulhern Hardwoods 136,28 9,9 - 15,9

Uniled Slales (98,9 - 159,18) Fine el al. 2001 b
Softwoods 42,6 3,6 - 4,7
(36,373 - 46,942)

The approximation value calculated from this works was 7,35. To calculate the
concentration value ofwood smoke, the concentration oflevoglucosan is multiplied by
7,35:
Wood smoke = Levoglucosan * 7,35

Table 3.28: Concentrations ofwood smoke (aC) for aHthe sampling sites [nglm)]
AZO AVE PID S1L SB) KPZ
A~ ~ A~ ~ A~ R3rga AVf?féY;13R3rga A~ ~ A~ Rarg:l
Entireperiod 104 8-585 2(0) 13-10064 352 21-2300 389 00-1041 142 12-1219 1756 15-5024
&.mrer period 00 12-491 294 13-700 845 188-2300 405 100-1041 149 12-750 1078 201-2515
'Mnterperiod 125 11-585 3800 691-10064 151 21-458 328 7~7oo 139 13-1219 200) 1234-4347

The site with the lowest wood smoke (aC) concentrations is AZO (104 ng/m), with a
range of 8 to 585 nglm3), that is followed for SBO (142 nglm3, with a range of 12-1219
nglm3). PDD and SIL present very similar average concentration ofwood smoke, 352
nglm3, ranging between 21 and 2360 nglm3 and 389 nglm3, ranging between 50 and 1041
nglm3, respectively. As expected, at KPZ and AVE, where the highest concentrations of
levoglucosan were observed, then the average concentrations of wood smoke were also
very high. At KPZ the average is 1756 nglm3, ranging between 15 and 5024 nglm3, and
for AVE it is 2006 nglm3, ranging between 13 and 10864 nglm3•
Ifwe want to calculate the contribution ofwood smoke to OM it is necessary to use some
conversion factors. The conversion from organic carbon mass to total organic compound

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mass or organic matter is using a factor that accounts for the hydrogen, oxygen, and
sometimes nitrogen and sulphur content ofthe organic compounds present (Fine et al.
2001). Fine calculated a scale factor typically ranging between 1,2 and 1,4 for typical
atmospheric samples or higher depending primarily on the oxygen content of the
compound. We use a scale factor of 1,7 (Puxbaum et al. 2004), as it was assumed that
these compounds involve more oxygenation ofthe compounds after long-range transport.
We show here the scheme ofthe contribution value ofwood smoke to OM calculation:

Wood smoke {OM)/OM (%) = [(Ievoglucosan * 7,35 * 1,7) / (Oe * 1,7)] * 100

Tables 3.29 and 3.30 present the average contribution ofwood smoke to OM, maximum
and minimum values, as well as the average of summer and winter periods and the ratio
between winter-summer periods.
The average contribution ofwood smoke to OM for all the sites ranges between 21 and
39 %. As was expected, the major contributions were observed at AZO, for the same
reason which was explained before. AZO is followed by KPZ (35 %) and AVE (34 %),
both low level sites with higher concentrations of levoglucosan. For the high levels sites,
the contribution is minor. For PDD it is 30 %, SIL is 24 %, and for SBO 21%.
In winter the contribution ofwood smoke to OM is generally higher than in summer.
Normally in this season the temperatures are very low, there is not much air mass
exchange in the atmosphere and the transport of this air mass is very slow furthermore
higher emissions can be expected during the cold season. These winter contributions
range between 39% and 52%.
We can summarize that the contribution ofwood smoke to OM is between 10 and 52%
for all these sampling sites in Europe.

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Table 3.29 Average of contribution ofwood smoke to OM (%), and maximum and minimum
values for all the sampling sites

Wood smoke/OM Azores Aveiro Puyde Dome Schauinsland Sonnblick K-Pusta

[%]
Average 39 34 29 24 21 35
Min 2,4 0,7 2,6 2,0 1 0,2
Max 273 113 112 84 174 272

Table 3.30 Average and ratio for winter and summer period

Wood smoke/OM Azores Aveiro Puy de Dome Schauinsland Sonnblick K-Puzta

[%]
Summer 27 10 30 11 11 25
Winter 50 52 39 40 41 39
Winter/Summer 2 5 1 4 4 2

3.2.7. Comparison of levoglucosan and K+

Potassium has been already widely used as tracer element for the qualitative
identification of biomass burning (Cachier et al. 1991) as well as for wood combustion.
However the emission of this tracer element is highly variable and must be determined
empirically for each situation (Sheffield et al. 1994). Thus Organic compounds are of
particular interest to be used as tracers of Biomass burning. The problem in using organic
compounds as tracers is that they can form and degrade in the atmosphere by chemical
reactions. As mentioned before, some studies show that levoglucosan is a good tracer for
wood combustion, specific for biomass burning and with a high stability in the
atmosphere during a relative large period.

Potassium can also be related to aerosols originating from the Earth's crust. Iron
concentrations were used to estimate contributions ofthe Earth's crust to observed K+
concentrations (Lewis et al. 1988). Lewis and collaborators reasoned that soil should be
the only one significant source of K+ in coarse particles and that, therefore, the KfFe ratio
in coarse particles would be equivalent to that in those fine particles originating from soil.

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They developed the following equation to calculate concentrations of non-crustal

potassium (K') in fine particles:
[K'] = [K] - 0,45[Fe]
We cannot calculate this potassium concentration (K'), as in the project "Carbosol"
concentration values of Fe were not determined. Potassium (and other ions) was analysed
by the Laboratory Environment Glaciology and Géophysique (Grenoble). Figures 3.69
and 3.70 presents the annual cycles, based on monthly average oflevoglucosan and K+
for AVE and KPZ respectively. We choose the two sampling sites with higher
concentrations of levoglucosan and thus high contribution of wood burning for this
companson.

AVEIRO

1200

1000 -----\:
OK
o Levoglucosan
800

1; 600
....
'"
.:.

400 --.

. ~'.
200

..
. ~
o

~~,~~,,~~.~,,~~,&~,,~,~
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~

Fig. 3.69. Monthly average of annual cycles oflevoglucosan and K+ for Aveiro.

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K-PU5ZTA

700

600 - - --
0K

500
J
0 Levoglucosan
, .
I
',. - .
400
, ,
oE ... ~
a. ,
.:. 300 ,---- , -- , --. - -j: --,
", .,..,
e ..
, f-'.
',1
,- ,.. ,. ,
200 - - ---, .. , \
'"
,:.:
.. "
- 1- .- " ., '-- '"

"
.'i
,.: , , j

-
i "
..
." .r"
"

0
'0
,.~
" ~: ;
..
'0

:
"

.' ..
. ...
'0
!
100 ,-,
-- - ,. -
.. r:
:.,; , ..
"
, ~~ ;
.'~! ,,
"
, ..
'. .
"
;I.
:,;
.L
,
1 l . -...
"

, .., : "
"

0
,
:
i ~ "
: : ;
I;' 0
fr.
I ;
~! "
L:
,. I
:.-
.'i

Fig. 3.70. Monthly average of annual cycles of levoglucosan and K+for K-Puszta.

Winter months for AVE showed higher concentration values oflevoglucosan than K+.
For summer months it was the opposite, the concentration values of K+ were higher than
levoglucosan. While for AVE, levoglucosan presented a very pronounced annual cycle
(high concentrations values in winter and lower in summer), the cycle for K+ was much
less pronounced. The differences between the winter and summer concentrations were
very small. However, for KPZ we observed very similar annual cycles for levoglucosan
and K+. Only in summer and autumn two potassium concentrations were much higher
than levoglucosan values.
Figures 3.71 and 3.72 show the ratio oflevoglucosan and K+ with oe for AVE and KPZ.
For AVE, during the winter the levoglucosan contributions predominate over the K+.
During the summer is the contrary; the contributions of K+ to oe are higher than
levoglucosan. In KPZ the contribution ofK+ and levoglucosan to oe are very similar. A
clear example is seems in March 2004 where the contribution was very high for both
compounds.

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AVEIRO

0.12

OK/oe

D,ID " OLevo/oe -

..
0,
- "
..
i, :
0,08 - "
- - ,0 0, ..
.. ':
; ,
02 " i

10 0006 - - ,- -- '0 - -
CIl: .. ;
..
"
.~. .,. 0' 0

" -,
j "

:
0,04 - - f- i - - - "
- - .. - : f- ,-
- - - f-- - " - ---

, .. 00

\, .,
00 " .'
"
0' 0'
{ r
" "
,
"

:
"
. ; ..
,', "
~
" ' ..
"
"0

.-
"
- ..

0.02 - - i
, i " r- , - ':f-- "
,
I:
..

.. , .. :":
"
~. , ; .- :'. 'J ;
,, .. " .-

n
.. " '0
~~ "

1
" "
"

- \J ; :.'
:l~ ~
..•.

0,00
..
~
,
"
"
./ " . 0<
,'4-
, .~ M .:
'1 ..
"
,0 "
"
:
"

~~,~~~,~~~,#~~~&~~#~~~,#
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~

Fig. 3.71. Monthly average ofK+/OC and LevoglucosaniOC ratio for Aveiro.

K-PUSZTA

0,16

0 14
0

OK/oe
I~

DLevoloe
0 12
0

D,ID ,-----,,--------, --

o :
"
~ 0,08 - -- ." . ----

0,06 -- -,- .----

,
"

,"
. r ---
"

- .. e
0,

,
, .. -
"; " 0,

0,04
t: .-
- .. J - ,if-- - -
:
'0
'-' :; .!.
.. ~: , I I
,
,0
" >.:

- '.; " "

0,02 " - f----- .. - "

,: , -I '!. , "
T

.. t>
"
, .;
.. . ;~
. ,i ..
" : ~l
, "

M ;;
~~ .. ,
,
" :..i

Ù 'Pl.,'
d

..
0'

~: .';
~ "- .. "j
~: ,;: ;l

"
~'

0 00
0

Fig. 3.72. Monthly average ofK+/OC and LevoglucosaniOC ratio for K-Puszta.

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We performed regressions analysis to evaluate a possible quantitative relationship

between K+ and levoglucosan ofboth sampling sites. For AVE, regression analysis gave
a correlation coefficient ofR2 = 0,4012 and for KPZ R2 = 0,4498. This is somewhat
surprising, especially since KPZ shows much better agreement between K+ and
levoglucosan annual cycles than AVE. Another regression analysis was performed
between levoglucosan and K+ with oe (Table 3.31). For AVE the regression between
levoglucosan and oe was R2 = 0,8186, a little better than for K+ and oe (R2 = 0,7047).
At KPZ, although the annual cycle between levoglucosan and K+ is very similar and also
the annual cycle ofthe ratios levoglucosan/Oe and K+/Oe, the regression analysis was
very different; for levoglucosan/Oe was obtained a very poor value R2= 0,2465 and for
K+/Oe was observed a very good regression R2 = 0,8368. Disregarding the average
months values from July to October 2002 correlation analysis yields R2 = 0,4143 and
0,8876 for levoglucosan/Oe and K+/Oe, respectively. Although the annual cycles in
monthly average for levoglucosan and K+ seem very similar, ifwe compare the annual
cycles oflevoglucosan and K+ with oe for KPZ (weekly samples), it can observe some
differences. The trend of weekly samples for K+ and oe is very agreed, but for
levoglucosan and oe is not so good.

Table 3.31: Regression analysis between levoglucosan, K+and oe for Aveiro and K-Puszta
R2 Levoglucosan/K+ Levoglucosan/Oe K+/Oe
AVEIRO 0,4012 0,8186 0,7047
K-PUSZTA 0,4498 0,2465 0,8368

Recent work from Brasil shows some regressions analysis between levoglucosan and K+.
The sampling was carried out during the day- and nighttime in Rôdonia, Brasil, during
the deforestation fires season (Schoklnik et al. 2005). During daytime, levoglucosan/K+
ratios were smaller than during the night. It was suggested that during daytime, when the
deforestation fires were set, flaming combustion prevails, while at nighttime, when the
fire has subside, smoldering processes were more dominant. Flaming combustion is a
very exothermic gas-phase combustion, during which organic compounds are oxidized to
a greater extent, thus leaving proportionally less levoglucosan. Another recent work from

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Kawamoto et al. 2003 has reported that in 400 DC (as opposed to 250-300 °C)
levoglucosan re-polymerizes into polysaccharides, which then furt~er react to form
organic solids containing conjugated double bonds and carbonyl groups, such as can be
found in HULlS. Smoldering combustion, on the other hand, is a slow solid-phase
oxidation process, which gives rise to more unbroken organic compounds, and possibly
to less levoglucosan re-polymerization, increasing the levoglucosan concentration in
comparison to inorganic species such as K+.
This could be the answer why there is not so much correlation between levoglucosan and
K+as expected.

3.2.8. Comparison of cellulose and Organic Carbon (OC)

3.2.8.1. Annual cycles of cellulose-C and OC

The annual cycles of the monthly average concentrations of cellulose-C and OC have a
very similar trend for the AVE, PDD and SBO the corresponding trend of cellulose-C
and OC was in agreement. Only at SBO the monthly average concentrations during the
winter months in 2004 presented very high values for cellulose-C and not for OC At
AZO no trends for both components were observed. At KPZ, it showed some differences
during winter, where the concentrations of OC present a maximum but not the
concentration of cellulose-C At SIL, it is possible to note two different trends, e.g. for
OC the maximum monthly average concentration was observed during the summer
months and for cellulose-C during the spring months. The figures from 3.73 to 3.78
represent these annual trends for the six sampling sites.

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 Resll/ts: Hif!h- Va/lime

AZORES

16 1000

16 900
~
~
!l 800
14 -~

I ~
700

..
12
Ë ~
a. 600
oS 10 ~
A. E
~ a.
CIl
In .,
)1 500 oS
0 6 f.--~' 0
2 \t
. r;" 400
0
Gi
0
6
300

4
200

2 ~ 100
,.
~t

o :" o
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~~'~~'~F~~~"~~~~~~F"~' ~.~ ~.~

Fig. 3.73: Annual cycle of cellulose-C and OC at Azores

AVEIRO

60 --_ ..
14000
Ga Cellulose-G
--OC
12000
50

..
E
m
40
10000

..
.:. 8000 E
~ 30 m
CI>
In
.:.
0
6000 u
0
:ä

-I
Qi
u 20 il
4000

10
~1 ,,-~-.
re .li
~
- ..I
Î. ~i
i
~
~
4-'-
ij
~
~
,~ 2000

I il
I ~ ~
«
i' '
~ ~ '" U
0
~ "'" ~ •.
:' 11l
0

Fig. 3.74: Annual cycle ofcellulose-C and OC at Aveiro

Page /07
 Resu/ts: Hi$!h- Va/ume

KPUSZTA

160 18000
GD Cellulose-G

, j
140 16000
---OC

~ 14000

..
'ill
E
120

100
.,
,;~--j"
g~. ~?;
~-
r..~

~-
t':
12000
..
.:. 10000 E
~ 80 - .. _~--~: ..
=<
~) 'ill
.:.
'"
0
CI> ,~
.~
\lj
. l'
~-
;1 8000 0
2 " 0
Qi 60 ~- t
0 l' 6000
~ "
.~

40
~ ~ 4000
.,
~ .~ r.
20
~ ~ ~ I'
~ ~
t /!
&
~ ~
~ !$ 'j;~
;;
" 2000

0 '" 0

Fig. 3.75: Annual cycle of cellulose-C and OC at K-Puszta

SCHAUINSLAND

120 5000
E::3 Cellulose-C
4500
---OC
100
4000

3500
ft
80
E
'ill 3000 ~
.:. ft

E
~ 60 .. ----- -_. __. 2500 'ill
.:.
'"o 0
2 2000 0
Qi
o 40
1500
~
Jj ,j

~ ~)~ 1000
20
.f
~-i ~
.. ~ ~ <;
500
t'
o
iJ.
~ If ~
1 ~
0

Fig. 3.76: Annual cycle ofcellulose-C and OC at Schauinsland

Page J08
 Results: Hif!h- Volume

PUYDE DOME

90 4500

80 4000
EEl Cellulose-C

70 --oe 3500

60 3000
Ë
m
.:. 50 2500 Ë
tl m
..
QI

0 40 l.;. ~ 2000
.:.
g
2 g
J ~
,S
ë;
u 30 ~- ~ ~ 1500
~
~ ~
,
"
l i
~
20 .~ i.. 1000
:.l
f. ~ ~
~_t
10
~ ..
,.
,..
500

II
.. ,
0 o

Fig. 3.77: Annual cycle ofcellulose-C and OC at Puyde Dôme

SONNBUCK

40 4500
I E9 Cellulose-C I
4000
35 I --oe
.. -
3500
30

3000
25
2500 E ft

20 . f--- .--.--- ~-- ---- m

.:.
2000 g
15

\ 1500
10 -I \-

'\~ 1000

5 -~
500

o o

Fig. 3.78: Annual cycle of cellulose-C and OC at Sonnblick

Page J09
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3.2.8.2. Contribution of cellulose-C to oc

The highest contribution of cellulose-C to OC is observed at the sampling site SBO (2,7
%, with a range of 0,3-18 %). The results at PDD were very similar to SBO (2,3 %, with
a range of 0,3-17 %), that is followed by SIL (2,0 %, with a range of 0,3-16,8 %). Thus
all the continental mountain sites show similar results, independent from the elevation of
the site. At AZO the results are in the middle, no so high as the mountain sampling site
but higher than the low level sites (1,7 %, with a range ofO,4-6,7 %). The lowest
concentration values were obtained in KPZ and AVE, where the contribution of

• cellulose-C to OC is 1,2 %, with a range of 0, 1-4,5 %, and 0,5 %, with a range of 0, 1-1,8
%, respectively. The low contribution in these sampling sites, especially at AVE. Table
3.32 summarizes the results of the contribution of cellulose-C to OC, average
concentration values, as well as maximum and minimum values. The figures from 3.79 to
3.84 represent these contributions for the six sampling sites.

Page I/O
 Resu/ts: HÜ!lI- Va/ume

AZORES

5.0

~
... 4.5

4.0
B
.9 3.5 -~
~
3.0
~ ~
'5
2.5
~ ~
'15 2.0
6
1.5
~
1.0

~ 0.5

0.0

~~,~~~",~."~~,~~~,,,~,
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~

AVEIRO

5.0

4.5
2!
Bg 4.0

3.5 ----_ ..

3.0 -.-- ..
~
'5
2.5
~
'tl 2.0
6 1.5 ... ----.
~
1.0

~ 0.5

• ...~
B
5.0

4.5

4.0
K-PU5ZTA

S 3.5

~ 3.0
'5
2.5
~
'15 2.0
~
6 1.5
~
1.0

~ 0.5

Fig. 3.79 - 81. Contribution ofCellulose-C to OC [%] for Azores, Aveiro,and K-Puszta

Page III
 Results: HiJ!h- Volume

SCHAUINSLAND

12

10

PUYDE DOME

12

10

4 ------

SONNBLICK

• 12

10

8
~---

"

4
,i ~ ~
:z ~
2 I
.. J ~.'

~. ~
;,

of
V!i'(
~
~-
~'i~
~ii!-<!
i!'l tj. t
~#~,,~~,,~~,~#~,,~.~,,~~,
~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .~ ~ ~ ~ ~

Fig. 3.82 - 84. Contribution ofCellulose-C to OC [%] for Schauinsland, Puy de Dôme and
Sonnblick

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Table 3.32: Average, minimum and maximum values ofthe six sampling sites
Cellulose-CIOC Azores Aveiro Puyde Dome Schauinsland Sonnblick K-Pusta
[%]
Average 1,7 0,5 2,3 2,0 2,7 1,2
Min 0,4 0,1 0,3 0,1 0,3 0,1
Max 6,7 1,8 17 13 18 4,5

Table 3.33 shows the average contribution of cellulose-C to OC for summer and winter
periods as well as the ratio between winter and summer for all the sampling sites. One
might comment about the results ofTable 3.33 that the major contribution of cellulose-C
to OC was obtained during the winter. At KPZ during the summer period, the
contribution was higher than the winter period; therefore, the winter/summer ratio is 0,4.
Ifthe ratio summer/ winter is calculated, the result is 2 and that means the contribution of
cellulose during the summer period is double with respect to the winter period. Another
important observation ofthis Table is the elevated winter/summer ratio for POD and
SBO, 3 and 4, respectively. It is observed that during the winter months, especially in the
second year 2004 that the contribution of cellulose-C to oe is very high if it is compared
with the winter 2003 for example. This coincident higher percentage of cellulose at both
these mountain sites could be the result oflong-range transport. Up to now trajectory
analysis did not give evidence for any special events.

Table 3.33: Average summer and winter period and winter/summer ratio
Cellulose-C/OC Azores Aveiro Puyde Dome Schauinsland Sonnblick K-Puzta
[%]
Summer 1,3 0,5 1,4 1,4 1,4 1,6
Winter 1,5 0,4 4,1 2,1 5,5 0,6
WinterlSummer 1 0,7 3 1 4 0,4

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 Resl/lts: Hü!h- Voll/me

3.2.8.3. Contribution ofPlant Debris to Organic matter (OM)

In leaves of terrestrial plants, the content of cellulose is around 50%, while lignin
amounts to <20% and hemicellulose 20-30% (Butler and Baily, 1973). As we assume that
the major fraction of cellulose in continental aerosol originates from decomposition
processes of leaves, the portion of plant debris in aerosol is proposed to be estimated
according to the mass fraction of cellulose in leaves by the following relation:
"Plant debris" = 2 • cellulose.

Plant debris appears to be an important contributor to oe in atmospheric aerosols

(Puxbaum and Kunit, 2003). Table 3.34 shows the average concentration values for
whole sampling period as well as for summer and winter period for plant debris in all six
sampling sites.

Table 3.34: Concentrations of plant debris for all the sampling sites [ng/m3]
AZO AVE POD SIL SBO KPZ
Average Range Average Range Average Range Average Range Average Range Averaqe Range
Entire period 24,S <10,5-100 103 12,6425 121 13-425 178 13-739 65,6 <10,2-311 266 45-872
Sumner period 27,2 11,5-100 67,8 12,6-154 196,0 13-452 227 1~ 87,S 13-248 336 14s.603
Winter period 20,1 <10,5-52 124 15-425 57,2 15,4-159 n,4 13-208 41,5 12,5-104 190 45-485

At AZO and SBO the lowest annual average concentration values ofplant debris were
observed. At AZO the value is 24,5 ng/m3, ranging between< 10,5 and 100 ng/m3, and at
SBO 65,6 ng/m3, ranging between< 10,2 and 311 ng/m3• AVE is the next sampling sites,
regarding increasing concentrations ofplant debris (103 ng/m3, ranging between 12,6 and
425 ng/m3). The value ofPDD is 121 ng/m3, ranging between 13 and 425 ng/m3• The
highest average concentrations were obtained at SIL and KPZ, although the average
concentration value of KPZ is almost the double of SIL. The average concentration value
of SIL is 178 ng/m3, ranging between 13 and 739 and for KPZ is 266, ranging between 45
and 872 ng/m3•

To convert the mass of organic carbon to an estimate of organic compound mass, it must
be multiplied by a scale factor (generally 1,2-1,4 for atmospheric samples) to account for
the oxygen, hydrogen, and other elemental content of the organic present (Fine et al

Page //4
 Resu/ts: Hif!h- Va/ume

2001 a, 200 1b). In the present study, a scale of factor1, 7 is used (Puxbaum, et al. 2004),
owing to the substantial number of oxygenated species. But for plant debris the
conversion factorwould be around 2,2, derived from stoichiometric considerations
(Puxbaum et al. 2004). Thus, to calculate the concentration ofplant debris to OM is the
concentration value of cellulose is multiplied by 2 and that is plant debris in Oe. If
multiply again by 2,2 is obtained the concentration ofplant debris expressed as OM. The
contribution ofplant debris on to OM, is obtained by dividing concentration ofplant
debris OM by OM (OC * 1,7, as mentionedbefore). The scheme ofthis calculation is as
follows:

• Plant debris (OM)/OM (%) = (Cellulose * 2 * 2,2/ oe * 1,7) * 100

Table 3.35 shows the contribution ofplant debris to organic matter (OM) for all the
sampling sites.
The contribution ofplant debris to OM at the background sampling site SBO), as it is
expected, is the major contribution of all sampling sites. The monthly average result of
SBO is 16 %, ranging from 1,7 to 106%. The following major contribution is observed at
PDD, 14 %, ranging from 1,5 to 98%. At SIL the contribution ofplant debris to OM is
12% (ranging from 0,8 to 75 %). At AZO is 11 %, ranging from 2,2 to 39 %, and for
KPZ the highest concentration values of cellulose are found, but the contribution of plant
debris to OM is not major (6,7 %, ranging from 0,6 to 26 %). Minor contributions are
observed at AVE (3,0 %, ranging from 0,4 to 10 %); it is a low level sampling site, and it
becomes influenced by other emission sources.
The season comparison of summer- winter shows that there are not many differences
between summer and winter at AZO, AVE, and SIL (Table 3.36). However at SBO and
POD, major contribution values are observed in winter rather than summer period, and
the ratio between winter-summer is 4 and 3 respectively. That is the time coincident of
high concentration values of cellulose during winter, especially in winter 2004, has also a
meaning to the contribution of plant debris to OM. At KPZ is the opposite, the
contribution is higher in summer than winter, therefore, a ratio is calculated between
summer-winter for KPZ, and this ratio is 3.

Page 115
 Results: Hif!h- Volume

Table 3.35: Contribution ofPlant Debris to OM for all the sampling sites

Plant debris/OM Azores Aveiro Puyde Dome Schauinsland Sonnblick K-Pusta

[%]
Average 11 3,0 13,6 12 16 6,7
Min 2,2 0,4 1,5 0,8 1,7 0,6
Max 39 10 98 75 106 26

Table 3.36: Average summer and winter period and ratio winter/summer

Plant debris/OM Azores Aveiro Puyde Dome Schauinsland Sonnblick K-Puzta

[%]
Summer 8,1 3,1 8,3 8,1 8,2 9,6
Winter 8,5 2,1 24 12 32 3,4
Winter/Summer 1 0,7 3 1,5 4 0,4

Page 116
 Results: Hif!h-Volume

3.2.9. Mass balance of OM using levoglucosan and cellutose as macrotracers

The following diagram is a mass balance of OM using levoglucosan and cellulose as

macrotracers. Levoglucosan is a macrotracer of "wood smoke" and cellulose for "plant
debris", as we mentioned in other chapters before. This diagram gives a general overview
ofthe importance ofthese macrotracers as organic species in atmospheric aerosols. The
contributions ofboth sources to OM range between 37 and 50 %, with higher percentages
for wood smoke (21 - 39 %) than for plant debris (3 - 16 %).
Thus the spatial differences ofthe contributions ofthe macrotracers to OM are less

•
pronounced than the absolute concentrations oflevoglucosan and cellulose .

100%

90%

80%

70%

60%

50%

40% 3
~~ ...
-

30%

20%

• 10%

0%
Azores Aveiro Puy de Dame Schaulnsland SonnblIck K-Pusta

ElWood smoke o Plant Debris OOthers

Page 117
 Results: HiJ!h-Volume

3.3. Size classified measurements of levoglucosan and cellulose

To check the size distribution of cellulose and levoglucosan six impactor runs with a
Sierra Series 230 High-Volume Cascade Impactor (first three samples with a PM 10 inlet;
last three samples with a TSP inlet) were carried out. These impactor measurements were
performed at the sampling site AVE, during the sampling period 2002-2003. The duration
ofthe runs was 7 days each. Figures 3.85 to 3.96 show the histograms for levoglucosan
and cellulose. For comparison the size distribution with the size distribution of
levoglucosan and cellulose OC and K+ is given as well.
The samples AVE 24 and 35 were collected during periods of rain. This might have led
to condensation/deposition of liquid water onto the impaction surfaces causing a washing
ofthe water soluble material to the borders ofthe filters. For AVE 24 the homogeneity is
observed principally in the stages 3 and 4, and for AVE 53 in stages 1 and 2. For
example, in AVE 24 sample concentration values of cellulose were not determined, and
for levoglucosan very low concentration values were obtained.
Summarizing the size distribution ofthese compounds we propose as "fine particles"
sizes which have< 3J!m AD and as "coarse particles" size which have> 3J!m AD.
Table 3.37 represents the percentage offine particles « 3J!m AD) determined with this
cascade impactor for each compound in every sample.

Table 3.37 Percentage offine particles size determined with the impactor at Aveiro.
AVE 11 AVE 24 AVE 35 AVE 48 AVE 53 AVE 58
<3~m (%) [ng/m3] [ng/m3] [ng/m3] [ng/m3] [ng/m3] [ng/m3]
Levoglucosan 34 97 93 69 59 55
Cellulose 28 0,0 89 93 95 94
OC 79 86 92 79 70 82
K+ 81 98 88 70 88 82

It is observed for cellulose and levoglucosan that only in the first sample higher

concentrations were observed in the coarse particles. In the rest ofthe samples the fine
particles predominate, for cellulose with a high percentage and for levoglucosan,
especially in samples AVE 53 and 58, were approximately half ofthe mass was
determined in the fine fraction.

Page 118
 Results: Hif!h- Volume

For oe and K+ major percentages of fine particles sizes were determined.

Aveiro sample-11

300
- Levoglucosan
250 -:: - Cellulose
M
..ê
0)
200
a
ê: 150
e. l-
I
0) !
.:-:
.2 , :
'C 100
o
'C

50

o
D,Di D,iD 1,00 10,00 100,00

log (Op - J,lm)

Fig. 3.85. Histogram of cellulose and levoglucosan for AVB 11 sample

Aveiro sample 11

7000~ 250
-Organic Carbon
6000 -R:>tassium
200
E
-
h"
5000 E
Cl 0)
c: 1--- 150 oS
...... 4000
ê: ê:
o e.
Ci 3000 0)
o 100 .2
'C 'C
o'C 2000 o
'C
50
1000

o
D,Di 0,10 1,00 10,00 100,00

log (Op - J,lm)

Fig. 3.86. Histogram ofOC and K+ for AVB Il sample

Page //9
 Results: Hif!h- Vall/me

Aveiro sample 24

250
.. - Levoglucosan
.. -Cellulose
200
c;;-
-.a:
E
Cl
150 -------------.-.
.
i
i .. -.. --.
--,,-.--
I
--- .... -----

Q:
e. ,
-j----.-.
g» 100 -ï
'0
U
'0
50

o
0,01
-.0,10 1,00 10,00 100,00

log (Op -lJm)

Fig. 3.87. Histogram of cellulose and levoglucosan for AVE 24 sample

Aveiro sample 24

8000 500

7000, -:j
--I-Organic
-Fbtassium
Car'bon 450

400
h' 6000

-
h'
E 350 E
g»...... 5000 300
Cl
.s
g 4000 Q:
250 0
Ci Ci
o 3000 200 .2
'0 '0
U 150 U
'0 2000 . -- -.-.i . '0
! 100
1000

o
0,01 0,10 1,00 10,00 100,00

log (Op - J.lm)

Fig. 3.88. Histogram ofOC and K+ for AVE 24 sample

Page /20
 Results: Hifzh- Volume

Aveiro sample 35

250
-Levoglucosan .
.:. -cellulose
200
c;;-
-E
Cl
..:!: 150--.-
Ci:
e.
Cl
o 100
'0
U
'0
50

0.!1-
0,01 0,10 1,00 10,00 100,00

log (Op - ~m)

Fig. 3.89. Histogram of cellulose and levoglucosan for AVE 35 sample

Aveiro sample 35

4000 )"'"~-~-~--~-----~-------_-._~~-~-~.-.- 100

~.___I_ . I-OrganicCarbon 90
3500. :--------:-:-.--------- -----------------
-~lassium
80
3000

-
h" h"
E 70 E
Cl
~ 2500 60 oS
Ci: Ci:
e. 2000 50 0
Cl
, I 40
Ci
2 1500 0
'0
U
'0 1000
30 -
'0
0
'0
20
500
10

o -,............,. 0
0,01 0,10 1,00 10,00 100,00

log (Op - ~m)

Fig. 3.90. Histogram ofOC and K+ for AVE 35 sample

Page 12/
 Results: HiJ!h- Volume

Aveiro sample 48

160

140

M 120

--=
E
0) 100.

Ci
e. 80
0)
o 60
'0
(3 .. _ - . -
'0 40 _ _~ .._ ~ - --- --- .. -.

20

o ~ ?Q\F'

0,01 0,10 1,00 10,00 100,00

log (Op - JAm)

Fig. 3.91. Histogram of cellulose and levoglucosan for AVE 48 sample

Aveiro sample 48

7000 160

-Organic Carbon 140

6000
-Fbtassium
120 ~
'Ë
C»
c::
5000

..... 4000
100 -.s
E
0)

Ci Ci
C
Ci 3000 ..
80
e-
O)
o 60 0
'0
(3 2000
'0 40
-
'0
0
'0

1000 .. -, -+--- 20

o " - :,-. , 0
0,01 0,10 1,00 10,00 100,00

log (Op - JAm)

Fig. 3.92. Histogram ofOe and K+ for AVE 48 sample

Page 122
 Results: Hif!h- Volume

Aveiro sample 53

- Levoglucosan

M
E
-
Cl
100
-Cellulose

-e..a:
Q.

0)
80

60
~

.
c_~_~~~

--- .. ---------.-- ,
.

..------------.
'_" __ ',

0
i5
0 40
" 20

0
0,01 0,10 1,00 10,00 100,00

log (Op - ~m)

Fig. 3.93. Histogram of cellulose and levoglucosan for AVE 53 sample

Aveiro sample 53

2000 J
1BOO 160
1600
~ 140 ~

-
E
0)
c:
......
1400

1200
120

100 :::
.ê
0)
c:
Ii 1000 0-
e e
Ci " 80 Ci
BOO o
-""
.2
0 600

400
-.
-...".,.--'-----
- - .- - - - -
- ... - -------
. -. -.. . -
"-" .. .. -- -- -.. -- . - .....
60

40
o
"

"

200 20

0 ."""""'.
0
0,01 0,10 1,00 10,00 100,00

log (Op - ~m)

Fig. 3.94. Histogram ofOC and K+ for AVE 53 sample

Page /23
 Results: Hif!h- Volume

Aveiro sample 58

300 rr.' L~:IUCOS:__ __ __

-.ê
250 -Cellulose
__ J
M

0)
200
.3:
Ci:
C 150
Ci
o
'C 100
o
'C . - .-i--
50

o ,,- ."' ..
0,01 0,10 1,00 10,00 100,00

log (Op - !Jm)

Fig. 3.95. Histogram of cellulose and levoglucosan for AVE 58 sample

Aveiro sample 58

12000 ~ -~ 400
-Organic Carbon
- -AJlassium 350
10000
300

-
h" h"
E E
0)
8000 C,
c 250
...... oS
Ci: Ci:
C
Ci
6000 200
e-
O)
0

-
'C
0
'C
4000
.... - ... - .....
150 0

100
-
'C
0
'C

2000
50

0 ~~Il~- --~...~~~~ .. ....",. • 0

0,01 0,10 1,00 10,00 100,00

log (Op - !Jm)

Fig. 3.96. Histogram ofOC and K+ for AVE 58 sample

Page 124
 Results: Hie.h- Va/ume

The sample AVE 58 corresponds to a period with important forest fires in Portugal.
Actually we expected high concentration values of levoglucosan as tracer of wood
combustion, but in this period no especially high concentration values were observed.
This phenomenon was also observed for filter samples collected during the time period of
"Easter fires" in Austria (Bauer, personal communication). As mentioned before, some
recent works [Schkolnik et al. 2005 and Kawamoto et al. 2003] determined that
levoglucosan at 400 oe re-polymerizes into polysaccharides. That could be a reason why
no higher are obtained. However, for K+, another wood combustion tracer, the
concentration values determined during this period are twice as much as obtained in the
others samples. Here, the influence of forest fires in the atmospheric samples of AVE
could be observed.

Page /25
 Summary

4. Summary

Within the framework of project "Backgroundmeasurements Sonnblick" the trace gases

sulphur dioxide, nitric acid and ammonia as well as the aerosol compounds nitrate,
sulphate, ammonium, oxalate and calcium, magnesium, sodium, potassium and chloride
were collected during the sampling period from December 2002 to October 2004 at the
Sonnblick Observatory. Daily samples were collected with a low-volume In-Line
filterpack system.
The first part of the project included some intercomparisons with Open-Face Filterpacks,
which already have been used earlier for aerosol sampling at SBO. The comparison
between in-line and open-face sampling system show a very good agreement for sulphate
(R2 = 0,9055). Regarding the semivolatils compounds ammonium and nitrate more
pronounced variations were observed. Both, the heated inlet of the in-line system and
snow depostions on the front filter ofthe open-face system, caused some variations ofthe
concentration data. The decision to use an in-line system presents a compromise to obtain
representative values at an extreme sampling site, such as the Sonnblick Observatory at
3106 m a.s.1.. A comparison of the current measurements with the open-face data,
obtained during the period of 1991 - 1993 at Sonnblick, showed that the concentration
values agree quite well. Especially during the cold period, when the site is characteristic
for free tropospheric conditions, the background concentration values are very similar.

For the aerosol compounds as well as for ammonia and acid nitric pronounced annual
cycles, with high values in summer and low in winter were determined. The ratio
between summer and winter periods (arithmetic average) ranges between 5 and 11. For
sulphur dioxide the situation was different and no variation was observed comparing
summer and winter values. To get information about the air concentrations and
seasonalities of organic acids oxalate was determined. The concentration values for
oxalate are much lower (approx. one order of magnitude) than the major inorganic
aerosol compounds, but still they show a very pronounced annual cycle.
Aerosol compounds as well as trace gases are precursors for ionic constituents in wet
deposition. The seasonal cycles of aerosol compounds are in accordance to the

Page /26
 Summary

seasonalities of ion concentrations in wet precipitation samples, although the summer /

winter variation is more pronounced for aerosols than for precipitation. Thus higher
scavenging ratios were calculated for the cold period than for the sumemr months.
Especially in winter the neutralization ratios, calculated from sulphate and ammonium
equivalent concentration, are below 1. This points to the influence of free tropospheric air
masses during this time period. During summer months absolute concentration values as
well as neutralization ratio increase due to the predominant influence of boundary layer
air.
Comparing aerosol concentrations and concentrations of trace gases, the system sulfate
and sulphur dioxide showed high aerosol fractions during days with elevated
concentration values. In case of particulate nitrate and nitric acid no dependency of the
aerosol fraction on annual cycles of concentration trends could be observed.

Within the framework of "CARBOSOL" the orgamc compounds levoglucosan and

cellulose were collected during two years (2002-2004) in six different sampling sites over
Europe. High Volume aerosol samples were collected on a weekly basis.
The average concentrations of the whole period for these sampling sites in Europe range
between 14 and 273 nglm) for levoglucosan. The lowest value corresponds for AZO, as
expected for a background site. SBO is the next sampling site with low concentration
values, as correspond for a mountain background site. The other mountain sites, POD and
SIL, are the next sampling sites regarding increasing concentration of levoglucosan. The
highest values are determined at KPZ and AVE. Especially AVE present very high
concentration values during cold seasons, a site likely influenced from wood combustion
for heating during the winter months. The annual cycles of levoglucosan change quite
much depending on the sampling site. At the background sampling sites, AZO and SBO,
no seasonality is observed. At the low levels sites, KPZ and AVE, the annual cycles show
high values during winter and low values during summer, especially for AVE the
difference between -winter and summer is very pronounced (ratio of 13). At SIL a hardy
seasonal cycles is determined and at POD, the values during summer are higher than in
winter, as expected for a typical mountain sampling site, which will be less influenced by
boundary layer air masses during winter time.

Page 127
 Summary

For cellulose the average concentration values range between 13,5 and 133 ng/m3• The
lowest values correspond also for AZO, followed for SBO. AVE and POO are the next
sampling site regarding increasing of concentration of cellulose. The highest values are
for SIL and KPZ, as rural sites. Especially KPZ presents very high values, as a low level
rural site. Just as for levoglucosan no seasonality of cellulose concentrations could be
determined at the background sites AZO and SBO. POO and SIL show the expected
annual variations with high values during spring and sommer months and lower
concentration levels during the cold season. This is typical for a mountain site because it
might be above the mixing layer during winter time and will be influenced more
effectively by boundary layer air masses during summer. At AVE the highest values of
cellulose are determined during the winter, just like for levoglucosan but still with much
lower concentration values. At KPZ the concentration values during spring and autumn
are very high but the difference between winter and summer seasons is not very
pronounced.

The annual cycles of levoglucosan-C and cellulose-C with OC were compared. For the
most the sampling sites the annual trends agreed quite well. The contribution of
levoglucosan-C and cellulose-C to OC (%) were also calculated. The average values of
these calculations range between 1,2 and 2,3 % for levoglucosan. There is almost no
difference between these results obtained for the single sites. For cellulose this average
contributions range between 0,5 and 2,7 %. For levoglucosan the highest contribution
corresponds for AZO, where the lowest concentration values were determined. As here
the air is very clean and there is no influence of other sources of pollutes like road traffic,
industry emissions, etc., probably the contribution to OC of other source is minor. The
lowest average contribution for levoglucosan corresponds to AVE, Where the highest
concentration values of levoglucosan were determined. In opposite to AZO, AVE is very
influenced for other sources of pollutes. For cellulose the highest contribution was
obtained at SBO the other background site and the lowest average contribution was for
AVE, as for levoglucosan.

Page 128
 Summary

Based on levoglucosan a wood smoke equivalent can be calculated, while cellulose can
be used as an indicator for plant debris. The contributions of wood smoke to OM range
between 2 I and 39 %, while the contribution of plant debris to OM is 3 and 16 %. Here
the highest percentage for wood smoke is for AZO due to the same reasons as mentioned
before and for plant debris is SBO, especially during the cold seasons. Regarding the
lowest contribution of wood smoke is at SBO obtained, although the difference of
percentage with the highest value is not very high. Very low contributions ofplant debris
to OM correspond to AVE, which shows the lowest concentration values of cellulose.

Furthermore the size distribution (10-7,2 /lm, 7,2-3,0/lm, 3,0-1,5/lm, 1,5-0,95/lm, 0,95-
0,49/lm, <0,49/lm) of cellulose, levoglucosan were determined with a cascade impactor
at AVE. In most of the samples, the major fraction of levoglucosan and cellulose was
associated with the fine particle fraction « 3/lg/m3).

Page /29
 Literature

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Page 9
ANNEX
 Annex

Aerosol and gases concentration values in JIg pro Normcubicmeter Dee, 02-0ct, 04 Filler from 0 10 563

Aerosol (Anions) lue INm'1 Aerosol (Kations) r~ INm'] Gas (~g/Nm'1

::;~mJ>lës'~;'jDatè.'.:? CIiJorldë Nitrate. Sulphate Ox'aläte Nà NH4. ~ Mg Ca ~~~H,~"c~Jkl:
~;!_~'s.bi~.~
i~::~~ijji)5'
BO 10,12.2002 0,0097 0,0264 02674 0,0044 0,0178 0,1187 0,0061 0,0042 0,0336 0,0905 0,2362 0,0335
Bl 12.12.2002 0,0097 0,0717 0,1989 0,0050 0,0178 0,0670 0,0061 0,0042 0,0461 0,1155 0,2955 0,1130
B2 13.12.2002 0,0097 0,0330 0,2640 0,0081 0,0178 0,0671 0,0061 0,0059 0,0325 0,1570 0,0219 0,1507
B3 14.12.2002 0,0097 0,0097 0,1534 0,0050 0,0178 0,0382 0,0061 0,0018 0,0338 0,1596 0,2412 0,1041
B4 15.12.2002 0,0097 0,1079 0,1430 0,0129 0,0178 0,0542 0,0061 0,0169 0,1316 0,0262 0,1495 0,2209
B5 16.12,2002 0,0097 0,0268 0,0945 0,0044 0,0178 0,0270 0,0061 0,0018 0,0211 0,0668 0,1534 0,0335
B7 17.12,2002 0,0097 0,0303 0,0788 0,0050 0,0178 0,0256 0,0061 0,0067 0,0401 0,0234 0,0219 0,1725
B8 18.12.2002 0,0097 0,0543 0,1475 00081 0,0178 0,0439 0,0061 0,0048 0,0523 0,2112 0,2298 0,1434
B9 19,12.2002 0,0097 0,0097 0,0033 0,0020 0,0711 0,0380 0,0061 0,0018 0,0413 0,1117 0,0219 0,0335
B 10 20.12.2002 0,0097 0,0097 0,0097 0,0020 0,0178 0,0059 0,0061 0,0018 0,0089 0,0072 0,1320 0,2455
B 11 21.12.2002 0,0097 0,0097 0,0285 0,0020 0,0178 0,0138 0,0061 0,0018 0,0089 0,0072 0,0219 0,1281
B 13 22,12.2002 0,0097 0,0097 0,0201 0,0115 0,0178 0,0059 0,0061 0,0018 0,0089 0,0072 0,0219 0,0335
B 14 23,12,2002 0,0097 0,0097 0,0033 0,0020 0,0178 0,0059 0,0061 0,0018 0,0089 0,0072 0,1056 0,0844
B15 24,12.2002 0,0097 0,0097 0,0131 0,0020 0,0178 0,0059 0,0061 0,0018 0,0089 0,0072 0,0219 0,1049
B 16 25.12.2002 0,0097 0,0097 0,0523 0,0020 0,0178 0,0176 0,0061 0,0018 0,0259 0,0170 0,1230 0,0676
B17 26.12.2002 0,0097 0,0424 0,0908 0,0020 0,0178 0,0469 0,0061 0,0018 0,0089 0,0183 0,0627 0,2894
B 19 27.12.2002 0,0097 0,0097 0,0302 0,0020 0,0178 0,0059 0,0061 0,0018 0,0089 0,0227 0,1129 0,0978
620 28.12.2002 0,0097 0,0750 0,0033 0,0020 0,0178 0,0407 0,0061 0,0018 0,0089 0,0072 0,0219 0,2468
B 21 29.12.2002 0,0097 0,0264 0,0667 0,0020 0,0178 0,0302 0,0061 0,0018 0,0089 0,0072 0,0667 0,0814
622 30.12.2002 0,0097 0,0097 0,0618 0,0020 0,0178 0,0239 0,0061 0,0018 0,0089 0,0780 0,0219 0,0335
A 23 17.01.2003 0,0097 0,0299 0,1242 0,0058 0,0178 0,0305 0,0061 0,0018 0,0089 0,0416 0,0405 0,0335
A 24 18.01.2003 0,0097 0,0280 0,3155 00056 0,0178 0,0865 0,0061 0,0018 0,0344 0,0366 0,0920 0,0335
A 25 19.01.2003 0,0097 0,6173 0,0274 0,0020 0,0178 0,1218 0,0061 0,0018 0,0089 0,0803 0,0462 0,0335
A 26 20.01.2003 0,0097 0,0097 0,1656 0,0020 0,0178 0,0389 0,0061 0,0018 0,0089 00960 0.0202 0,0335
A 27 21.01.2003 0,0097 0,0430 0,0693 0,0076 0,0178 0,0175 0,0061 0,0018 0,0191 0,0072 0,0202 0,1737
A 28 23.01.2003 0,0097 0,0097 0,2156 0,0020 0,0178 0,0560 0,0061 0,0018 0,0089 0,0072 0,3128 0,0335
A 30 24.01.2003 0,0097 0,0248 0,1796 0,0054 0,0178 0,0308 0,0061 0,0018 0,0089 0,0204 1,5009 0,0335
A 31 26.01.2003 0,0097 0,0273 0,1849 0,0101 0,0178 0,0315 0,0061 0,0018 0,0452 0,0350 0,0202 0,0335
A 32 27.01.2003 0,0097 0,0097 0,0333 0,0020 0,0178 0,0139 0,0061 0,0018 0,0089 0,0072 0,0202 0,0335
A 33 28.01.2003 0,0097 0,0462 0,1803 0,0108 0,0178 0,0357 0,0061 0,0018 0,0089 0,0273 0.0462 0,0335
A 34 29.01.2003 0,0097 0,0419 0,1558 0,0020 0,0178 0,0280 0,0061 0,0018 0,0089 0,0072 0,0202 0,0335
A 36 30.01.2003 0,0097 0,0248 0,1837 0,0020 0,0178 0,0294 0,0061 0,0018 0,0089 0,0445 0,1190 0,0335
A 37 31.01.2003 0,0097 0,0350 0,2992 0,0020 0,0178 0,0534 0,0061 0,0018 0,0089 0,2025 0,6359 0,0335
A 38 09.02.2003 0,0130 0,0572 0,6368 0,0167 0,0239 0,1181 0,0082 0,0024 0,0577 0,1229 0,1298 0,0335
A 39 10.02.2003 0,0130 0,1112 0,7284 0,0212 0,0239 01240 0,0359 0,0057 0,0921 0,0174 0,0202 0,0335
A 40 11.02.2003 0,0130 0,0130 0,4798 0,0101 0,0239 0,0955 0,0082 0,0024 0,0403 0,0418 0,1442 0,0335
A 42 12.02.2003 0,0130 0,1429 1,2286 0,0160 0,0239 0,2120 0,0082 0,0108 0,1137 0,0784 0,1724 0,0335
A 43 13.02.2003 0,0130 0,0456 0,7375 0,0325 0,0239 0,1700 0,0082 0,0024 0,0587 0,0714 0,1056 0,0335
A44 01,02.2003 0,0130 0,0292 0,4411 0,0020 0,0239 0,1053 0,0082 0,0024 0,0339 0,4605 0,4942 0,0335
A 45 02.02.2003 0,0130 0,0130 0,5612 0,0020 0,0239 0,1178 0,0082 0,0024 0,0119 0,0527 0,0606 0,0335
A 46 03,02.2003 0,2379 0,0779 0,3906 0,0111 0,0239 0,0888 0,0082 0,0024 0,1050 0,0330 0,0202 0,0335
A 48 04.02,2003 0,0130 0,0266 0,5498 0,0066 0,0239 0,1153 0,0082 0,0024 0,0119 0,0786 0,3226 0,0335
A 49 05.02.2003 0,0130 0,0130 0,5324 0,0182 0,0239 0,1909 0,0082 0,0024 0,0119 0,1005 0,0202 0,0335
A 50 06.02.2003 0,0130 00130 0,2477 0,0197 0,0239 0,0637 00082 0,0024 0,0119 0,0785 0,0202 0,0335
A 51 07.02.2003 0,0130 0,0130 0,1742 0,0042 0,2278 0,0454 0,0082 0,0024 0,0272 0,1989 0,0202 0,0335
A 52 14.02.2003 0,0130 0,1343 1,0598 0,0259 0,0239 0,2231 0,0082 0,0129 0,1854 0,0596 0,1500 0,0449
A 54 15,02.2003 0,0130 0,0308 0,5440 0,0144 0,0239 0,1547 0,0082 0,0024 0,0119 0,0951 0,3286 0,0449
A 55 16.02.2003 0,0130 0,0130 1,7887 0,0098 0,0239 0,3333 0,0304 0,0024 0,0119 0,0460 0,5585 0,0449
A 56 17.02,2003 0,0130 0,0130 0,6290 0,0087 0,1225 0,1461 0,0082 0,0024 0,0241 0,1247 0,3438 0,0449
A 57 18.02.2003 0,0130 0,0130 0,1662 0,0061 0,0239 0,0628 0,0082 0,0024 0,0537 0,0603 0,0271 0,0449
A 58 19.02,2003 0,0130 0,0130 0,1803 0,0027 0,0536 0,0662 0,0082 0,0024 0,0119 0,0346 0,0271 0,0449
A 60 20.02.2003 0,0130 0,0130 0,0719 0,0027 0,0510 0,0262 0,0082 0,0024 0,0119 0,0487 0,0271 0,0449
A 61 21.02,2003 0,0130 0,0130 0,0474 0,0027 0,0239 0,0255 0,0082 0,0024 0,0119 0,0615 0,0271 0,0449
A 62 22,02.2003 0,0130 0,0130 0,0749 0,0027 0,0239 0,0355 00082 0,0024 0,0119 0,0724 0,0271 0,0449
A 64 24.02,2003 0,0130 0,0130 0,0784 0,0027 0,0483 0,0273 0,0082 0,0024 0,0119 0,0862 0,0271 0,0449
A 66 25,02.2003 0,0130 0,0130 0,0435 0,0027 0,0239 0,0079 0,0082 0,0024 0,0119 0,0096 0,C553 0,0449
A 67 26.02,2003 0,0130 0,0130 0,0460 0,0252 0,0239 0,0318 0,0082 0,0024 0,0119 0,1239 0,0271 0,0449
A 68 27.02,2003 00130 0,0279 0,1601 0,0390 00239 0,0807 0,0082 0,0058 0,0476 0,2671 0,0919 0,0449
A 69 28,02.2003 0,0130 0,0130 0,0045 0,0448 0,0239 0,0079 0,0082 0,0024 0,0119 0,2439 0,1654 0,2289
8 70 01.03.2003 00130 0,8307 0,3851 0,0327 0,0681 0,2807 0,0254 0,0024 0,0477 0,2095 0,0271 0,2661
8 72 02.03.2003 0,0130 0,0387 0,0731 0,0027 0,0239 0,0272 0,0082 0,0024 0,0119 0,0317 0,0271 0,3131
8 73 03.03.2003 00130 0,0130 0,1952 0,0027 0,0239 0,0079 0,0082 0,0024 0,0782 0,0096 0,0271 0,0449
8 74 04.03.2003 0,0130 0,0649 0,0776 0,0027 0,0239 0,0306 0,0082 0,0024 0,0263 0,0719 0,0664 0,1730
8 75 05.03.2003 0,0130 0,0130 0,0045 0,0027 0,0239 0,0079 0,0082 0,0024 0,0119 0,0096 0,0271 0,2826
8 76 06.03.2003 0,0130 0,0263 0,0633 0,0027 0,0239 0,0273 0,0082 0,0024 0,0119 0,0780 0,0940 0,3561
8 78 07.03.2003 0,0130 0,1484 0,2621 0,0108 0,0239 0,0980 0,0082 0,0024 0,0320 0,3397 0,3499 0,1957
8 79 08.03.2003 0,0130 0,0935 0,2978 0,0067 0,0785 0,1179 0,0082 0,0024 0,0119 0,1644 0,0271 0,1006
8 80 09,03.2003 0,0130 0,0412 0,3015 0,0065 0,0239 0,1188 0,0082 0,0024 0,0402 0.0771 1,4370 0,0449

Page 1
 Annex

Aerosol and gases concentration values in JIg pro Normcubicmeter Dec. 02-0cl. 04 Filter from 0 to 563

Aerosol (Anions\ [u( INm'l Aerosol (Kations) [IJ INm'J Gas luolNm']
$âÏ1'iples~;,6Dât~i;.i: Chlc)rldè , Nit~ate: 5ùlphate ,Oxalate 'Na- ,NH4' K -- Mg Ca ;IHN.ôi/, 4L:l~i~O~(~j:
~'~NH3::1
8 81 11.03.2003 0,0130 0,0821 0,2141 0,0128 0,0239 0,0788 0,0082 0,0024 0,0319 0,3324 0,1665 0,1550
882 12.03,2003 0,0130 0,1170 0,1973 0,0127 0,0239 0,1002 0,0082 0,0024 0,0119 0,0777 0,2263 0,2798
884 13.03.2003 0,0130 0,0733 0,0983 0,0027 0,0239 0,0535 0,0082 0,0024 0,0119 0,0096 0,0271 0,1489
885 28.03.2003 0,0302 4,4751 1,8817 0,1391 0,0239 0,2542 0,0209 0,0024 0,0288 0,1762 03076 0,7657
886 30,03.2003 0,0130 0,4803 0,5065 0,0312 0,0239 0,3164 0,0262 00024 0,0824 0,1086 0,1734 0,9010
887 31.03.2003 0,0130 0,1817 0,2343 0,0094 0,0239 0,1946 0,0082 0,0024 0,0769 01308 0,0919 0,4855
888 01,04.2003 0,0130 0,9596 0,8848 0,0336 0,0239 0,5735 0,0332 0,0100 0,0724 0,2279 0,2189 0,4418
890 02.04.2003 0,0130 0,0130 0,0632 0,0027 0,0239 0,0274 0,0082 0,0024 0,0119 0.0447 0,1500 0,0972
891 03.04.2003 0,0130 0,1844 0,0999 0,0027 0,0620 0,0487 0,0395 0,0024 0,0119 0,0681 0,2172 0,1649
892 04.04.2003 0,0130 0,4961 0,1972 0,0124 0,0239 0,1355 0,0082 0,0024 0,0606 0,0551 0,1026 0,3697
893 05.04,2003 0,0130 0,2330 02162 0,0212 0,0239 0,0600 00082 0,0059 0,1025 0,0850 0,0637 0,1649
894 06.04.2003 0,0130 0,2271 0,4112 0,0061 0,0239 0,1847 0,0229 0,0024 0,0119 0,0534 0,1293 0,4196
896 07.04.2003 0,0130 0,0621 0,4011 0,0027 0,0239 0,1472 0,0082 0,0024 0,0119 0,0503 0,1313 0,1315
897 08.04.2003 0,0130 2,2686 1,4020 0,0477 0,0239 1,1156 0,0599 0,0058 0,0359 0,9695 1,0122 0,2626
898 09.04.2003 0,0282 2,0099 0,8845 0,0371 0,0239 0,9131 0,0527 0,0024 0,0524 0,7967 0,7169 0,4823
899 10.04.2003 0,0130 0,2313 0,3367 0,0176 0,0239 0,1689 0,0200 0,0024 0,0119 0,1367 0,1296 0,4223
8100 13.04.2003 0,0130 0,0974 0,3992 0,0126 0,0239 0,1674 00082 0,0024 0,0289 0,3833 0,1913 0,2508

•
8102 14.04.2003 0,0130 0,4735 1,0303 0,0435 0,0239 0,4411 0,0337 0,0050 0,0643 0,1791 0,1106 0,3738
8103 15.04.2003 0,0130 0,0707 0,3831 0,0099 0,0239 0,1384 0,0312 0,0024 0,0425 0,1277 0,1446 0,0449
8104 16.04.2003 0,0130 0,6908 2,6332 0,0920 0,0239 0,9380 0,0538 0,0024 0,0119 0,2509 0,3842 0,3513
8105 17.04.2003 0,0130 1,3016 2,0719 0,1120 0,0239 0,9679 0,0764 0,0103 0,0874 0,2433 0,7282 0,2787
8106 18.04.2003 0,0130 1,0643 1,4556 0,0439 0,0239 0,7224 0,0315 0,0024 0,0119 0,0981 0,6018 1,2157
8108 19.04,2003 0,0130 0,1063 0,4298 0,0182 0,0239 0,2195 0,0082 0,0024 0,0119 0,1036 0,1533 0,2594
8109 20.04.2003 0,0130 0,0130 0,2630 0,0061 0,0239 0,1370 0,0082 0,0024 0,0119 0,0775 0,2881 0,2834
8110 21.04.2003 0,0130 0,0668 1,1013 0,0498 0,0239 0,4267 0,0325 0,0024 0,0119 0,2452 0,0271 0,0449
8111 22.04.2003 0,0130 1,5978 2,3227 0,1092 0,0666 1,0396 0.0627 0,0226 0,2029 0,1645 0,2455 0,5991
8112 24.04.2003 0,0130 2,6352 2,4458 0,1191 0,0724 1,3811 0,0897 0,0234 0,2010 0,1461 0,0900 1,1173
8113 25.04.2003 0,0130 27444 2,5029 0,1379 0,0239 1,4399 0,0839 0,0232 0,2009 0,2533 0,1820 1,4193
8115 26.04.2003 0,0130 0,5860 0,7616 0,0408 0,0239 0,3420 0,0211 0,0073 0,0584 0,0733 0,1164 0,6422
8116 27.04.2003 0,0130 0,0835 0,1736 0,0128 0,0239 0,0675 0,0062 0,0024 0,0119 0,0321 0,0271 0,6276
8117 28.04.2003 0,0130 1.0097 1,0751 0,0539 0,0239 0,5682 0,0222 0,0091 0,0491 0,4308 0,0271 0,8337
8118 29.04.2003 0,0130 1,9924 2,0614 0,0903 0,0239 1,0378 0,0412 0,0150 0,0963 0,3497 0.0271 0,7603
8119 30,04.2003 0,0728 1,0873 1,9905 0,1213 0,1462 0,5000 0,0688 0,0463 0,9535 0,0659 0,2149 1,1654
8120 01.05.2003 0,0130 0,4398 1,1422 0,0448 00239 0,4851 0,0199 0,0079 0,0252 0,0410 0,0271 0,6381
8121 02.05.2003 0,0130 0,3404 0,7866 0,0270 0,0239 0,3055 0,0230 0,0081 0,0644 0,0291 0,0271 0,9429
8122 16.05.2003 0,0130 1,0153 1,0019 0,0343 0,0239 0,4694 0,0366 0,0084 0,0614 0,1996 0,2074 0,3560
8123 17.05.2003 0,0565 0,4653 0,8285 0,0278 0,0239 0,2842 0,0580 0,0024 0,0297 0,2586 0,1108 0,3395
8126 18.05.2003 0,0130 0,2540 0,7205 0,0216 0,0239 0,2567 0,0082 0,0024 0,0119 0,2081 0,0271 0,4028
8127 19.05.2003 0,0130 0.6598 0,9472 0,0235 0,0239 0,3920 0,0299 0,0024 0,0246 0,1231 0,0271 0,6555
B 128 20.05.2003 0,0130 0,0302 0,0338 0,0027 0,0239 0,0079 00082 0,0024 0,0119 0,0363 0,0271 0,1280
B 129 21.05.2003 0,0130 0,0130 0,0319 0,0027 0,0239 0,0079 0,0082 0,0024 00119 0,0439 0,0766 0,1158
B 130 22.05.2003 0,0130 0,0130 0,0528 0,0027 0,0239 0,0171 0,0082 0,0024 0,0119 0,0887 0,0271 0,0449
B 132 23.05.2003 0,0618 0,4774 0,4130 0,0169 0,1007 0,1374 00300 0,0193 0,2325 0,0765 0,0918 0,2139
B 133 24.05.2003 0,0130 0,7472 1,1158 0,0581 0,0239 0,4037 0,0332 0,0158 0,1108 0,1965 0,1263 0,5751
B 134 25.05.2003 0,0130 0,3630 1,5503 0,0239 0,0239 0,4816 0,0256 0,0024 0,0448 0,2523 0,1285 0,6396
B 135 26.05.2003 0,3841 1,7299 2,9165 0,0982 0,3520 0,5774 0,1847 0,0779 0,5610 0,2628 0,0271 0,2317
B 136 27,05.2003 0,0130 0,4605 1,3751 0,0307 0,0239 0,4214 0,0307 0,0049 0,0625 0,2223 0,0888 0,5641
B 138 12.06.2003 0,0130 0,3476 1,4042 0,1212 0,0239 0,4409 0,0179 0,0097 0,1228 0,5794 0,1921 0,7846
8139 13.06.2003 0,0130 0,5979 1,3997 0,1042 0,0656 0,4183 0,0338 0,0349 0,6236 0,4972 0,1440 0,5208
B 140 14.06.2003 0,0914 0,8629 1,5678 0,0903 0,0664 0,3733 0,0313 0,0419 0,7275 0,2326 0,2575 0,9311
B 141 15,06.2003 0,0130 0,5780 1,1047 0,0838 0,0239 0,3183 0,0082 0,0177 0,2484 0,1914 0,1584 0,5953
B 142 16.06.2003 0,0401 0,5007 1,3303 0,1208 0,0239 0,5109 0,0170 0,0152 0,1603 0,4454 0,1616 0,9075
B 143 17.06.2003 0,0130 0,3451 0,9230 0,1065 0,0239 0,3071 0,0172 0,0171 0,2553 0,3627 0,1188 0,9187
B 144 18.06.2003 0,0558 0,0487 0,2759 0,0102 0,0918 0,0813 0,0082 0,0024 0,0293 0,1042 0,0271 0,4712
B 145 19.06.2003 0,0130 0,0945 0,1916 0,0319 0,0239 0,0267 0,0082 0,0024 0,0641 0,0750 0,0766 0,3928
B 146 20.06.2003 0,0130 0,2247 0,4862 0,0420 0,0239 0,1892 0,0082 0,0067 0,0480 0,3220 0,1521 0,6313
B 147 21.06.2003 0,0130 01234 0,5385 0,0357 0,0239 0,2347 0,0208 0,0055 0,0546 0,3291 0,1062 0,4272
B 148 22.06.2003 0,0280 0,1822 0,7418 0,0743 0,0239 03375 0,0082 0,0077 0,0867 0,6814 0,2502 0,6079
B 150 23.06.2003 00130 0,3526 1,1068 0,1432 0,0239 0,5101 0,0183 0,0139 0.3255 0,0096 0,1705 0,7428
B 151 24.06.2003 0,0316 1,3386 2,7104 0,2260 0,0480 1,1143 0,0284 00298 0,3561 0,5655 0,2422 1,2243
B 152 25.06.2003 0,0130 0,7459 1,4185 0,1066 0,0947 1,1600 0,0485 0,0411 0,5452 0,2213 0,2492 0,8904
B 153 26.06.2003 0,0502 1,7152 4,0944 0,2629 0,0239 0,6478 0,0393 0,0220 0,2640 0,3197 0,2012 0,7382
B154 27.06.2003 0,0408 0,8546 1,5106 0,1000 0,0239 0,5971 0,0489 0,0182 0,2427 0,2658 0,1809 0,5268
B 155 28.06.2003 0,1156 0,1969 0,8177 0,0560 0,0239 0,3378 00287 0,0024 0,0759 0,5601 0,1549 0,4197
B 157 29.06.2003 0,0130 0,3084 0,7724 0,0555 0,0239 0,2708 0,0082 0,0024 0,0810 0,3598 0,1548 0,5392
B 158 30.06.2003 0,0130 0,8562 2,5151 0,2011 0,0239 0,8833 0,0396 0,0215 0,2899 0,5906 0,6551 0,8807
B 159 01,07.2003 0,1490 0,4737 0,8373 0,0407 0,0239 0,3020 0,0253 0,0024 - 0,2499 0,0825 0,0917 0,6411
B 160 02,07.2003 0,0328 0,0531 D,lIDO 0,0027 0,0239 0,0178 0,0082 0,0024 0,4199 0,0535 0,2547 0,5788

Page 2
 Annex

Aerosol and gases concentration values in IJg pro Normcubicrneter Dee, 02-0ct. 04 Filter from 0 to 563

Aerosol (Anions) [IJ~INm') Aerosol (Kations) fu INm'\ Gas [1Jg/Nm'l

Sàmplës: ~~;A~Dàtè':1r'~
CtiIOrjd!!'Nitr~tê. Sulphate .Oxalate Nai NH4 ecK. Mg .Ca i::,:so';~t,~
~,{~~O~W -tNf:I~:?~:;
8 161 03,07.2003 0,0130 0,0130 0,1283 0,0027 0,0239 0,0386 0,0082 0,0024 0,1132 0,7559 0,2128 0,5283
8 163 05.07.2003 0,0130 0,0130 0,0045 0,0027 0,0239 0,1027 0,0082 0,0024 0,0381 0,5865 0,0939 0,3013
8 164 06.07.2003 0,0130 0,0628 0,7500 0,0342 0,0239 0,2791 0,0082 0,0024 0,0401 0,9001 0,2719 0,7510
8 165 07.07.2003 0.1893 0,3942 1,5948 0,0653 01054 0,4897 0,0689 0,0078 0,1144 1,8447 0,3046 0,5133
8 166 08.07.2003 0,2059 0,7281 2,3318 0,1335 0,0698 0,8419 0,0620 0,0102 0,0831 2,5675 0,3966 0,5727
8 167 09.07.2003 0,0447 0,1682 1,6277 0,0458 0,0239 0,5528 0,0225 0,0061 0,1760 2,4978 0,2596 0,5093
8 169 11.07.2003 0,0130 0,4196 2,7388 0,1174 0,0239 0,9370 0,0411 0,0118 0,1936 3,1139 0,4424 0,5832
8 170 12.07.2003 0,0130 0,4210 3,0045 0,1886 0,0239 1,0710 00244 0,0186 0,1493 2,3911 0,3276 0,8052
8 171 13.07.2003 0,0391 0,1875 1,8856 0,1573 0,0880 0,6394 0,0426 0,0191 0,1629 1,8635 0,1808 0,7209
8 172 14.07.2003 0,0704 0,3861 1,3760 0,1329 0,0624 0,4747 0,0317 0,0558 4,2276 1,3428 0,2572 0,9830
8 173 15.07.2003 0,0130 0,2105 1,8026 0,1668 0,0239 0,5612 0,0082 0,0219 0,2617 0,0096 0,2009 1,1046
8 175 17.07.2003 0,Q130 0,0261 0,2484 0,0216 0,0239 0,0784 0,0082 0,0024 0,0119 0,5041 0,1754 0,8632
8 176 18.07.2003 0,0130 0,0840 0,5616 0,0345 0,0239 0,2202 0,0082 0,0075 0,0696 0,6417 0,0764 0,5848
8177 19.07.2003 0,0130 0,0725 0,5214 0,0502 0,0239 0,2769 0,0082 0,0175 0,1027 0,8490 0,1467 0,8579
8 178 20.07.2003 0,0130 0,2211 1,6243 0,1747 0,0239 0,5575 0,0178 0,0260 0,2529 1,6053 0,2490 1,6379
8 179 21.07.2003 0,0130 0,2397 0,6821 0,0429 0,0239 0,1976 0,0082 0,0024 0,2034 1,6845 0,2326 0,7285
8180 22.07.2003 00130 0,1276 0,7773 0,0647 00239 0,2339 0,0082 0,0166 0,2109 0,3568 0,1727 0,6746
8182 24.07.2003 0,0130 0,0130 0,0347 0,0027 0,0239 0,0079 00082 0,0024 0,0650 0,1710 0,1194 0,3908
8 183 25.07.2003 0,0130 0,1353 0,6946 0,0433 0,0239 0,1362 0,0082 0,0061 0,0786 0,4104 0,3121 0,5040
8184 26.07.2003 0,0130 0,2132 1,2799 0,0989 0,0239 0,4017 0,0082 0,0130 0,1311 0,0096 0,2673 0,6148
8 185 27.07.2003 0,0130 0,0475 0,2494 0,0174 0,0239 0,0739 0,0082 0,0024 0,0282 0,7667 0,8594 0,7357
B 186 28.07,2003 0,0130 0,0305 0,0751 0,0122 0.0239 0,0166 0,0082 0,0024 0,0257 0,1644 0,1216 0,3890
B 187 29.07.2003 0,0130 0,1544 0,3913 0,0252 0,0239 0,4250 0,0082 0,0024 0,0277 1,9323 0,1589 0,1313
B 189 30.07.2003 0,0130 0,0130 0,0045 0,0111 0,0239 0,0494 0,0082 0,0024 0,0119 0,3331 0,1141 0,2893
B 190 01.08.2003 0,0125 0,0130 0,1335 0,0031 0,0204 0,0873 0,0087 0,0069 0,0282 0,1188 0,3273 0,4957
B 191 02.08.2003 0,0125 0,0460 0,7269 0,0225 0,0204 0,5316 0,0238 00069 0,0788 0,5627 0,1581 0,6496
B 192 03.08.2003 0,0125 0,0130 0,2509 0,0106 0,0204 0,1138 0,0087 0,0069 0,0413 0,1734 0,1450 0,9477
B 193 04.08.2003 0,0125 0,1079 0,8445 0,0779 0,0204 0,3585 0,0087 0,0225 0,2231 0,5007 0,1840 0,9183
B 194 05.08.2003 0,0125 0,7623 1,4129 0,1141 0,0204 0,6665 0,0450 0,0328 0,5319 0,6185 0,2575 0,5646
B 196 07.08.2003 0,0125 1,3736 2,4319 0,2217 0,0965 1,2934 0,1543 0,0546 1,3291 2,1910 0,5372 2,0873
B 197 09.08.2003 0,0125 1,2189 2,3398 0,1929 0,0555 1,0270 0,1006 0,0388 0,5605 1,4067 0,4192 0,8793
8 198 10.08.2003 0,0125 1,9267 4,7747 0,4267 0,1004 2,1720 0,2447 0,0718 0,8036 2,9008 0,9581 1,5301
B 199 11.08.2003 0,0125 0,0130 0,0163 0,0031 0,0204 0,0273 0,0087 0,0069 0,0127 1,5912 0,4721 1,2399
B 200 12.08.2003 0,0125 1,6676 6,9805 0,5356 0,0204 0,4718 0,0270 0,0069 0,1267 4,9940 1,0426 0,6233
B 201 13.08.2003 0,0125 0,6775 3,3098 0,3364 0,0501 1,3162 0,1582 0,0742 1,0039 2,6156 0,1962 1,4536
B 202 14.08.2003 0.0125 0,5296 2,1522 0,1289 0,0204 0,6052 0,0622 0,0208 0,3288 0,9344 0,4237 0,9442
B 203 15.08.2003 0,0125 0,7608 1,6938 0,0966 0,0538 0,4740 0,0481 0,0533 0,7378 0,5397 0,2561 0,7946
B 204 16.08.2003 0,0125 0,6023 2,2079 0,1529 0,0447 0,7637 0,0835 0,0403 0,4930 0,9416 0,3455 0,6604
B 205 17.08.2003 0,0125 0,5905 3,6585 0,2256 0,0534 1.3020 0,1484 0,0248 0,3358 1,4286 0,5756 0,9446
B 206 18.08.2003 0,0125 0,0985 0,8350 0,0331 0,0204 0,1436 0,0087 0,0069 0,0597 0,4542 0,1855 0,4057
B 207 19.08.2003 0,0125 1,7441 5,1413 0,4085 0,0869 2,2470 0,1768 0,1023 0,9046 0,8842 0,1433 0,3691
B 208 20.08.2003 0,0125 0,0987 1,9040 0,1192 0,0204 0,7311 0,0375 0,0248 0,3659 1,0419 0,1630 0,5663
8 210 21.08.2003 0,0125 0,2322 1,5537 0,1536 0,0204 0,6407 0,0298 0,0213 0,3364 0,8693 0,0285 0,3683
8 211 22.08.2003 0,0125 0,2271 1,2461 0,1649 0,0204 0,0640 0,0087 0,0069 0,0262 1,3158 0,2785 0,3460
8212 23.08.2003 00125 0,1573 1,5233 0,1355 00204 0,6716 0,0381 0,0155 0,1428 1,5149 0,0713 2,2801
B 213 24.08.2003 00125 0,3563 1,6177 01742 0,0204 0,7561 0,0512 0,0251 0,1664 1,4764 0,1988 1,1602
B 215 25.08.2003 0,0125 0,3370 14443 0,1637 0,0204 0,6317 0,0314 0,0544 0,6890 1,6357 0,1717 0,9571
B 216 26.08.2003 0,0125 1,0467 2,3007 0,1656 0,1076 1,1371 0,1124 0,1132 2,6382 0,0097 0,4015 0,7543
8217 27.08,2003 0,0125 0,3430 0,4237 0,0425 0,0204 0.2986 0,0438 0,0513 0,7197 1,8899 0,2151 0,9365
8 218 28.08.2003 0,0125 0,0130 0,2921 0,0071 0,0204 0,1697 0,0087 0,0069 0,0894 0,6881 0,1474 0,8704
8 219 29.08.2003 0,Q125 0.0299 0,1109 0,0081 0,0204 00256 0,0087 0,0069 0,5340 1,6969 0,1846 1,3300
8221 30.08.2003 0,0125 0,0528 0,3654 0,0115 0,0204 0,1702 0,0087 0,0069 0,0388 1,0612 0,2077 0,5719
8 222 31.08.2003 0,0125 0,2300 0,4769 0,0444 0,0204 0,1284 0,0087 0,0069 0,3973 0,7474 0,0808 0,3076
B 223 01.09.2003 0,0124 0,0483 0,4561 0,0112 0,0195 0,2269 0,0082 0,0061 0,0731 0,0826 0,0283 0,4214
8224 03.09.2003 0,0124 0,0344 0,2024 0,0324 0,0195 0,0989 0,0082 0,0061 0,1971 0,4634 0,1437 0,2914
8 225 04.09.2003 0,0124 0,0140 0,1892 0,0110 0,0195 0,0841 0,0082 0,0061 0,1163 0,6777 0,1050 0,1872
B 227 05.09.2003 0,0124 0,1239 0,7632 0,0775 0,0195 0,3538 0,0082 0,0061 0,0764 1,0893 0,2394 0,6028
8228 06.09.2003 0,0124 0,1854 1,2767 0,0573 0,0195 0,5464 0,0674 0,0061 0,1180 1,4376 0,1531 0,6721
8229 07.09.2003 0,0124 0,1117 1,5547 0,0688 0,0195 0,6050 0,0527 0,0061 0,0535 1,3791 0,1739 0,2709
8230 08.09.2003 0,0124 0,0320 0,0400 0,0073 0,0195 0,0148 0,0082 0,0061 0,0174 0,3860 0,1268 0,3001
B 231 09.09.2003 0,0124 0,0140 0,0831 0,0032 0,0195 0,0148 0,0082 0,0061 0,0174 0,4695 0,1245 0,2470
8233 10.09.2003 0,0124 0,0140 0,7783 0,0073 0,0195 0,4008 0,0082 0,0061 0,0174 00097 0,0997 0,4822
8234 11.09.2003 0,0124 0,0355 0,3133 0,0207 0,0195 0,1007 0,0082 0,0061 0,1693 0,3867 0,1243 0,0366
8 235 25.09.2003 0,0124 0,0140 0,2321 0,0417 0,0195 0,1320 0,0082 0,0061 0,0174 0,3452 0,1873 0,0366
8236 26.09.2003 0,0124 0,0716 0,3978 0,0242 0,0195 0,2033 0,0082 0,0061 0,0463 0,8286 0,1013 0,3035
8237 27.09.2003 0,0124 0,1478 0,9904 0,0431 0,0195 0,4588 0,0249 0,0061 0,0584 1,2501 0,1051 0,5404
8239 28.09.2003 0,0124 0,0776 0,4663 0,0144 0,0195 0,2365 0,0082 0,0061 0,0499 1,1421 0,3553 0,4088
8240 29.09.2003 0,0124 0,0962 0,8966 0,0298 0,0195 0,3888 0,0082 0,0061 0,0174 1,1446 0,0646 '0,2597

Page 3
 Annex

Aerosol and gases concentration values in /lg pro Normeu bicmeter Dec. 02-0cl. 04 Filler from 0 10 563

Aerosol (Anions) [!Je/Nm31 Aerosol (Kations) [IJ j/Nm'] Gas f!JQ/Nm'l

~ampl~s;):;'I.D~te _:};Chloride Nitrate, Sulphate Oxalate >Na .. NH4 K Mg Ca.. !~IiIl103\ ;:::';SO:i'.~;:
,;.i(NH3i;~?
8 241 30,09.2003 0,0124 0,1438 0,8803 0,0240 0,0195 0,3874 0,0185 0,0061 0,0376 2,6431 03001 0,7198
8242 01.10.2003 0,0117 0,0812 0,3812 0,0096 0,0196 0,1913 0,0082 0,0034 0,0939 0,6645 0,3176 0,3100
8 243 02.10.2003 0,0117 0,2503 0,7387 0,0212 0,0411 0,3093 0,0304 0,0073 0,1636 0,6205 0,1085 0,6790
8245 03.10.2003 0,0117 0,1712 0,3694 0,0139 0,0196 0,1544 0,0082 0,0108 0,5735 0,4903 0,1866 0,4519
8246 04.10.2003 0,0117 0,0914 0,0622 0,0032 0,0196 0,0100 0,0082 0,0034 0,0571 0,2269 0,1741 0,0366
8247 05.10.2003 0,0117 0,0547 0,1334 0,0203 0,0196 0,0100 0,0082 0,0034 0,1536 0,1473 0,1173 0,0366
8 248 06.10.2003 0,0117 0,0142 0,1087 00032 0,0196 0,0526 0,0082 0,0034 0,0171 0,3489 0,0872 0,1453
8249 07.10,2003 0,0117 0,0478 0,1405 0,0104 0,0196 0,0444 0,0082 0,0034 0,0792 0,6391 0,2080 0,0366
8251 08.10.2003 0,0117 00455 0,1261 0,0114 0,0196 0,0100 0,0082 0,0034 0,0858 0,2624 0,2535 0,0366
8252 09.10,2003 0,0412 0,0719 0,1782 0,0032 0,0196 0,0388 0,0082 0,0034 0,0171 0,2467 0,2822 0,0795
8253 10.10,2003 0,0117 0,0376 0,2494 0,0032 0,0196 0,0835 0,0082 0,0034 0,1071 0,7918 0,4498 0,0813
8254 11.10,2003 0,0117 0,0790 0,4535 0,0095 0,0196 0,2121 0,0082 0,0034 0,0617 0,9338 0,1873 0,0366
8 255 12.10,2003 0,0117 0,0142 0,4717 0,0158 0,0196 0,2092 0,0082 0,0034 0,0679 0,2980 0,1678 0,1271
8 257 13.10.2003 0,0117 0,0438 0,2943 0,0032 0,0196 0,1337 0,0082 0,0034 0,0655 0,4285 0,1490 0,1282
8 258 14.10,2003 0,0117 0,0142 0,2465 0,0130 0,0196 0,1012 0,0082 0,0034 0,0560 0,1159 0,0283 0,1449
8259 16.10.2003 0,0117 0,0142 0,6796 0,0131 0,0196 0,2018 0,0191 0,0034 0,0513 0,1631 0,0292 0,0366
8260 17,10.2003 0,0117 0,0142 0,6115 0,0032 0,0196 0,2025 0,0082 0,0034 0,0171 0,2458 0,0292 0,0366
8 261 18.10.2003 0,0117 0,0285 0,4600 0,0032 0,0196 01409 0,0082 0,0034 0,0171 0,2834 0,0693 0,0366
8262 19.10.2003 0,0117 0,0142 0,0053 0,0120 0,0196 0,0100 0,0082 0,0034 0,0347 0,0713 0,0292 0,0366
8 263 20.10.2003 0,0117 0,0142 0,3042 0,0032 0,0196 01162 0,0082 0,0034 0,0375 0,3844 0,1141 0,0844
8 264 21.10.2003 0,0117 0,0142 0,0460 0,0032 0,0196 0,0100 0,0082 0,0034 0,0171 0,0621 0,6495 0,0366
8265 22.10.2003 0,0117 0,0938 0,5579 0,0289 0,0196 0,2305 0,0082 0,0034 0,0171 1,4176 0,0753 0,0366
8266 23.10.2003 0,0117 0,0142 0,4298 0,0032 0,0196 0,1650 0,0082 0,0034 0,0171 0,6784 0,1955 0,0366
8 267 24.10.2003 0,0117 0,0142 0,6984 0,0175 0,0196 0,2386 0,0082 0,0034 0,0171 0,4632 0,0852 0,0366
8269 27.10.2003 0,0117 0,0142 0,3515 0,0032 0,0196 0,1331 0,0082 0,0034 0,0171 0,5397 0,0292 0,0366
8270 28.10.2003 0,0271 0,0142 0,3510 0,0032 0,0196 0,0771 0,0082 0,0034 0,0171 0,3117 0,1397 0,1375
8271 29.10.2003 0,0117 0,0142 0,0762 0,0032 0,0196 0,0100 0,0082 0,0034 0,0171 0,1526 0,0292 0,0366
8272 05.11.2003 0,0118 03173 1,2989 0,1534 0,0201 0,4371 0,1607 0,0105 0,1439 0,5881 0,0294 0,3179
8273 06.11.2003 0,0118 0,1555 0,7637 0,0356 0,0201 0,2258 0,0345 0,0168 0,3492 0,8492 0,0720 0,0386
8275 07.11.2003 0,0118 0,0142 10741 0,0035 0,0201 02639 0,0083 0,0034 0,0590 0,3640 0,5038 0,0386
8276 08.11.2003 0,0118 0,0306 0,2909 0,0261 0,0201 0,0389 0,0083 0,0034 0,1319 0,3162 0,2024 0,1024
8277 09.11.2003 0,0118 0,0583 0,2865 0,0130 0,0201 0,1074 0,0180 0,0034 0,0173 0,7151 0,0738 0,0386
B 278 10.11.2003 0,0118 0,0142 0,1642 0,0035 0,0201 0,0483 0,0083 0,0034 0,0173 0,2897 0,0294 0,0386
8279 11.11.2003 0,0118 00611 0,3209 0,0145 0,0201 01043 0,0083 0,0034 0,0173 0,4412 0,0294 0,1603
B 281 12.11.2003 0,0118 0,0947 0,3871 0,0185 0,0201 0,1563 0,0083 0,0034 0,0923 0,5101 0,0294 0,1058
B 282 13.11.2003 0,0118 0,0142 0,2280 0,0035 0,0201 0,0675 0,0083 0,0034 0,0475 0,8512 0,2575 0,0386
8 283 14.11.2003 00118 0,0142 0,5298 0,0086 0,0201 0,1260 0,0083 0,0034 0,0567 0,8153 0,0849 0,0386
B284 15.11.2003 0,0118 0,0142 0,2084 0,0283 0,0201 0,0392 0,0083 0,0034 0,0910 0,3458 0,0917 0,0386
8285 16.11.2003 0,0118 0,0533 0,8013 0,0241 0,0201 0,2751 0,0185 0,0034 0,0983 0,0895 0,0671 0,0386
B 287 17.11.2003 0,0118 0,0590 0,2966 0,0657 0,0201 0,0731 0,0083 0,0068 0,1184 0,2599 0,0294 0,0386
B 288 18.11.2003 0,0118 0,0142 0,0802 0,0174 00201 0,0101 0,0083 0,0034 0,0485 0,1628 0,1139 0,0386
B 289 19,11,2003 0,0118 0,0581 0,1391 0,0035 0,0201 0,0421 0,0083 0,0034 0,2158 0,2715 0,1008 0,0386
B 290 20.11.2003 00423 0,2699 13631 0,0139 0,0201 0,0579 0,0083 0,0034 0,0389 0,2723 0,0294 0,0386
B 291 21.11.2003 0,0118 0,2004 09070 0,0170 0,0201 0,3112 0,0347 0,0235 0,4225 0,2353 0,2128 0,0386
B 292 22.11.2003 0,0118 0,1089 0,6744 0,0083 0,0201 0,3012 0,0405 0,0196 0,3806 01423 0,0294 0,0386
B 293 23.11.2003 0,0118 0,1033 0,2597 0,0035 0,0201 0,1513 0.0083 0,0034 0,0173 0,0568 0,2568 0,0386
B 294 24.11.2003 0,0118 0,0650 0,1714 0,0035 0,0201 0,0995 0,0083 00034 0,0369 0,3350 0,0294 0,0386
B 295 25.11.2003 0,0118 0,0358 0,1227 0,0035 0,0201 0,0101 0,0083 0,0034 0,0173 0,2075 0,0294 0,0386
B 296 26.11.2003 0,0118 0,0469 0,0222 0,0146 0,0201 0,0101 0,0083 0,0215 0,0759 0,0981 0,0294 0,0386
B 297 27.11.2003 0,0118 0,0524 0,0551 0,0474 0,0201 0,0101 0,0083 0,0747 0,2887 0,0918 0,0294 0,0386
8 298 28.11.2003 0,0118 0,0142 0,0267 0,0035 0,0201 0,0101 0,0083 0.0034 0,0173 0,0614 0,2337 0,0386
B 299 29.11.2003 0,0118 0,0874 0,2393 0,0035 0,0201 0,0331 0,0083 0,0324 0,1561 0,4389 0,2716 0,0386
B 300 30.11.2003 0,0118 0,0142 0,8679 0,0098 0,0201 0,2897 0,0083 0,0122 0,0368 0,3096 0,4798 0,0386
8301 01.12.2003 0,0118 0,0321 0,1214 0,0100 0,0201 0,0299 0,0083 0,0299 0,1557 0,1040 0,0294 0,0386
B 302 02,12.2003 0,0118 0,1309 0,2787 0,0035 0,0640 0,1136 0,0370 0,0034 0,0173 0,2595 35002 0,0386
B 303 03.12.2003 0,0118 0,0142 0,6602 0,0035 0,0201 0,1808 0,0083 0,0034 0,0173 0,9772 5,8230 0,0386
B 304 04.12,2003 0,0118 0,3100 0,5582 0,0256 0,0409 0,1872 0,0699 0,0259 0,3153 0,3575 0,4046 0,3021
B 305 05,12.2003 0,0118 0,0505 0,1809 0,0245 0,0201 0,0524 0,0083 0,0034 0,0690 0,1276 0,2529 0,0386
B 306 07.12.2003 0,0118 0,2190 0,2651 0,0292 0,0201 0,0377 0,0197 0,0034 0,1396 0,1166 0,0900 0,0386
B 307 08.12.2003 0,0118 0,0142 0,1157 0,0035 0,0201 0,0382 0,0083 0,0034 0,0173 0,1046 0,0976 0,0386
B 308 09.12,2003 0,0118 00891 0,2110 00235 0,0201 0,0402 0,0083 0,0089 0,0788 0,1512 0,0901 0,0386
B 309 10,12.2003 0,0118 0,0142 0,1393 0,0035 0,0201 0,0260 00083 0,0034 0,0173 0,1037 0,3080 00386
8 311 11.12.2003 0,0118 0,0142 0,0363 0,0035 0,0201 0,0101 0,0083 0,0034 0,0173 0,0795 0,0294 0,0386
8312 12.12.2003 0,0118 0,0293 0,2772 0,0035 0,0201 0,0689 0,0083 0,0034 0,0173 0,2718 0,1143 0,0386
8313 13.12,2003 0,0118 0,0142 0,1019 0,0035 0,0201 0,0371 0,0083 0,0034 0,0173 0,1907 0,0294 0,0386
B 314 14,12,2003 0,0704 0,0935 0,0880 0,0123 0,0424 0,0208 0,0400 0,0034 0,0484 0,0846 0,0294 0,0386
8315 15,12.2003 0,0118 0,0142 0,0837 00035 0,0201 0,0335 0,0083 0,0034 0,0173 0,1024 0,0709 0,0386
B 317 16.12,2003 0,0118 0,0309 0,1380 0,0035 0,0201 0,0597 0,0083 0,0034 0,0173 0,0459 0,1496 0,0386

Page 4
 Annex

Aerosol and gases concentration values in pg pro Normcubicmeter Dec. 02-0ct. 04 Filter from 0 10 563

Aerosol (Anions) r~!INm'] Aerosol (Kations) [~ j1Nm'] Gas lualNm']

:~amples}"D.â~è;Ç~"Chloride -Nitrate Sulphatè:Ox!llate' Na ,NH4 K Mg Ca ~iI-!N.oir!;_:::SO~f'i) 'J'N.t13¥{
B 318 18.12.2003 0,0118 0,0737 0,4040 0,0148 0,0201 0,1419 0.0083 0.0034 0,0513 0,1070 0,1050 0,0386
B 319 19.12.2003 0,0118 0.0865 0,4111 0,0456 0,0462 0,1647 0.0083 0,0067 0.0418 0,1485 0,0294 0,0386
B 320 20.12.2003 0,0118 0,0587 0,3276 0,0072 0,0201 0,1335 0,0083 0,0034 0,0173 0.2143 0,0294 0,0386
B 321 21.12.2003 0,0118 0,0478 0,0528 0,0118 0,0201 0,0218 0,0083 0,0034 0,0173 0,0897 0,0294 0,0386
B 323 22.12.2003 0,0118 0,0778 0,2793 0,0035 0,0201 0,0846 0,0083 0,0034 0,0173 0,1046 0,0294 0,0386
B 324 23.12.2003 0,0118 0,1264 0,2205 0,0259 0,0201 0,0890 0,0083 0,0072 0,0173 0,0935 0,0611 0,0386
B 325 24.12.2003 0,0118 0,0853 0,3098 0,0119 0,0417 0,1129 0,0083 0,0069 0,0173 0,1154 0,0294 0,0386
B 326 25.12.2003 0,0118 0,1477 0,2285 0,0107 0,0201 0,0849 0,0083 0,0080 0,0678 0,1606 0,0663 0,0386
B 327 26.12.2003 0,0118 0,0695 0,0998 0,0035 0,0201 0,0448 0,0083 0,0034 0,0364 02863 0,1010 0,0386
B 329 03.01.2003 0,0058 0,0649 0,5131 0,0488 00217 01556 0,0028 0,0091 0,0950 0,0984 0,9009 0,0306
B 330 04.01.2003 0,0175 0,2028 0,5774 0,1595 0,0217 0,1439 0,0060 0,0240 0,2523 0,2308 0,2949 0,0306
B 331 05.01.2003 0,0371 0,1287 0,3061 0,1254 0,0581 0,0835 0,0178 0,0182 0,1776 0,1046 0,1455 0,0306
B 332 06.01.2004 0,0058 0,0709 0,2130 0,0717 0,0217 0,0558 0,0028 0,0091 0,1455 0,2380 0,1167 0,0306
B 333 07.01.2004 0,0058 0,0973 0,1968 0,0518 0,1693 0,0926 0,0066 0,0091 0,1031 0,2613 0,0843 0,0306
B 335 15.01.2004 0,0058 0,0584 0,0990 0,0104 0,0796 00467 0,0028 0,0091 0,0158 0,2048 0,2414 0,0306
B 336 16.01.2004 0,0170 0,0764 0,2342 0,0104 0,0900 0,0900 0,0162 0,0091 0,0662 0,3938 0,3565 0,0306
B 337 17.01.2004 0,0058 0,0246 0,0953 0,0104 0,0503 0,0467 0,0145 0,0091 0,0478 0,2930 0,1213 0,0306
B 338 18.01.2004 0,0058 0,0790 0,1717 0,0211 0.0217 0,0385 0,0028 0,0091 0,0671 0,3253 0,2496 0,0306
B 339 19.01.2004 0,0058 0,0246 0,0550 0,0104 0,0217 0,0267 0,0028 0,0091 0,0158 0,3625 0,1744 0,0306
B 341 20.01,2004 0,0119 0,1347 0,2239 0,0104 0,0217 0,0325 0,0028 0,0091 0,0444 0,1825 0,4355 0,0306
B 342 21.01.2004 0,0058 0,2440 0,6747 0,0329 0,0846 0,2593 0,0189 0,0091 0,2071 0,3452 0,3986 0,0306
B 343 22.01.2004 0,0058 0,0246 0,1485 0,0104 0,0217 0,0298 0,0028 0,0091 0,0158 0,0543 0,0131 0,0306
B 344 23.01,2004 0,0058 0,1273 0,2966 0,0104 0,0691 0,0657 0,0028 0,0091 0,1577 0,2031 0,1652 0,Q306
B 345 24.01.2004 0,0058 00631 0,1341 0,0104 0,0217 0,0213 0,0028 0,0091 0,0158 0,1240 0,1795 0,0306
B 347 25.01.2004 0,0058 0,0511 0,4157 0,0104 0,0217 0,1649 0,0074 0,0091 0,0158 0,1752 0,4695 0,0306
B 348 26.01.2004 0,0058 0,1019 0,6863 0,0104 0,0217 0,1142 0,0028 0,0091 0,0158 0,4060 0,0580 0,0306
B 349 27.01.2004 0,0058 0,0246 0,2448 0,0104 0,0217 0,0969 0,0108 0,0091 0,0156 0,1068 0,4241 0,0306
B350 28.01.2004 0,0058 0,0832 0,6158 0,0104 0,0217 0,1737 0,0066 0,0091 0,0158 0,3195 0,5686 0,0306
B 351 29.01.2004 0,0056 0,0877 0,3413 0,0226 0,0645 0,1341 0,0057 0,0091 0,0580 0,2180 0,3151 0,0306
B 353 30.01.2004 0,0058 0,0246 01023 0,0104 0,0217 0,0515 0,0028 0,0091 0,0158 0,1779 0,0131 0,0306
B 354 31,01.2004 0,0056 0,0619 0,1506 0,0104 0,0217 00197 0,0026 0,0091 0,0158 0,2531 0,1435 0,0306
B 355 01.02.2004 0,0407 0,1399 0,3678 0,0104 0,0757 0,0956 0,0142 0,0091 00612 0,2257 0,0639 0,0306
B 356 02.02.2004 0,0056 0,0583 0,1527 0,0104 0,0217 0,0549 0,0061 0,0091 0,0763 0,2225 0,0783 0,0306
B 357 03.02.2004 0,0203 0,0956 0,1685 00104 0,0542 0,0445 0,0026 00091 0,0728 0,2390 0,1081 0,0306
B 359 18.02.2004 0,0056 0,0246 0,0117 00104 0,0217 0,0075 0,0026 0,0091 0,0158 0,3094 0,6947 0,3488
B 360 19.02.2004 0,0058 0,0667 1,8856 0,0397 0,0217 0,5034 0,0409 0,0091 0,0158 0,3624 1,9680 0,0306
B 361 20.02.2004 0,0058 0,0246 0,1116 0,0104 0,0217 0,0366 0,0028 0,0091 0,0158 0,1630 0,0550 0,0893
B 362 21.02.2004 0,0056 0,0533 0,0117 0,0104 00217 00075 0,0026 0,0091 0,0158 0,0703 0,0488 0,1090
B 363 22.02.2004 0,0123 0,0246 0,0331 0,0254 0,0217 0,0075 0,0026 0,0091 0,0447 0,0739 0,0960 0,0652
B 365 23.02.2004 0,0211 0,2965 0,4311 0,0104 0,0217 0,0957 0,0214 0,0091 0,0777 0,0603 0,7122 0,0306
8 366 24.02.2004 0,0056 0,4369 0,2157 0,0845 0,6707 0,1781 0,0065 0,0444 0,1454 00661 0,1313 0,0306
8 367 25.02.2004 0,0058 0,0246 0,0561 0,0104 0,0217 0,0428 0,0028 0,0091 0,0339 0,2366 0,0702 00670
8 368 26.02.2004 0,0058 0,0938 0,2803 0,0104 0,0217 0,0857 0,0060 0,0091 0,1589 0,1646 0,1704 0,1153
8374 27.02.2004 0,0058 0,1926 1,4108 0,0276 0,0217 0,4833 0,0236 0,0091 0,1106 0,3827 1,0380 0,0306
8375 28.02.2004 0,0058 0,3494 0,7530 0,1438 0,1818 0,3668 00135 0,0091 0,0980 0,5732 0,7187 0,0306
8 376 29.02.2004 0,0625 0,3974 2,7442 0,1082 0,0822 0,9392 0,0456 0,0357 0,3795 1,5737 3,7843 0,0306
8377 01.03.2004 0,0058 0,0246 1,0305 0,0104 0,0217 0,3711 0,0060 0,0091 0,0347 0,6399 0,5484 0,0306
8379 02.03,2004 00056 0,1182 0,4546 0,0247 0,0775 0,1057 0,0028 0,0091 0,0333 0,2070 0,2105 0,0306
8380 03.03.2004 0,0058 0,1405 0,4831 00234 0,0217 0,1195 0,0028 0,0091 0,1960 0,3233 0,0352 0,0306
8381 04.03.2004 0,0058 0,4606 0,4362 0,0449 0,3200 0,2556 0,0104 0,0189 0,0939 0,4675 0,1481 0,0306
8 382 05.03,2004 0,0058 0,0616 0,2447 0,0104 0,0692 0,0926 0,0028 0,0091 0,1383 0,1175 0,0131 0,0306
B 383 06.03.2004 0,0056 0,0246 01805 00104 0,0217 0,1173 0,0026 0,0091 0,0158 0,3761 0,0487 0,0306
8385 07.03.2004 0,0134 0,7165 0,2915 0,0614 0,0217 0,1249 0,0072 0,0315 0,2276 0,1610 0,0712 0,0306
8 386 08.03.2004 0,0058 0,4650 1,1010 0,0532 0,0217 04504 00131 0,0091 0,0722 0,4375 0,5693 0,1020
8 387 09.03.2004 0,0056 26897 0,9127 0,1550 0,0217 05708 0,0110 0,0743 0,3357 0,6065 0,1316 0,0306
8388 10.03.2004 0,0056 0,5675 0,7611 0,0615 0,0217 0,2971 0,0058 0,0242 0,1050 0,8653 0,3329 0,0306
8389 11.03.2004 0,0058 0,2123 0,2951 0,0217 0,0217 0,0785 0,0028 0,0091 0,1164 0,2331 0,1490 0,0669
8391 12.03.2004 0,0058 0,6721 0,5165 0,1143 0,0217 0,2636 0,0061 0,0294 0,1328 0,7074 0,2016 0,0306
8392 13.03.2004 0,0662 0,8318 1,6646 0,0786 0,0217 0,4086 0,0426 0,0666 2,2701 0,4736 0,1004 0,1376
8 393 14.03.2004 0,0058 0,5550 07211 0,0583 0,0217 02448 0,0089 0,0212 0,3449 0,3997 0,0543 0,1809
8394 15.03.2004 0,0167 0,2422 03003 0,0307 0,0217 0,0633 0,0028 0,0091 0,0681 0,1943 0,2670 0,0787
8 395 16.03.2004 0,0058 0,0545 0,2795 0,0104 0,0217 0,0801 0,0028 0,0091 0,0156 0,2179 0,1536 0,1050
B 397 17.03.2004 0,0150 0,2926 0,2592 00414 0,0217 0,0670 0,0060 0,0213 0,2698 0,2624 0,0765 0,2061
8398 18.03.2004 0,0121 0,7983 0,4062 0,0655 0,0217 02165 0,0161 0,0390 0,2954 0,4336 0,1226 0,4505
8 399 19.03.2004 0,0058 2,4373 0,5980 0,0425 0,0217 1,2154 0,0406 0,0304 0,2111 2,1725 0,4218 09167
B 400 20.03.2004 0,0058 1,1568 1,3331 0,0771 0,0217 0,2939 0,0152 0,0091 0,0914 2,1570 0,2806 0,1853
B 401 21.03.2004 0,0237 1,9484 0,6376 0,0784 0,0217 0,3150 0,0094 00564 0,2703 1,2612 0,1048 0,3922
B 403 22.03.2004 0,0058 0,0747 0,0257 0,0104 0,0217 0,0181 0,0026 0,0091 0,0712 0,1213 0,1263 0,1399

Page 5
 Annex

Aerosol and gases concentration values in Ilg pro Normcubicmeter Dee, 02-0et. 04 Filter from 0 to 563

Aerosol (Anions) [IJ~INm'} Aerosol (Kations) IlJoINm'] Gas [1Jg/Nm'j-

:~ainJlI,ès F~;Oàte,:':\' C!1loriifè Nitrate Sulphate Oxalàte : Nà NH4 K Mg 'Ca, }:Ht'lP~1;iJ0~9~
.K'~}
. ;:/NHi>,
8404 23,03,2004 0,0234 0,4151 0,1423 0,0668 0,0217 0,0234 0,0057 0,0472 0,4194 0,1628 0,1399 0,0996
8405 24.03,2004 0,0058 0,1993 0,3274 0,0104 0,0217 0,0749 0,0028 0,0091 0,1768 0,1236 0,7848 0,0306
8 406 25.03,2004 0,0153 0,4310 0,8982 0,0329 0,0217 0,0963 0,0028 0,0091 0,1219 0,1376 0,1923 0,0306
8407 03.04.2004 0,0150 1,0424 2,6258 01229 0,0190 0,5152 0,0168 0,0343 0,5188 1,3410 0,0839 0,5504
8409 04,04,2004 00056 0,1629 0,8943 0,0379 0,0190 0,3724 0,0122 0,0105 0,1080 1,0805 0,1162 0,3329
8410 05,04,2004 0,0125 1,1946 0,7876 0,0528 0,0190 0,1637 0,0031 0,0105 0,1149 0,3586 0,0356 0,2434
8411 06,04.2004 0,0335 0,0653 0,1092 0,0134 0,0190 0,0165 0,0031 0,0105 0,1807 0,0555 0,0356 0,1000
8412 07.04,2004 0,0127 0,0653 0,3137 0,0358 0,0190 0,0907 0,0031 0,0105 0,1443 0,2364 0,0356 0,0774
8413 08.04.2004 0,0056 0,3699 0,5438 0,0134 0,0190 0,1949 0,0031 0,0105 0,0245 0,8031 0,1963 0,0378
8415 09.04.2004 0,0056 0,0653 0,8733 0,0285 0,0190 0,2453 0,0076 0,0105 0,1105 0,5488 0,2079 0,0378
8416 10.04,2004 0,0240 0,0653 0,5495 0,0399 0,0190 0,1241 0,0098 0,0105 0,0727 0,2859 0,1626 0,0378
8418 12.04.2004 0,0056 0,1361 1,1531 0,0540 0,0190 0,2296 0,0031 0,0105 0,0796 0,2669 0,1068 0,0378
8419 13.04.2004 0,0125 0,0653 1,3648 0,0357 0,0190 0,2670 0,0031 0,0105 0,1310 0,3847 0,7414 0,0378
8421 14.04.2004 0,0056 0,0653 1,2669 0,0411 0,0190 0,3483 0,0098 0,0105 0,0883 0,4233 0,3071 0,0378
8422 15.04.2004 0,0260 0,2202 0,2109 0,1903 0,0190 0,0399 0,0031 0,0334 0,1267 0,1284 0,0356 0,0378
8423 16.04.2004 0,0157 0,0653 0,1970 0,0134 0,0190 0,0165 0,0074 0,0105 0,0776 0,1246 0,1949 0,1518
8424 17.04.2004 0,0166 0,4284 0,6367 0,1084 a 0190 0,1048 0,0031 0,0348 0,1638 0,3018 0,0803 0,6569
8425 18.04.2004 0,0143 0,2630 0,0368 0,3351 0,0190 0,0165 0,0031 0,0540 0,1657 0,0555 0,1331 0,1162
8427 19.04.2004 0,0142 0,0653 0,1064 0,0134 0,0190 0,0165 0,0031 0,0105 0,0558 0,0555 0,0356 0,0378
8428 20.04.2004 0,0135 0,0653 0,4224 0,0734 0,0190 0,1294 0,0031 0,0105 0,1069 0,4387 0,0356 0,2197
8429 21.04.2004 0,0149 0,0653 0,6362 0,0307 0,0190 0,1680 0,0100 0,0105 0,0662 0,3601 0,1031 0,0378
8430 22.04.2004 0,0056 0,5444 0,6417 0,0486 0,0190 0,2367 0,0150 0,0105 0,0245 1,1480 0,2349 0,7640
8431 23.04.2004 0,0056 0,2989 0,7415 0,1215 0,0190 0,2335 0,0100 0,0212 0,0786 1,5651 0,0960 0,4608
8433 24.04,2004 0,0056 0,0653 0,2212 0,0701 0,0190 0,0749 0,0031 0,0105 0,0245 0,2621 0,0896 0,2336
8434 25.04.2004 0,0056 0,0653 0,2542 0,0134 0,0190 0,0732 0,0031 0,0105 0,0245 0,1309 0,0356 0,0378
8435 26.04.2004 0,0056 0,3908 1,6290 0,1452 0,0190 0,6374 0,0142 00224 0,1127 0,6260 0,0356 0,1392
8436 27.04.2004 0,0229 0,7033 1,5299 0,2212 0,0190 06563 0,0210 0,0253 0,1109 0,9832 0,0356 0,5851
8437 28.04.2004 0,0056 0,2419 0,9261 0,0789 0,0190 0,7914 0,0173 0,0105 0,0759 1,5590 0,1316 0,3967
8439 29.04.2004 0,0056 0,0653 0,9845 0,0134 0,0190 0,2563 0,0031 0,0105 0,0245 0,6840 0,1790 0,1137
8440 30.04.2004 00330 0,1877 00645 0,0702 0,0190 0,0165 0,0031 0,0105 0,0603 0,0555 00356 0,0378
B441 01.05.2004 0,0056 0,2136 0,2810 0,1193 0,0190 0,0796 0,0031 0,0105 0,0490 0,4713 0,1061 0,0378
B442 02,05.2004 0,0056 0,0653 1,0166 0,0524 0,0190 0,1636 0,0031 0,0105 0,0245 0,6050 0,2026 0,0378
8443 03.05.2004 0,0056 0,3382 0,3627 0,1115 0,0190 0,0592 0,0031 0,0105 0,0720 0,2003 0,1168 0,1301
B 444 04.05.2004 0,0056 0,0653 0,0577 0,0134 0,0190 0,0165 0,0031 0,0105 0,0245 0,0555 0,3043 0,1532
8 445 05.05.2004 0,0056 0,0653 0,0459 0,0134 0,0190 0,0165 0,0031 0,0105 0,1205 0,1242 0,0946 0,2011
B 446 06.05.2004 0,0056 0,0653 0,2335 0,0134 0,0190 0,0475 0,0031 0,0105 0,0245 0,2135 0,0356 0,1220
B 447 07.05.2004 0,0304 0,0653 0,2255 0,0432 0,0190 0,0420 0,0071 0,0105 0,1026 0,2696 0,0934 0,0378
B 448 08.05.2004 0,0141 0,0653 0,1595 0,0300 0,0190 0,0366 0,0031 0,0105 0,1323 0,4008 0,0356 0,0378
B 449 09.05.2004 00056 0,0653 0,0754 0,0611 0,0849 0,0334 0,0031 0,0105 00245 0,2478 0,1193 0,2352
B 451 10.05.2004 0,0056 0,0653 0,6230 0,0304 0,0190 0,2291 0,0031 0,0105 0,0245 0,9565 0,0356 0,0378
B 452 12.05.2004 0,0056 0,4266 0,6385 0,0505 0,0190 0,1968 00031 0,0105 0,0245 0,9545 0,0356 0,5810
B 453 13.05.2004 0,0056 0,4153 0,0637 0,0698 0,0190 0,0165 0,0031 0,0105 0,0245 0,4460 0,0356 0,5330
8 454 14.05.2004 0,0056 0,4072 0,2978 0,0925 0,0190 0,1268 0,0031 0,0105 0,0688 0,8911 0,0356 0,8363
B 455 15.05.2004 0,0957 2,3273 0,0093 0,2183 0,0190 0,1587 0,0031 0,0245 0,1803 0,2842 0,0356 1,1718
B 457 16.05.2004 0,0056 0,4390 0,0768 0,0640 0,0190 0,0165 0,0031 0,0105 0,0952 0,3165 0,0356 0,3243
B 458 17.05.2004 0,0056 0,4078 0,3754 0,0516 0,0190 0,1426 0,0031 0,0105 0,0245 0,7327 0,0356 1,0532
B 459 18.05.2004 0,0056 1,9052 1,6512 01901 0,0190 0,6589 0,0126 0,0105 0,1042 2,2620 0,1839 0,8785
8 460 19.05.2004 0,0148 2,7273 4,0515 0,2172 0,0190 1,6005 0,0305 0,0211 0,1150 3,6980 0,2759 0,9920
8 461 20.05.2004 0,0056 2,4353 3,6256 0,2311 0,0190 1,2985 0,0220 0,0227 0,1422 2,4648 0,2804 0,8549
B 463 21.05.2004 0,0056 0,4436 1,1726 0,1564 0,0190 0,4855 0,0072 0,0105 0,1165 2,4117 0,0356 1,3672
B 464 22.05.2004 0,0056 0,5062 0,0713 0,0318 0,0190 0,0165 0,0031 0,0105 0,0245 0,4154 0,0356 0,2287
B 465 23.05.2004 0,0284 1,7186 0,6209 0,1016 0,0190 0,2653 0,0031 0,0238 0,2078 0,6353 0,0356 0,7690
8466 24.05.2004 0,0056 0,8487 0,7920 0,1331 0,0190 0,3716 0,0102 0,0105 0,0840 0,7462 0,1879 0,1891
8 467 25.05.2004 0,0268 0,4757 1,3292 0,0794 0,0190 0,3116 0,0077 0,0105 0,0245 1,9479 0,1022 0,2878
B 469 05.06.2004 0,0056 0,3206 0,2666 0,1084 08933 0,2044 0,0031 0,0427 0,3321 06537 0,1162 0,2109
8470 06.06.2004 0,0056 0,0653 0,2704 0,0629 0,0190 0,0165 0,0031 0,0105 0,0245 0,5561 0,1194 0,0378
8 471 07.06.2004 0,0056 0,1325 04959 0,1120 0,0190 0,1701 0,0031 0,0105 0,0245 0,9817 0,0356 0,0997
8472 08.06.2004 0,0056 0,2400 0,8779 0,1640 0,0190 0,3131 0,0105 0,0105 0,0245 1,6128 0,1424 0,2725
B 473 09.06.2004 0,0056 0,5490 0,9978 0,1904 0,0190 0,3959 0,0130 0,0105 01077 2,1119 0,2967 0,0378
8 475 10.06.2004 0,0056 0,0653 1,8076 0,0134 0,0190 0,4490 00151 0,0105 00687 19204 0,3350 0,8080
8 476 11.06.2004 0,0138 1,0119 1,6358 0,2354 0,0190 0,5125 0,0031 0,0518 02677 1,5416 0,1626 0,9297
8477 12.06.2004 0,0056 2,0080 0,1756 0,1910 0,0190 0,1481 00031 0,0629 0,2816 0,7095 0,0356 0,4237
B 478 13.06.2004 0,1501 11,6574 0,0230 0,6046 0,0190 0,8632 0,0031 0,3516 1,5788 0,4538 0,0356 0,2615
8 479 14.06.2004 0,0056 0,2899 0,6167 0,0698 0,0190 0,2271 0,0031 0,0105 00245 0,7501 0,1021 0,4324
8481 15.06.2004 0,0056 0,6999 1,4799 0,1170 0,0190 0,3277 0,0031 0,0251 0,1413 1,4296 0,0979 0,4473
8482 16,06,2004 0,0112 0,5912 0,4765 0,0134 0,0190 0,1503 0,0031 0,0368 0,1664 1,3864 0,0356 0,4657
8483 22.06.2004 0,0056 0,1745 0,9055 0,0658 0,0190 0,1960 0,0031 0,0105 0,0245 1,5820 0,0992 0,3956
8484 23.06.2004 0,0056 0,3118 0,6237 0,0869 0,0190 0,2327 0,0031 0,0105 0,0245 1,3641 0,0356 0,5665

Page 6
 Annex

Aerosol and gases concentration values in ~g pro Normcubicmeter Dec. 02-0ct. 04 Filter from 0 to 563

Aerosol (Anions) [~\ INm'] Aerosol (Kations) ru [l/Nm'] Gas [~g/Nm'l

Samphis :i;",~Dätiî,.$~
ChlorldèNitrate Sulphate 'Oxalate .Na: .. NH4. K .• Mg .Ca !.Ht:Jo.3;~ ~~.:S:oi:j.: ,;>'~H3':%
B 485 24.06.2004 0,0056 1,7330 0,0093 0,0408 0,0190 0,0401 0,0031 0,0414 0,3364 0,2388 ". 0,2347 0,7024
B 487 25.06.2004 0,0209 1.2311 0,4254 0.1364 0,0190 0,3255 0,0070 0,0909 0.3804 0,9006 0,0754 0,8069
B 488 26.06.2004 0,0056 0,1347 1,1951 0,0624 0,0190 0,4015 0,0091 0,0105 00245 1,5600 0,1168 0,4768
B 489 27.06.2004 0,0269 0,9559 3,2167 0,1307 0.0190 0,9223 0,0031 0,0267 0,1169 2,1645 0,2025 0,4141
B 490 28.06.2004 0,0056 0,2453 2,1037 0,1058 0,0190 0,5115 0,0065 0,0105 0,0245 1,2768 0,0768 0,2373
B 491 29.06.2004 0,0056 0,3646 1,3770 0,1601 0,0190 0,5222 0,0111 0,0105 0,0245 1,7532 0,1389 0,4097
B 493 01.07.2004 0,0056 0,1674 0,8930 0,0755 0,0190 0,5642 0,0085 0,0105 0,0245 1,8641 0,1750 0,6971
B 494 02.07.2004 0,0056 0,8774 0,1092 0,0134 0,0190 0,2282 0,0031 0,0483 0,3312 1,1556 0,1496 0,2329
B 495 03.07.2004 0,0056 0,5408 0,5286 0,0879 0,0780 0,2331 0,0031 0,0215 0,1815 1,2527 0,1013 0,2551
B 496 04.07.2004 0,0056 6,0266 0,0391 0,1072 0,0190 0,0165 0,0672 0,0105 0,0245 3,5848 0,1059 0,5213
B 497 05.07.2004 0,0056 0,2919 2,0779 0,1127 0,0190 0,8553 0,0211 0,0105 0,0937 2,0433 0,0937 0,4976
B 499 11.07.2004 0,0056 0,5433 0,2106 0,0564 0,0190 0,0500 0,0031 0,0233 0,1863 0,4159 0,1643 0,0939
B 500 12.07.2004 0,0056 0,2195 0,1718 0,0422 0,0190 0,0165 0,0031 0,0105 0,1074 0,3649 0,1240 0,1575
B 501 13.07.2004 0,0056 0,0653 0,1318 0,0134 0,0190 0,0165 0,0031 0,0105 0,0245 0,4643 0,1429 0,0378
B 502 14.07.2004 0,0056 0,4648 0,8244 0,1152 0,0190 0,1595 0,0078 0,0105 0,3182 0,8474 0,1911 0,2285
B S03 15.07.2004 0,0056 0,0653 0,1785 0,0432 0,0190 0,0364 0,0031 0,0105 0,0245 0,0555 0,0356 0,2997
B 505 16.07.2004 0,0137 0,5717 0,4832 0,1119 0,0190 0,0833 0,0072 0,0474 0,7255 0,7298 0,2695 0,2754
B 506 17.07.2004 0,0175 1,2276 1,0425 0,1636 0,0190 0,2829 0,0031 0,0475 0,2917 0,9958 0,2340 0,4061
B S07 18.07.2004 0,0056 0,2411 3,6397 0,2241 0,0190 1,3684 0,0239 0,0105 0,0245 3,0966 0,2947 0,8351
B 508 19.07.2004 0,0122 0,7368 3,3278 0,2020 0,0190 0,9886 0,0251 0,0395 0,3099 1,9961 0,7882 0,6062
B S09 30.07.2004 0,0056 0,5645 2,4856 0,1971 0,0190 0,7519 0,0316 0,0105 0,0245 3,1743 0,0878 0,7904
B 511 31.07.2004 0,0056 0,3925 3,6146 0,2158 0,0190 1,4355 0,0525 0,D105 0,0245 1,6976 0,2123 1,2401
B 512 01.08.2004 0,0056 3,6067 0,0492 0,0134 0,0190 2,1367 0,0156 0,0105 0,0245 4,1266 0,1115 0.6671
B 513 02.08.2004 0,0056 0,4811 3,8896 0,2196 0,0190 1,4484 0,0594 0,0105 0,0245 3,5441 0,0903 0,8312
B 514 03.08.2004 0,0056 0,5824 4,2711 0,2280 0,0190 1,0041 0,0517 0,0105 0,0245 2,9577 0,2392 1,1209
B 515 04.08.2004 0,0056 0,1996 2,4456 0,1345 0,0190 0,6682 0,0232 0,0105 0,0245 0,7063 0,0356 0.2933
B 517 05.08.2004 00056 0,0653 1,5498 0,0761 0,0190 0,4835 0,0153 0,0105 0,0245 1,4246 0,1099 0,3305
B 518 06.08.2004 0,0056 0,3627 4,8456 0,2199 0,0190 1,6920 0,0673 0,0105 0,0245 4,5245 0,2033 0,9906
B 519 07.08.2004 0,0056 0,8792 4,2216 0,2043 0,0190 1,2814 0,0451 0,0105 0,0245 2,9242 0,5137 0,9390
B 520 08.08.2004 00056 0,4991 4,3846 0,1818 00190 1,3469 0,0398 0,0105 0,0245 2,5760 0,1652 0,4693
B 521 09.08.2004 0,0056 0,1715 2,1118 0,1379 0,0190 0,6861 0,0166 0,0105 0,0245 2,7839 0,1833 0,2749
B 523 10.08.2004 0,0056 0,1867 1,6131 0,1076 0,0190 0,3169 0,0153 0,0105 0,0245 1,8394 0,2209 0,5776
B 524 03.09.2004 0,0056 0,0653 1,7467 0,0908 0,0190 0,6401 0,0192 0,0105 0,0245 1,4655 0,0928 0,6578
B 525 04.09.2004 0,0056 1,6181 0,8276 0,0290 0,0190 0,4692 00031 0,0105 0,0245 1,8576 0,0356 0,2009
B 526 05.09.2004 00056 0,0653 17522 0,0645 00190 0,6922 0,0123 0,0105 0,0245 0,0555 0,0356 0,3561
B 527 06.09.2004 0,0056 0,0653 0,3211 0,0134 0,0190 0,0816 0,0031 0,0105 00245 0,3790 0,1509 0,1168
B 529 07.09.2004 0,0056 0,0653 0,7168 0,0328 0,0190 0,2189 0,0132 0,0105 0,5377 1,0536 0,1567 0,4168
B 530 08.09.2004 0,0056 0,3095 14700 0,0313 0,0190 0,4392 00102 0,0105 0,2033 16342 0,4919 0,7958
B 531 09.09.2004 0,0056 0,0653 0,3213 0,0134 0,0190 0,0593 0,0031 0,0105 0,0245 0,6988 0,2347 0,6350
B 532 10.09.2004 0,0056 0,2214 0,8385 0,0293 0,0190 0,3222 0,0088 0,0105 0,3259 0,9663 0,2084 0,4863
B 533 11.09.2004 0,0056 0,3506 21066 0,1002 0,0190 0,6828 0,0342 0,0105 0,3104 1,4452 0,0733 0,3675
B 535 12.09.2004 0,0056 0,0653 0,6794 0,0806 0,0190 0,1882 0,0079 0,0105 0,0245 0,8419 0,0356 0,5513
B 536 13.09.2004 0,0056 0,0653 0,6161 0,0134 0,0190 0,1535 0,0031 0,0105 0,0245 1,1595 0,2097 0,2539
B 537 14.09.2004 0,0056 0,0653 00093 0,0334 00190 0,0165 0,0031 0,0105 0,0245 0,4475 0,5612 0,1462
B 538 15.09.2004 0,0152 3,9651 0,0565 0,2694 0,0190 0,0973 0,0031 0,1058 0,5149 0,5953 0,1285 0,0378
B 539 16.09.2004 0,0056 1,0973 01297 01194 0,0190 0,0165 0,0031 0,0369 0,1631 0,4661 0,1201 0,0378
B 541 17.09.2004 0,0056 0,9770 0,2591 0,1979 0,0190 0,1505 0,0031 00341 0,1275 0,5652 0,1386 0,2866
B 542 18.09.2004 0,0056 0,4235 0,4019 0,1093 0,0190 0,1545 0,0031 0,0105 0,1139 0,0555 0,1008 0,1511
B S44 19,09.2004 0,0056 0,0653 0,5717 0,0572 0,0190 0,0524 0,0031 0,0105 0,0245 1,0959 0,3708 0,4919
B S45 20.09.2004 0,0056 0,2745 0,9639 0,0398 0,0190 0,3848 0,0031 0,0105 0,0245 1,8496 0,1277 0,3603
B 547 21.09.2004 0,0269 0,1333 0,6678 0,0285 0,0190 0,1990 0,0077 0,0105 0,2948 0,8615 0,0740 0,2444
B 548 22.09.2004 0,0307 0,1908 0,3785 0,0134 0,0387 0,0165 00061 0,0105 0,6366 0,3289 0,1023 0,1177
B 549 23.09.2004 0,0056 0,0653 0,0547 0,0134 00190 0,0165 0,0031 0,0105 0,0245 0,3063 0,0810 0,1401
B 5SO 24.09.2004 0,0056 0,0653 0,0651 0,0134 0,0190 0,0165 0,0031 0,0105 0,0245 0.1340 0,0356 0,0378
B 551 25.09.2004 0,0056 0,0653 00282 0.0134 0,0190 0,0165 0,0031 0,0105 00245 0,1930 0,0843 0,0378
B 553 26.09.2004 0,0056 0,0653 0,1076 0,0134 0,0190 0,0165 0,0031 0,0105 0,0245 0.3278 0,0356 0,0378
B 554 27.09.2004 0,0056 0,0653 0,2078 0,0134 0,0190 0,0541 0,0031 0,0105 0,0245 0,3168 0,0356 0,0378
B 555 29.09.2004 0,0056 0.0653 0,2337 0,0134 0,0190 0,0523 0,0031 0,0105 0,0245 0,4525 0,0356 00893
B 556 30.09.2004 0,0056 0,0653 0,2056 0,0134 0,0190 0,0511 0,0031 0,0105 0,0245 0,3869 0,0356 0,0378
B 5S7 01.10.2004 0,0056 0,0653 0,4572 0,0134 0,0190 0,1044 0,0031 0,0105 0,0245 0,6772 0,0356 0,3189
B 559 02.10.2004 0,0056 0,0653 11360 0,0586 0,0190 0,4216 0,0133 00105 0,0245 1,2624 0,0356 0,2980
B 560 03.10.2004 0,0056 0,0653 1,4469 0,0651 0,0190 05054 0,0155 0,0105 0,0245 1,4949 0,0356 0,2840
B 561 04.10.2004 0,0056 0,0653 0,9896 0,0479 0,0190 0,3751 00171 0,0105 0,0507 0,8498 0,0356 0,0812
B 562 05.10.2004 0,0056 0,2148 1,5984 0,0847 0,0190 0,5644 0,0350 0,0105 0,1747 1,0517 0,0356 0,4042
B 563 06.10.2004 0,0056 0,6646 2,3687 0,1070 0,0190 0,9290 0,0448 0,0105 0,3678 1,5591 0,0356 0,5704

Page 7
 Annex

Aerosol and gase monthly average in /lg pro Normeubiemeter Dee 02-0cI04 Filler from 0 10 563

Aerosol (Anions) [IJ~ INm'] Aerosol (Kalions) ru ~/Nm'l Gas [lJg/Nm'!

({~~iitti~~i 'Ctilorid. Nitrat Sufa~ Oxalat- 'Na' . ."NH4: K Mg Ca ',~J::i~P.~'\~~
;::?;<.~O~;\'~'I,:~.~~H,~.;»
Dec.02 0.010 0,030 0.087 0.004 0.020 0,034 0.006 0.003 0.027 0,057 0,104 0.121
Jan.OJ 0,000 0,000 0.000 0,005 0,000 0,000 0,000 0,000 0,000 0,047 0,223 0.044
Feb.03 0,000 0,000 0,000 0,013 0,000 0,000 0.000 0.000 0,000 0,103 0,131 0,047
March OJ 0,014 0,445 0,319 0,019 0,030 0,114 0,011 0,002 0,034 0,122 0,205 0,301
Apr.03 0,016 0,827 1,037 0,047 0,033 0,515 0.035 0,008 0,090 0.212 0,238 0,490
Mav03 0,046 0,501 0,923 0,030 0,053 0,303 0,036 0,011 0,090 0,146 0,073 0,418
Jun,OJ 0,031 0,541 1,311 0,104 0,037 0,461 0,023 0,016 0,242 0,353 0.192 0,692
Jut,OJ 0,038 0,189 0,974 0,065 0,033 0,346 0,018 0,010 0,287 1,055 0,242 0,654
Aug.03 0,013 0,527 1,799 0,144 0,036 0,656 0,059 0,032 0,474 1,269 0,303 0.895
Sep.03 0,012 0.073 0,595 0,030 0,019 0,266 0,016 0,006 0,068 0,858 0,152 0.361
Oct.OJ 0.013 0,026 0,377 0,009 0,020 0,137 0,009 0,003 0,033 0,409 0,125 0,064
Nav,OJ 0,014 0,075 0,390 0,017 0,020 0.108 0,013 0.014 0,129 0,211 0.127 0,039
Dec,OJ 0,014 0,077 0,233 0,012 0,026 0,076 0,014 0,006 0,052 0,183 0,479 0,050
Jan,04 0,009 0,084 0,295 0,031 0,044 0,088 0,007 0.010 0,072 0,231 0,267 0,031
Feb.04 0,014 0,152 0,577 0,035 0,085 0,197 0,013 0,013 0,088 0,316 0,651 0,071
March 04 0,012 0,624 0,573 0,048 0,038 0,240 0,009 0,023 0,245 0,531 0,211 0,137
ADr.04 0,013 0,261 0,730 0.075 0.019 0,224 0,007 0,016 0,106 0,528 0,130 0,206
May04 0,013 0,690 0,744 0,091 0,022 0,266 0.006 0,013 0,076 0,906 0,104 0,462
Jun.04 0,015 1,113 0,836 0,134 0,063 0,318 0,005 0,041 0,191 1,247 0.125 0,422
Jut.04 0,007 0,812 1.235 0,111 0,023 0,443 0,017 0,021 0,170 1,484 0,199 0,449
Aug.04 0.007 0,437 1,235 0,078 0,019 0,447 0,015 0,014 0,106 1,262 0,137 0,367
Sep,04 0,007 0,356 0,719 0,056 0,020 0,247 0,009 0,015 0,131 0,814 0,121 0,281

Page 8
 Annex

Average, rredian, rmxim.m and rrinim.m

;Ji: NOj'~t: max. nin Average M!dian <.1~,,:SQ.2:.~~~ max. rrin Aver.I9ll M!dian (H;v:,;.) tnaK. nin Average M!dian
Dee. 02 1,7 0,2 0,5 0,3 Dee. 02 2,8 0,0 0,9 0,7 Dee. 02 6,2 0,3 1,9 1,6
Jan. OJ 10,0 0,4 1,2 0,5 Jan. OJ 3,3 0,3 1,7 1,9 Jan. OJ 6,8 0,8 2,5 1,8
Feb.OJ 2,3 0,2 0,6 0,2 Feb.OJ 18,6 0,0 4,6 4,3 Feb.OJ 18,5 0,4 5,7 5,1
Mär.OJ 72,2 0,2 7,2 1,3 Mär.OJ 19,6 0,0 3,3 2,2 Mär.OJ 17,6 0,4 6,3 5,4
IAIr.OJ 44,3 0,2 13,3 8,0 AIr.OJ 27,4 0,7 10,8 9,2 IAlr.OJ 80,0 1,5 28,6 23,7
MaI.OJ 27,9 0,2 8,1 7,3 MaI.OJ 3),4 0,3 9,6 9,2 MaI.OJ 32,1 0,4 16,9 19,4
JunOJ 27,7 0,8 8,7 5,7 JunOJ 42,7 2,0 13,7 11,5 JunOJ 61,9 1,1 25,6 2fJ,7
JuI.OJ 11,7 0,2 3,2 2,4 Jut.OJ 31,3 0,0 10,8 8,0 JuI,OJ 59,5 D,S 19,7 15,4
Aug.OJ 31,1 0,2 9,0 5,5 Aug.OJ 72,7 0,1 19,8 16,2 AuaOJ 124,8 1,4 38,5 35,1
I~OJ 3,0 0,2 1,2 1,0ISenOJ 16,:;; 0,4 6,2 4,8 ~OJ 33,6 0,8 14,8 12,9
OId.OJ 4,0 0,2 0,8 0,3 OId.OJ 7,7 0,1 3,4 3,4 OId.OJ 17,2 0,8 6,2 5,1
Nov.OJ 5,1 0,2 1,2 0,9 Nav.OJ 14,2 0,2 4,6 3,0 Nov.OJ 24,3 0,6 7,0 4,8
Dez.OJ 5,0 0,2 1,2 1,0 Dez.OJ 6,9 0,4 2,4 2,2 Dez.OJ 10,4 0,6 4,2 3,1
Jän.04 3,9 0,4 1,3 1,1 Jän.04 7,1 0,6 3,1 2,4 Jän.04 14,4 1,1 4,9 4,1
Feb.04 7,1 0,4 2,4 1,5 Feb.04 19,6 0,1 4,4 2,1 Feb.04 52,2 0,4 10,9 4,8
Mir.04 43,4 0,4 10,1

•
7,0 Mär.04 17,3 0,3 6,0 4,7 Mär.04 67,5 2,4 16,4 13,6
Apr.04 19,3 1,1 4,2 2,2 Alr.04 27,4 0,4 7,6 6,6 ADr.04 44,0 0,9 12,4 9,3
MaI.04 44,0 1,1 11,1 6,6 MaI.04 42,2 0,1 7,8 3,4 MaI.04 88,9 0,9 14,8 7,5
Jun04 32,4 1,1 9,0 5,0 Jun04 33,5 0,1 8, 6,5 Jun04 51,2 0,9 17,7 15,2
JuI.04 97,2 1,1 13,1 8,1 JuI.04 37,9 0,4 12,9 7,0 JuI.04 79,8 0,1 24,5 12,8
Aug.04 58,2 1,1 11,3 6,8 Aug.04 50,5 D,S 3>,6 33,0 Aug.04 118,7 17,6 61,S 63,5
~04 64,0 1,1 6,3 1,1 Sen04 21,9 0,1 6,1 3,9 Sep.04 38,5 0,9 10,8 5,4
0Id.04 10,7 1,1 3,1 1,1 0Id.04 24,7 4,8 13,9 13,5 0Id.04 51,6 5,8 26,9 25,8

',(i:itA\,i max. nin Average M!dian i~t~.;.~ /JBlC, rrin Aver.I9ll Nt!dan ,'~:.~"Ib~ /JBlC, nin Average M!dian
Dee. 02 3,4 0,1 0,9 0,4 Dee. 02 3,8 0,3 1,6 1,3 Dee. 02 16,1 2,0 7,1 6,1
Jan. OJ 3,2 0,1 0,7 0,7 Jan. OJ 9,9 0,3 1,8 D,S Jan. OJ 10,2 2,0 2,6 2,0
Feb.OJ 7,3 0,2 2,2 2,7 Feb.OJ 8,7 0,5 2,1 0,7 Feb.OJ 13,5 2,6 3,1 2,6
Mir.OJ 5,4 0,2 1,9 1,2 Mär.OJ 5,5 0,5 1,8 1,2 Mär.OJ 53,( 2,€ 17,7 15,7
Apr.OJ 15,4 0,5 3,4 2,2 Apr.OJ 15,8 0,5 3, 2,3 IApr.OJ 83,5 2,6 28,8 22,0
MaI.OJ 4,2 0,5 2,3 2,5 MaI.OJ 3,2 D,S 1,2 0,8 MaI.OJ 55,1 2,4 24,6 22,3
JunOJ 10,8 0,2 5,6 5,2 JunOJ 10,2 0,5 3,0 2,5 JunOJ 68,9 21,3 40,7 37,1
JuI,OJ 49,2 0,2 16,6 12,1 Jut.OJ 13,4 1,2 3,9 3,8 JuI.OJ 93,2 15,7 40,6 36,9
Aug.OJ 79,3 0,2 2fJ,6 16,5 Aug.OJ 16,3 0,4 4,9 3,4 Aug.OJ 134,1 20,4 54,6 51,7
1Sep.0J 42,0 0,2 13,6 12.0 Sep.03 5,6 0,4 2,4 2.0 1Sep.0J 42,3 2,2 21,3 17,8
OId.OJ 22,5 1,0 6,7 5,2 0Id.03 10,1 0,5 2,! 2,0 0Id.03 39,9 2,2 6,6 2.2
Nov.03 13,5 0,9 5,4 4,8 Nav.03 7,9 0,5 2,0 1,1 Nov.03 18,7 2,3 3,5 2,3
Dez.03 15,5 0,7 2,9 1,8 Dez.OJ 6,3 0,5 1,5 1,1 Dez.03 17,8 2.3 2,9 2,3
Jän.04 6,5 0,9 3,9 3,8 Jän.04 8,9 0,2 3,7 2,8 Jän.04 1,8 1,8 1,8 1,8
Feb.04 25,0 1,0 5,0 3,6 Feb.04 31,1 0,8 6, 1,9 Feb.04 20,5 1,8 4,0 1,5
Mir,04 34,S 1,9 8,4 6,0 Mär.04 12,3 0,2 3,3 2,3 Mir.04 53,9 1,8 8,1 3,9

•
ADr.04 24,8 0,9 8,4 5,7 Apr.04 11,6 0,6 2.0 1,5 AIr.04 44,9 2,2 12,1 6,7
MaI.04 58,7 0,9 14,4 8,5 MaI.04 4,8 0,6 1,6 1,0 MaI.04 80,4 2,2 27,2 15,4
Jun04 34,4 3,8 19,8 21,8 Jun04 5,2 0,6 1,9 1,7 Jun04 54,7 2.2 24,8 24,6
JuI.04 50,4 0,9 23,6 19,1 Jut.04 12,3 0,6 3,1 2,5 Juf.04 72,9 2,2 26,4 20,8
Aug.04 71,8 11,2 43,5 45,3 Aug.04 8,0 0,6 2.9 2,7 Aug.04 65,9 16,2 38,2 36,6
Sep.04 29,S 0,9 11,7 9,0 Sen04 8,8 0,6 2.2 1,6 ~04 49,1 2,2 16,0 11,8
0Id.04 24,7 10,7 18,3 18,5 0Id.04 0,6 0,6 0,6 0,6 0Id.04 33,6 4,8 19,2 18,1

Page 9
 Annex

Field blanks of Filter pack A Dec. 02- Oct. 04

Teflon IIJg/ml] Oxalic

:.Ç!.oi:li1e.~fJNi~râtê::,.JSûlpliät~ ';\~,;Nä:i\ti\;"NH!lo,:~':7YK~:;~(,~''Mg::?' :~/ca:;~~,:i
gNH4:LI;' ::,~:~H3\:¥,
A 0-22 0,010 0,069 0,010 0,026 0,103 0,026 0,009 0,063 0,266 0,251
0,018 0,078 0,024 0,102 0,037 0,070 0,084 0,517 0,488
0,031 0,046 0.009 0,035 0,043 0,029 0,042 1,129 1,066
A 23-51 0,100 0,015 0,025 0,069 0,038 0,049 0,248 0,234
0,199 0,023 0,019 0,038 0,041 0,041 0,271 0,256
0,036 0,035 0,018 0,046 0,036 0,060 0,306 0,289
0,033 0,026 0,024 0,104 0,039 0,033 0,402 0,380
A 52-84 0,028 0,030 0,138 0,038 0,039 0,044 0,318 0,300
0,009 0,027 0,018 0,297 0,104 0,032 0,180 0,170
0,007 0,021 0,028 0,276 0,100 0,035 0,039 0,220 0,208
0,023 0,076 0,008 0,018 0,022 0,019 0,084 0,721 0,681
0,067 0,043 0,029 0,104 0,047 0,080 0,110 0,369 0,349
0,016 0,027 0,018 0,054 0,035 0,054 0,087 0,166 0,157
A 85-121 0,102 0,078 0,045 0,267 0,142 0,250 0,008 0,144 0,160 0,151

•
0,140 0,093 0,085 0,065 0,085 0,075 0,021 0,264 0,198 0,187
0,Q20 0,028 0,064 0,123 0,090 0,049 0,022 0,152 0,595 0,562
0,050 0,073 0,095 0,128 0,046 0,058 0,030 0,233 0,534 0,504

A 122-152 0,083 0,179 0,041 0,070 0,026 0,028 0,003 0,162 0,615 0,581
0,027 0,032 0,032 0,059 0,035 0,019 0,003 0,148 0,337 0,318
0,036 0,046 0,050 0,072 0,144 0,034 0,003 0,104 0,480 0,453
0,061 0,016 0,036 0,065 0,134 0,012 0,004 0,060 0,449 0,424
A 153-186 0,194 0,044 0,039 0,044 0,023 0,038 0,004 0,081 0,371 0,350
0,043 0,030 0,034 0,132 0,084 0,088 D,DOS 0,091 0,694 0,655
0,109 0,028 0,070 0,078 0,065 0,040 0,001 0,079 0,295 0,279
0,114 0,036 0,031 0,174 0,026 0,061 0,097 0,475 0,449
0,148 0,516 0,212 0,379 0,082 0,206 0,073 0,326 0,986 0,931
A 187-220 0,014 0,088 0,102 0,017 0,158 0,014 0,004 0,048 0,501 0,473
0,034 0,062 0,043 0,087 0,214 0,022 0,016 0,120 0,426 0,402
0,031 0,174 0,077 0,138 0,047 0,027 0,016 0,154 0,286 0,270
0,068 0,212 0,403 0,121 0,164 0,071 0,046 0,870 0,378 0,357
0,033 0,073 0,057 0,068 0,111 0,096 0,019 0,223 0,654 0,618
A 221-258 0056 0,024 0,045 0,072 0,175 0,067 0,012 0167 0,254 0,240
0,052 0,078 0,048 0,067 0,071 0,063 0,014 0,209 0,347 0,328
0,015 0,017 0,039 0,033 0,061 0,034 0,007 0,085 0,667 0,630
0,031 0,020 0,033 0,065 0,101 0,058 0,013 0,131 1,735 1,639
0,065 0,030 0,063 0,069 0,236 0,061 0,011 0,178 0,432 0,408
0,029 0,005 0,025 0,034 0,141 0,036 0,005 0,054 0,186 0,176
A 259-294 0,068 0,022 0,054 0,046 0,018 0,008 0.145 0,443 0,419

•
0,022 0,003 0,016 0020 0032 0,022 0,006 0,085 0,534 0,505
1,372 0,059 1,051 0,586 0,044 0,020 0,005 0,076 0,293 0,277
0023 0023 0,017 0.040 0.041 0,034 0,011 0148 1,291 1,219
A 295-331 0,007 0007 0026 0,037 0,024 0033 0,008 0,050 0137 0,130
0011 0,009 0,030 0131 0064 0032 0,010 0056 0,180 0,170
0,006 0041 0078 0,157 0.061 0034 0,013 0,114 0167 0,158
0,033 0,039 0,031 0,179 0,084 0,030 0,017 0,168 0,401 0,379
A 332-366 0,016 0,065 0078 0,118 0,114 0,028 0,030 0,160 0,198 0,187
0,008 0,041 0021 0158 0110 0018 0014 0088 0,049 0,046
0,012 0,060 0,073 0,323 0162 0,025 0,029 0,216 0,084 0,080
0012 0028 0,027 0080 0.093 0,017 0,016 0091 0127 0,120
0,057 0,241 0,706 0,181 0.086 0,024 0,021 0,139 0,296 0,279
0010 0,033 0032 0074 0076 0018 0,026 0124 0,272 0,256
A 367-406 0011 0,034 0,039 0117 0159 0030 0,025 0089 0,111 D,lOS
0,007 0,054 0,041 0,110 0,097 0,036 0,016 0.128 0,283 0,267
0,023 0,274 0118 0,054 0,210 0,050 0,108 0336 0198 0,187
0,009 0,085 0065 0,032 0114 0032 0,031 0,128 0,249 0,235
0,021 0,185 0,081 0,017 0,103 0,025 0,065 0,185 0,214 0,202
A 407-442 0,022 0,392 0,035 0,033 0,097 0,026 0,063 0,306 0,198 0,187
0,045 0,247 0,068 0,029 0,098 0,033 0,125 0,432 0,259 0,244
0,025 0,145 0,053 0,127 0,074 0,069 0,024 0,163 0,169 0,160
0,035 0,117 0,056 0,096 0,046 0,042 0,022 0,092 0,094 0,089
0,011 0,175 0,042 0,047 0,052 0,021 0,022 0,114 0,059 0,055
0,031 0,225 0,055 0,043 0,097 0,038 0,077 0,276 0,234 0,221

Page JO
 Annex

Field blanks of Filter pack A Dec. 02- Oct. 04

Teflon (~g/ml] Oxalic

':Clori(fë~ )Niträt~, t~ùlphiitEi,:.i'Nä:l:'~ ~6NH4j;;~! "'X\K;.<' ~. 'Mg"~'; c;ài?> ;;\~1:I4~~:;?;NH3';i;i~
A 443-478 0,009 0,Q38 0,047 0,110 0,050 0,021 0,016 0,094 0,255 0,241
0,004 45,190 0,006 0,962 0,908
0,017 0.376 0,038 0,031 0,045 0;023 0,016 0,098 0,126 0,119
0,024 0,341 0,051 0,106 0,047 0,023 0,029 0,122 0,134 0,127
0,017 0,369 0,048 0,018 0,111 0,011 0,069 0,278 0,139 0,131
A 479-513 0,027 1,078 0,037 0,019 0,116 0,008 0,083 0,281 0,385 0,364
0.000
0,012 0,545 0,073 0,042 0,154 0,010 0,091 0,353 0,161 0,152
0,029 0,674 0,107 0,211 0,126 0,017 0,017 0,145 0,375 0,354
0,010 0,377 0,042 0,044 0,139 0,024 0.020 0,126 0,065 0,062
0,004 0,460 0,040 0,012 0,040 0,015 0,002 0,028 0,801 0,756
B 514-563 0,006 0,066 0,025 0,032 0,031 0,015 0,002 0,033 0,047 0,044
0,005 0,217 0,011 0,035 0,009 0,012 0,002 0,044 0,134 0,126
0,002 0,070 0,019 0,016 0,013 0.015 0,002 0,033 0,460 0,434
0.002 0,075 0,013 0,027 0,014 0,013 0,017 0,561 0.529
0,007 0,038 0,014 0,024 0,051 0,022 0,001 0,022 0.657 0,620
0,010 0,038 0,012 0,010 0,079 0,007 0,001 0,007 0,210 0,199
0,003 0,136 0,012 0,011 0,128 0,018 0,001 0,014 0,160 0,151
0,011 0,026 0,016 0,009 0,055 0,008 0,001 0,009 0,280 0,264

Page II
 Annex

Field blanks of Filter pack B Dec. 02- Oct. 04

Teflon [lJg/ml]
"

Ac,etate' Formiate Chlor/Cll! Nitrate 'Sulphate. .pxalâie' Nä NH4'. K' . , Mg Ca

0,106 0,014 0,014 0,139 0,019 0,019 0,071 0,031 0,036 0,013 0,115
0,107 0,017 0,023 0,067 0,008 0,219 0,122 0,052 0,045 0,010 0,105
BO-22 0023 0,029 0,187 0,016 0,011 0,024 0,123 0,027 0,015 0,188
0,145 0,042 0,009 0,212 0,014 0,006 0,038 0,080 0,065 0,077
0,050 0,033 0,006 0,044 0,025 0,020 0,085 0,046 0,055 0,031
B 23-51 0,066 0,044 0,022 0,049 0,030 0,012 0,057 0,046 0,068 0,107
0,111 0,048 0,012 0,029 0,123 0,049 0,045 0,060
0,011 0,013 0,008 0,038 0,026 0,018 0,026 0,031 0,047 0,082
0,078 0,016 0,014 0,029 0,011 D,DOS 0,133 0,025 0,057 0,043
B 52-84 0,039 0,015 0,017 0,115 0,050 0,018 0,222 0,036 0,059 0,072
0,038 0,012 0,059 0,053 0,004 0,104 0,026 0,111 0,087
0,031 0,010 0,047 0,065 0,012 0,028 0,050 0,023 0,067 0,042
0,066 0,016 0,287 0,354 0,032 0,038 0,361 0,051 0,199 0,069
0,069 0,017 0,084 0,066 0,036 0,009 0,083 0,017 0,060 0,068
0,049 0,014 0,021 0,019 0,007 0,010 0,025 0,013 0,033 0,021
B 85-121 0,062 0,018 0,081 0,093 0,023 0,011 0,090 0,020 0,079 0,072
0,077 0,018 0,021 0,081 0,078 0,017 0,226 0,035 0,128 0,020 0,096
0,085 0,018 0,132 0,111 0,033 0,050 0,097 0,027 0,120 0,087
0,128 0,023 0,036 0,145 0,025 0,013 0,069 0,031 0,009 0,000 0,045
0,065 0,021 0,077 0,051 0,027 0,010 0,143 0,015 0,069 0,004 0,127
B 122-152 0,016 0,014 0,026 0,017 0,022 0,025 0,028 0,020 0,003 0,093
0,126 0,016 0,083 0,010 0,012 0,007 0,050 0,035 0,035 0,002 0,039
0,151 0,019 0,063 0,127 0,041 0,006 0,083 0,043 0,056 D,DOS 0,250
0,116 0,017 0,141 0,041 0,037 0,009 0,315 0,036 0,151 0,006 0,149
B 153-186 0,098 0,018 0,130 0,077 0,046 0,030 0,200 0,043 0,170 0,008 0,202
0,184 0,034 0,026 0,017 0,011 0,020 0,037 0,015 0,004 0,048
0,213 0,034 0,037 0,075 0,029 0,009 0,037 0,016 0,020 0,007 0,101
B 187-220 0,213 0,029 0,019 0,086 0,027 0,008 0,027 0,134 0,024 0,021 0,275
0157 0,021 0031 0,095 0,109 0061 0,210 0,154 0,028 0,045 0,274
0,157 0,020 0,024 0,153 0,127 0,057 0,157 0,150 0,026 0,037 0,417
0,161 0,072 0,084 0,093 0,725 0,041 0,145 0,140 0,125 0,120 3,983
0,115 0,018 0010 0,009 0013 0,004 0,046 0,133 0,084 0,084
B 221-258 0015 0016 0086 0,066 0,055 0020 0073 0,022 0,073 0,010 0,176
0,014 0,007 0,010 0,107 0,038 0,028 0,035 0,045 0,032 0,006 0,124
0,017 0,006 0,030 0,134 0,048 0,011 0,034 0,032 0,036 0,008 0,147
0,015 0,005 0,028 0,192 0,115 0,035 0058 0,036 0,044 0,013 0,333
0,015 0,006 0,019 0,319 0,055 0,015 0,094 0,024 0,076 0,009 0,165
B 259-294 0,029 0,010 0,060 0,043 0,022 0,020 0,036 0,016 0,040 0,014 0,132
0,023 0,008 0,034 0,014 0,009 0,003 0,018 0,028 0,027 0,004 0,024
0,023 0,006 0,034 0,029 0,015 0,007 0,020 0,026 0,031 0,005 0,103
0043 0,007 0,035 0,037 0,022 0,021 0,017 0,026

•
0,031 0,006 0,080
B 295-331 0039 0008 0020 0,071 0019 0,020 0,045 0,025 0,028 0010 0,076
0,071 0,013 0,027 0,160 0,026 0,033 0,100 0,069 0,019 0,022 0,114
0,034 0,008 0,026 0,191 0,037 0,034 0,107 0,068 0,020 0,019 0,120
0,044 0,007 0,024 0,128 0,026 0,024 0113 0,064 0014 0014 0,092
B 332-366 0,042 0,015 0,084 0,213 0,072 0,044 0,278 0,118 0,057 0,034 0,208
0,059 0,011 0,030 0,110 0,032 0,009 0,154 0,110 0,020 0,011 0,096
0,056 0014 0,030 0149 0,064 0,022 0335 0,152 0,018 0,020 0087
0,074 0014 0,033 0,117 0,021 0,027 0066 0081 0017 0,015 0,069
0,073 0,013 0,033 0,191 0,092 0,039 0,186 0,090 0,022 0,027 0,199
0,074 0,012 0,038 0,177 0,025 0,069 0,073 0,080 0,020 0,022 0,106
B 367-406 0169 0,046 0,033 0,736 0,166 0,218 0844 0,224 0,027 0,069 0,318
0,229 0,090 0,046 2,788 0,076 0,358 0,037 0,115 0021 0,088 0,464
0,288 0,051 0,021 0,487 0,093 0,079 0,062 0,086 0,014 0,038 0,152
0,195 0,053 0,042 1,212 0,074 0,160 0,027 0,144 0,010 0,072 0,262
0307 0,099 0,084 8,207 0,200 0273 0063 0,465 0,011 0,203 0,776
B 407-442 0,295 0,089 0,067 4,852 0,028 0,561 0,051 0,495 0,011 0,199 0,993
0,206 0,045 0,034 0,275 0,032 0,026 0,058 0,035 0,020 0,017 0,074
0,200 0,048 0,039 0,561 0,033 0,120 0,042 0,050 0,015 0,049 0,146
0,183 0,034 0,043 0,531 0,047 0,038 0,073 0,048 0,020 0,022 0,098
0,184 0,051 0,026 0,413 0,024 0,273 0,008 0,043 0,015 0,042 0,154
0,205 0,059 0,042 1,227 0,050 0,434 0,046 0,063 0,016 0,057 0,203

Page 12
 AI/I/ex

Field blanks of Filter pack B Dee, 02- Oct. 04

Teflon [~g/ml]
Aceta'te Formiate .Chlörlöê :'Nltrate'. 'Sulphate .Oxalate '.Na' . :NH4 K .
. Mg Ca.,
B 443-478 0,158 0,023 0,010 0,166 0,023 0,066 0,061 0,036 0,007 0,014 0,068
0,370 0,044 0,018 0,538 0,045 0,094 0,026 0,042 0,009 0,018 0,094
0,273 0,063 0,043 0,950 0,056 0,127 0,013 0,080 0,012 0,031 0,161

0,228 0,037 0,040 2,771 0,047 0,214 0,013 0,076 0,010 0,053 0,251
B 479-513 0,185 0,040 0,039 1,738 0,034 0,195 0,009 0,071 0,009 0,075 0,310
0,159 0,013 0,006 0,144 0,024 0,019 0,041 0,032 0,009 0,007 0,047
0,186 0,024 0,017 0,383 0,053 0,071 0,022 0,051 0,011 0,026 0,127
0,158 0,024 0,038 0,379 0,037 0,077 0,063 0,059 0,017 0,023 0,109
0,171 0,021 0,006 0,158 0,018 0,019 0,034 0,023 0,007 0,009 0,075
0,135 0,009 0,021 0154 0037 0,032 0,018 0,017 0,015 0,009 0,064
B 514-563 0,146 0,009 0,009 3,530 0,026 0,016 0,007 0,276 0,014 0,002 0,029
0,155 0,009 0,009 0,221 0,036 0,024 0,014 0,013 0,014 0,002 0,028
0,151 0,008 0,004 0,099 0,015 0,010 0,015

•
0016 0,008 0,002 0,018
0,146 0,008 0,009 0,164 0,012 0,009 0,Q18 0011 0,021 0,002 0,024
0,191 0,013 0,006 0,073 0,012 0,184 0,016 0,017 0,015 0,001 0,016
0,191 0,008 0,014 0,116 0,110 0,010 0,044 0,031 0,014 0,002 0,037
0,189 0,008 0,006 0,074 0,007 0,009 0,007 0,011 0,009 0,002 0,014
0,180 0,009 0,016 0,029 0,018 0,014 0,033 0,011 0,012 0,003 0,031

Page f 3
 Annex

Field blanks of Filter pack B Dec. 02- Oct. 04

Nylon KOH
: "'?NO".';. ;':;Ht'[Q~;::, '.,'S.04~'t. >:;sQiPY (;~;~5Pï~~';~
::t;:f~~$Q~~~;~::;
0,045 0,046 0,203 0,135 0.401 0,267
0,025 0,025 0,118 0,079 0,240 0,160
B 0-22 0,028 0,029 0,094 0,062 0,285 0,190
0,040 0,041 0,143 0,095 0,254 0,169
0,021 0,021 0,088 0,059 0,216 0,144
B 23-51 0,035 0,036 0,092 0,061 0,234 0,156
0,020 0,020 0,070 0,047 0,058 0,039
0,042 0,043 0,091 0,061 0,340 0,227
0,020 0,020 0,096 0,064 0,165 0,110
B 52-84 0,029 0,029 0,080 0,053 0,149 0,099
0,049 0,050 0,189 0,126 0,436 0,291
0,067 0,068 0,099 0,066 0,394 0,263
0,036 0,037 0,161 0,107 0,367 0,245
0,068 0,069 0,189 0,126 0,281 0,187
0,080 0,081 0,273 0,182 0,516 0,344
B 85-121 0,085 0,086 0,281 0,187 0,776 0,517
0,082 0,083 0,241 0,161 0,318 0,212
0,116 0,118 0,169 0,113 0,351 0,234
0,229 0,233 0,360 0,240 0,055 0,037
0,058 0,059 0,402 0,268 0,225 0,150
B 122-152 0,070 0,071 0,170 0,113 0.431 0,287
0,212 0,215 0,125 0,083 0,524 0,349
0,100 0,102 0,329 0,219 0,341 0,227
0,074 0,075 0,540 0,360 0,622 0,415
B 153-186 0,125 0,127 0,354 0,236 0,441 0,294
0,096 0,098 0,217 0,145 0,539 0,359
0,070 0,071 0,508 0,339 0,866 0,577
B 187-220 0,279 0,284 0,214 0,143 0,260 0,173
0,278 0,283 0,251 0,167 0,303 0,202
0,424 0,431 0,406 0,271 0.478 0,319
4,047 4,113 0,137 0,091 0,531 0,354
0,085 0,087 0,225 0,150 0,458 0,305
B 221-258 0,089 0,090 0076 0,051 0,282 0,188
0,230 0,234 0,285 0,190 0,358 0,238
0,280 0,284 0,627 0,418 0,657 0,438
0,285 0,289 0,414 0,276 0,303 0,202
0,240 0,244 0,613 0,409
B 259-294 0,000 0,077 0,051 0,204 0,136

•
0,163 0,166 0,184 0,123
0,133 0,135 0,248 0,165 0,082 0,055
0,156 0,158 0,337 0,225 0,134 0,090
B 295-331 0223 0,226 0,335 0,224 0,067 0,044
0,194 0,197 0,290 0,194 0067 0,045
0,198 0,202 0,139 0,093 0,130 0,087
0,162 0,164 0,139 0,092 0,090 0,060
B 332-366 0209 0,212 0,260 0,173 0,125 0125
0,218 0,222 0145 0,097 0,208 0,138
0,037 0,038 0,082 0,055 0,080 0,080
0,016 0,016 0,100 0,067 0,089 0,059
0,Q18 0,019 0,116 0,078 0,156 0,104
0,009 0,009 0,083 0,055 0169 0,113
B 367-406 0,033 0,034 0,120 0,080 0031 0,021
0,037 0,038 0,125 0,084 0,058 0,038
0,059 0,060 0,095 0,064 0,161 0,107
0054 0,055 0096 0,064 0171 0,114
0,037 0,037 0,090 0,060 0,208 0,139
B 407-442 0,000 0,113 0,075 0,255 0,170
0,020 0,021 0,122 0,081 0,243 0,162
0,023 0,024 0,104 0,069 0,243 0,162
0,028 0,028 0,114 0,076 0,192 0,128
0,030 0,030 0,075 0,050 0,157 0,105
0,048 0,048 0,127 0,085 0,181 0,121

Page 14
 Annex

Field blanks of Filter pack B Dec. 02- Oct. 04

Nylo,n KOH
' ..
\~;N03,LJ; ,H.N,q~:< ''''ßQ4:'-': ,!:;. 5.02' -;i. ,;;;~,s.~i:,/
':,~;:';~:Qf'Yf,
B 443-478 0,163 0,166 0,283 0,189 0,822 0,548
0,366 0,372 0,291 0,194 0,070 0,047
0,301 0,306 0,330 0,220 0,020 0,013
0,263 0,268 0,455 0,303 0,088 0,059
0,302 0,307 0,347 0,231 0,145 0,097
B 479-513 0,345 0,351 0,384 0,256 0,129 0,086
0,291 0,296 0,334 0,222 0,282 0,188
0,278 0,283 0,397 0,265 0,363 0,242
0,380 0,386 0,500 0,333 0,562 0,375

• B 514-563
0,248
0,269
0,577
0,328
0,270
0,252
0,273
0,586
0,333
0,274
0,490
0,344
0,481
0,445
0,363
0,327
0,229
0,321
0,297
0,242
0,352
0,212
0,061
0,021
0,146
0,235
0,142
0,041
0,014
0,097
0,262 0,266 0,645 0,430 0,176 0,117
0,273 0,277 0,502 0,335 0,178 0,119
0,280 0,284 0,340 0,227 0,370 0,247
0,221 0,224 0,398 0,266 0,228 0,152
0,264 0,268 0,297 0,198 0,451 0,300

.'

Page 15
 Annex

Percentage values above Detection limit

cr N03° 50.20 - Oxalat Na' NH; K' Mg<' Ca" HN03 502 NH3
Dez.02 0 10 17 9 1 15 0 6 10 13 12 15
n =20 0% 50% 85% 45% 5% 75% 0% 35% 50% 65% 60% 75%
Jän.03 0 10 13 6 0 13 0 0 3 9 7 1
n =13 0% 77% 100% 46% 0% 100% 0% 0% 23% 69% 54% 8%
Feb.03 1 10 25 19 5 25 2 4 12 22 20 1
n =26 4% 38% 96% 73% 19% 92% 8% 15% 46% 85% 77% 4%
Mär.03 15 2 1 6 13 2 12 16 6 3 5 2
n =16 6% 87% 94% 62% 19% 92% 8% 15% 46% 85% 77% 4%
Apr.03 2 25 27 24 4 27 19 12 16 27 23 26
n =27 7% 93% 100% 92% 15% 100% 70% 44% 59% 100% 87% 96%
Mal;03 3 12 14 11 2 12 10 7 10 14 7 13
n =14 27% 86% 100% 79% 14% 86% 71% 50% 71% 100% 50% 93%
Jun.03 8 19 19 19 5 19 13 15 19 18 18 19
n =19 42% 100% 100% 100% 26% 100% 68% 79% 100% 95% 95% 100%
Jul.03 8 23 25 23 4 26 10 15 25 25 27 27

•
n =27 30% 85% 93% 85% 18% 96% 37% 55% 93% 93% 100% 100%
Aug.03 0 25 29 27 9 29 19 18 28 28 28 29
n =20 0% 86% 100% 93% 31% 100% 65% 62% 97% 97% 97% 100%
Sep.03 0 12 16 15 0 14 4 0 11 15 15 14
n =20 0% 75% 100% 94% 0% 88% 25% 0% 69% 94% 94% 88%
Old.03 2 13 25 13 1 20 2 2 15 26 20 11
n =20 8% 50% 96% 50% 4% 77% 8% 8% 58% 100% 77% 42%
Nov.03 1 18 26 17 0 21 6 17 20 26 19 4
n =20 4% 70% 100% 65% 0% 81% 23% 65% 77% 100% 73% 15%
Dez.03 1 18 24 13 5 23 4 18 10 24 15 1
n =20 4% 75% 100% 54% 21% 96% 16% 75% 42% 100% 63% 4%
Jan.04 4 17 22 8 8 22 10 2 12 22 20 0
n =22 18% 77% 100% 36% 36% 100% 45% 9% 54% 100% 91% 0%
Feb.04 5 11 13 6 5 12 9 2 11 15 15 6
n =15 33% 73% 87% 40% 33% 80% 60% 13% 73% 100% 100% 40%
Mär.04 8 23 25 19 3 25 15 12 23 25 24 13
n = 25 32% 92% 100% 76% 12% 100% 60% 48% 92% 100% 96% 52%
Apr.04 15 14 27 21 0 22 12 7 22 23 17 16
n = 27 55% 52% 100% 78% 0% 81% 44% 26% 81% 85% 63% 59%
Mal.04 6 16 23 21 1 19 7 4 14 23 12 19
n = 24 25% 67% 96% 87% 4% 79% 29% 17% 58% 96% 50% 79%
Jun.04 5 18 19 18 1 19 7 9 11 20 15 18
n=20 25% 90% 95% 90% 5% 95% 35% 45% 55% 100% 75% 90%
Jul.04 3 14 16 14 1 13 9 6 9 15 15 15
n=26 11% 54% 61% 54% 4% 50% 35% 23% 35% 58% 58% 58%
Aug.04 0 9 10 9 0 10 10 0 0 10 9 10
n= 10 0% 90% 100% 90% 0% 100% 100% 0% 0% 100% 90% 100%
Sep.04 3 11 26 16 1 20 9 3 10 25 19 20
n = 27 11% 41% 96% 59% 4% 74% 33% 11% 37% 93% 70% 74%

CI- N03- 5042- Oxalat Na+ NH4+ K+ Mg2+ Ca2+ HN03 502 NH3
90 330 442 334 69 408 189 175 297 428 362 280
Above DL 2% 72% 96% 73% 15% 89% 41% 38% 65% 93% 79% 61%
BellowDL 98% 28% 4% 27% 85'1'. 11% 59"1, 62% 35% 7% 21% 39%

Page 16
 Annex

SCAVENGING RATIOS Dec.02-Sep.04

Aerosols [jJg/m']
~':lMö'lÏth's~J~' NO; SO/- NH4, :.~;.;'l:Li:t.Nô';.t',>F ,',':N03fH~qà~:'
Dec.02 29,6 86,5 34,1 57,4 87,0
Jan.03 72.9 164,2 44,2 47,2 120,0
Feb.03 34,3 446,3 102,9 102,6 136,9
Mar.03 445,3 319,5 114,3 121,8 567,1
Abr.03 826,9 1037,0 515,2 211,6 1038,4
May03 500,6 922,6 303,4 145,6 646,3
Jun.03 540,7 1311,0 461,0 353,3 894,0
Jul.03 188,8 974,5 345,5 1055,3 1244,1
Ago.03 526,5 1798,9 656,1 1269,1 1795,6
Sell.03 72,8 595,0 265,8 858,5 931,2
Oct.03 26,0 377,3 137,0 409,4 435,3
No v.03 74,8 389,7 107,7 211,2 286,0
May03 689,9 744,0 266,3 906,3 1596,2
Jun.04 1112,8 835,7 318,2 1247,4 2360,2
Jul.04 812,3 1234,9 442,9 1483,7 2295,9
Ago.04 436,8 1235,3 447,0 1261,9 1698,7
Sell.04 356,0 719,2 247,2 813,8 1169,8

Precipitations [Ugtl] Scavenging Ratios

rl:t}JI9,iit)Wi::~g - NHt NO~' '. 'sol' ~;~Hàf:\W
:~:i{l:!'iWJ6~i~t:" s1d~~~~~~V
;:.fFf.7~Wlii.~.:.;~fiij;~
Dec.02 50,3 507,8 375,3 8,8 4,3 1,5
Jan.03 31,3 247,1 124,7 5,2 0,8 0,7
Feb.03 37,0 80,8 31,9 0,8 0,1 0,4
Mar.03 152,9 717,0 305,4 5,9 1,0 1,3
Abr.03 613,5 1265,4 1260,6 6,0 1,2 1,2
May03 616,2 1260,S 1130,7 8,6 1,2 2,0
Jun.03 657,6 1155,7 1051,8 3,3 0,8 1,4
Jul.03 574,7 1207,9 1049,8 1,1 1,1 1,7
Ago.03 552,6 1096,3 1106,S 0,9 0,6 0,8
Sep.03 436,3 1402,7 1026,2 1,6 1,7 1,6
Oct.03 59,6 227,1 184,0 0,6 D,S 0,4
Nov.03 10,0 166,1 170,2 0,8 0,4 0,1
May03 457,7 1420,1 748,8 1,6 1,0 1,7
Jun.04 441,0 1184,1 720,1 0,9 0,9 1,4
Jul.04 384,0 998,4 775,3 0,7 0,6 0,9
Ago.04 381,6 1051,2 879,1 0,8 0,7 0,9
Sell.04 300,5 819,7 459,3 1,0 0,6 1,2

Page /7
 Annex

Aerosol and gases concentration values in Jlg pro Normcubicmeter Dec.02/ May 03/ JuI.04

Aerosol (Anions) IUQ/Nm'] Aerosol (Kations) ruÇ Nm'] Gas [1Jg/Nm']

:~mple~:«{Qât~;i~~Chloride Nitrate. Sùlp~ate .Na " NH4 .. K :Mg. Ca S~~~9if:; ~J.{~1-I3~1~:
';~';,t1N,c>;j'<
co 10.12.2002 0,0020 0,0247 0,3111 0,0026 0,0728 0,0029 0.0654 0,1055 0,4021 0,0121
C1 12.12.2002 0,0060 0,0247 0,1676 0,0098 0,0106 0,0010 0,0340 0,0556 0,2765 0,0903
C2 13.12.2002 0,0121 0,1320 0,2284 0,8215 0,0494 0,0045 0,0834 0,0091 0,1657 0,0121
C3 14.12.2002 0.0020 0,0247 0,1696 0,0054 0,0363 0.0010 O,09n 0,2982 0,0712 0,0121
C4 15.12.2002 0.0020 0,on4 0,2137 0,0026 0,0360 0,0021 0,0802 0,0817 0,0980 0,0121
CS 16.12.2002 0,0020 0,0247 0,0383 0,0055 0,0106 0,0010 0,0145 0,0672 0,0351 0,0121
C7 17.12.2002 0,0020 0,0247 0,0699 0,0026 0,0106 0,0010 0,0145 0,0956 0.0991 0,0121
CS 18.12.2002 0,0020 0,0247 0,2354 0,0026 0,0718 0,0051 0,0399 0,4914 0,2576 0,0121
C9 19.12.2002 0,0045 0,0247 0,1098 0,0026 0,0106 0,0010 0,0673 0,0429 0,0351 0,0121
C10 20.12.2002 0,0049 0,0247 0,0447 0,0026 0,0106 0,0040 0,0554 0,0329 0,1211 0.0121
C11 21.12.2002 0,0348 0,0247 0,0513 0,Q285 0,0106 0,0226 0,0145 0,0098 0.0351 0,0121
C13 22.12.2002 0,0020 0,0247 0,0112 0,0026 0,0106 0,0010 0,0145 0,0028 0,0351 0,0121
C14 23.12.2002 0,0069 0,0247 0,0024 0,0026 0,0106 0,0029 0,0145 0,0024 0,0351 0,0121
C1S 16.05.2003 0,0018 0,9220 1,4767 0,0180 0,5875 0,0405 0,0318 0,2336 0,0916 0,7952

•
0,2130
C16 17.05.2003 0,0086 0,0448 0,5400 0,0180 O,14n 0,0276 0,0072 0,0571 0,1196 0,3030 0,1748
C17 18.05.2003 0,0059 0,0714 1,3830 0,0180 0,4355 0,0589 0,0202 0,1122 0,0386 0,3660 0,3562
C19 19.05.2003 0,0018 0,6547 1,4661 0,0180 0,5492 0,0678 0,0187 0,0892 0,1542 0,3188 0,4600
C20 20.05.2003 0,0018 0,0135 0,0334 0,0180 0,1813 0,0082 0,0110 0,0600 0,0148 0,0516 0,0674
C21 21.05.2003 0,0018 0,0135 0,1113 0,0366 0,0314 0,0235 0,0031 0,0222 0,0105 0,0854 0,0674
C22 22.05.2003 0,0018 0,0135 0,1199 0,0180 0,0231 0,0082 0,0069 0,0226 0,0102 0,1438 0,0674
C23 23.05.2003 0,0939 0,8545 0,8500 0,1630 0,2001 0,0578 0,0439 0,5624 0,0176 0,0985 0,1600
C2S 24.05,2003 0,0094 0,3676 1,5136 0,0180 0,4373 0,0598 0,0335 0,2176 0,1119 0,4890 0,3963
C26 25.05.2003 0,0052 0,0654 2,6521 0,0180 0,8206 0,0679 0,0253 0,1096 0,0733 0,4574 0,3500
C27 26.05,2003 0,0018 0,0135 2,8129 0,0180 1,0018 0,0400 0,0242 0,0871 0,0784 0,3252 0,0674
C2S 27.05.2003 0,0054 0,3030 2,3633 0,0180 0,6192 0,0660 0,0278 0,3116 0,0389 0,3992 0,0674
C30 01.07.2004 0,0020 0,6379 2,2846 0,0145 0,3879 o,oon 0,0216 0,1028 0,1609 0,4437 0,1083
C40 02.07,2004 0,0020 53,6212 0,1538 0,0026 1,1247 0,0010 0,0008 0,0145 0,0496 O,82n 0,2736
C41 03,07,2004 0,0076 0,0247 0,5150 0,0170 0,0632 0,0100 0,0008 0,0145 0,0708 0,1847 0,1105
C42 04.07.2004 0,0020 0,1653 1,1374 0,0335 0,2642 0,0150 0,0031 0,0901 0,1397 0,3141 0,0121
C44 05.07.2004 0,0020 70,4590 2,m5 0,0061 0,8908 0,0028 0,0008 0,0145 0,1417 1,1470 0,1248
C4S 06.07.2004 0,0020 0,3014 1,0689 0,0202 0,2215 0,0142 0,0309 0,1992 0,1207 0,3613 O,08n
C46 11.07,2004 0,0097 0,3649 0,1505 0,0108 0,0334 0,0050 0,0226 0,1896 0,0271 0,0871 0,2714
C47 12.07,2004 0,0020 0,0247 0,0066 0,0062 0,0106 0,0035 0,0008 0,0145 0,1111 0,1058 0,0273
C48 13,07,2004 0,0148 0,0247 0,1506 0,0093 0,0106 0,0113 0,0008 0,1307 0,0004 0,1585 0,2687
C49 14.07.2004 0,0020 0,0247 0,4762 0,0196 0,0106 0,0168 0,0108 0,3495 0,0226 0,1988 0,2238
CSO 15.07.2004 0,0020 0,0247 0,3231 0,0766 0,0457 0,0203 0,0008 0,0145 0,0303 0,1688 0,3792
CS2 16.07.2004 0,0230 0,8324 0,7583 0,0755 0,0106 0,0396 0,0256 1,9286 0,0004 0,1481 0,4934
C53 17.07.2004 0,0020 0,3268 1,3993 0,0334 0,4178 0,0425 0,0091 0,1341 0,0593 0,6223 0,3383

Page 18
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT AZORES Jul. 02 - Jul. 04

l:f':.l..•t.~'-~\:.: :~I~." ';l~""':' :,.........
\,.•. ;..."11.,,;:.:. .' .; .:-; :,:..,:" .:';;'~: ,__,,:,"!:- ~~:'~.:(~~.~..:.:'.:::.:~~"/I,.~ '-"q;.,'{ ~t";":i,\~;''11:"'i~,,;'''' ':~;d,~ ',:'.;:,.~-~
-j;" i.': ,::-it \ '~:~~.;- -.-:~t"J~y.:, .: ~~.i..Wo'od- ,t":~' ~... iPlaiit:,\ .. o.:..~
~~;.;:"
Sample ('Startlngdâte :;;'ë~Rë~ of Ei1~~'date'of.':~l.,;:l1\f' 'I~'~1Wo()d i;:'., ~'~;,Woci(1;4t; P..lant;OebrlS P.lantD.ebris ~~,t';'~'(ÖM~ài;;-i)-ij{>:",~,' ..Q.
É.~:~~'::J{~~ ~~~~T:~!~~~;1~.~
~:,::.i~~~~&.~ilp~~X;:4 ~t!t'.~E~l9.~i
;Dn~f\}:ii~;r~.~~~~\~F)i:
~~'r,:~r~~1t'1 f.~;:~{~~~i~fr.~
~r~~l{~ç}~~~~' I;' ~~\l?~,tîj~-!~~j~
b}~i~~%'~8T;::;*
(odlmmlwyy) (ddlminlwyy) [nglm'] (nglm'] [nglm'] STP [ngIm']5TP [nglm'] STP [nglm'] 5TP
STP 5TP
AZO 01 8.Ju12002 15.Ju12002 0,71 11,7 19,9 2.4
AZO 02 15.Ju12002 22.Ju12002 3,01 8,03 49,9 84,8 36,2 79,6 2,4 2,2
AZO 03 29,JuI2002 5.Au!l2002 0,72 11,9 20,3 5,7
AZO 04 5Aug2002 12.Aua2002 0,70 11,5 19,6 5,7
AZO 05 12.Aua2002 19,Au!l2oo2 3,37 6,24 55,8 94,9 28,1 618 302 196
AZO 06 19.Aua2002 26,Aua2002 1,70 350 282 479 15,8 347 7,2 52
AZO 07 26.AuQ2002 2.5ep2002 1,07 2,98 17,8 30,2 13,4 29,6 6,0 5,9
AZO 08 25e02002 9.5e02002 846 0,0 38,1 838 0,0 39,1
AZO 09 95ep2002 16,Sep2002 24,78 9,96 410,1 697,2 449 98,7 97,1 13,7
AZO 10 16.Se02002 24.5ep2oo2 13,67 226,3 384,7 39,8
AZO 11 24.5e02002 3O,5e02002 6,74 3047 111,6 1896 137,3 3020 251,9 4011
AZO 12 3O.Sep2002 70kt2002 14,25 1155 235,9 401,1 52,0 1144 34,9 10,0
AZO 13 28.0k12002 4.Nov2002 3,30 54,6 92,8 22,2
AZO 14 11.Nov2002 18.Nov2002 19,56 323,8 550,5 81,6
AZO 15 20.Nov2002 28.Nov2002 1,39 259 22,9 39,0 117 25,7
AZO 16 5Dez2002 12.Dez2002 35,33 584,9 994,3 273,1
AZ017 12.Dez2oo2 19,Dez2002 0,69 11,4 19,5 137
AZO 22 3O.J3n2003 6,Feb2003 8,88 392 146,9 249,8 17,7 389 555 86
AZO 23 6Feb2003 13,Feb2003 4,67 2,42 77,4 131,5 10,9 24,0 48,9 8,9
AZO 24 13.Feb2003 20,Feb2003 3,02 4,39 50,0 850 19,8 43,S 10,1 5,1
AZO 25 20.Feb2003 27Feb2003 26,86 868 4446 7559 39,1 861 198,8 22,6
AZO 26 6 Mar2003 13.M3r2003 0,96 S,59 15,9 27,0 25,2 55,4 12.4 25,4
AZO 27 13.Mar2003 20.Mar2003 8,60 620 142,4 242,1 279 615 74,9 19,0
AZO 28 20.Mar2003 27.M3r2003 6,43 2,46 106,4 180,9 11,1 24,4 67,2 9,1
AZO 29 27Mar2003 4.Apr2003 1,36 22,6 38,4 8,3
AZO 30 4.Aor2003 11.ADr2003 3,35 55,5 94,4 38,7
AZO 32 2.Mai2oo3 8.Mai2003 1,67 6,04 27,7 47,0 27,2 59,8 8,7 11,1
AZO 33 8.Mai2003 15.Mai2003 0,65 10,8 18,3 0,0 4,5
AZO 34 15.Mai2003 22 Mal2003 625 3,49 1035 176,0 15,7 34,6 25,0 4,9
AZO 35 22.Mai2oo3 29.Mai2003 6,59 3,71 109,1 185,4 16,7 36,8 25,8 5,1
AZO 36 29.Mai2oo3 5.Jun2003 730 396 1209 205,5 17,8 39,2 24,8 4,7
AZO 37 5.Jun2003 12.Jun2003 9,14 3,63 151,3 257,2 163 35,9 17,3 2,4
AZO 38 12 Jun2003 26.Jun2003 2,33 2,55 38,6 65,7 11,5 25,3 10,6 4,1
AZ040 3Jul2003 10,Ju12003 3,31 54,8 932 24,9
AZO 41 10.Ju12003 17,Ju12003 5,86 6,56 971 165,0 29,S 65,0 23,3 9,2
AZO 42 17,Jul2003 24.Ju12003 12,21 3,98 202,2 343,7 17,9 39,4 79,7 9,1
AZO 43 24.Ju12003 31.Ju12003 29,66 490,9 8346 1676
AZO 44 31.Ju/2oo3 7.Aua2oo3 4,79 5,68 79,2 134,7 25,6 56,3 15,8 66
AZO 45 7.Aug2003 15,Aua2oo3 9,37 2,97 155,1 263,8 13,4 29,4 43,7 4,9
AZO 46 15Au!l2003 23.Aug2003 17 70 22,19 2931 498,2 100,0 219,9 43,4 19,1
AZO 47 23.Aua2003 28,Aua2oo3 2,60 3,73 431 73,2 16,8 37,0 80 4,0
AZ048 28.Aua2003 3 Seo2oo3 5,82 96,3 163,7 16,5
AZO 49 3.Seo2oo3 18.Seo2oo3 3,97 65,7 111,7 34,3
AZO 50 18.5ep2003 25.Seo2oo3 472 78,1 132,8 26,1
AZO 51 255ep2003 2.0kt2oo3 4,77 3,51 79,0 134,3 15,8 34,8 19,9 5,2
AZO 52 2.0k12003 9.0kt2oo3 10,16 623 168,2 2860 28,0 617 48.4 104
AZO 53 9.0k12003 16.0kt2003 4,36 4,84 72,1 122,6 21,8 47,9 11,8 4,6
AZO 54 160kl2oo3 230kt2oo3 4,41 3,95 73,0 124,1 17,8 39,1 16,7 5,3
AZO 56 13.Nov2003 2O.Nov2oo3 2,15 35,6 605 34,S
AZO 57 20.Nov2003 27.Nov2oo3 5,88 265 97,4 165,5 11,9 26,2 80,2 12,7
AZO 58 27.Nov2003 4Dez2oo3 5,14 85,1 144,7 26,8
AZO 59 4.Dez2003 11.Dez2003 5,62 930 158,2 29,2
AZO 60 11.Dez2003 17.Dez2oo3 1,47 4,70 24,4 415 21,2 46,6 4,7 5,3
AZO 61 17Dez2003 23.Dez2oo3 10,60 5,62 175,5 298,3 25,3 55,7 64,1 12,0
AZO 62 23.Dez2003 7.Jan2004 184 3,68 305 51,9 166 36,4 145 10,1
AZO 63 7.Jan2004 15.J3n2004 7,47 123,7 210,3 41,4
AZO 84 15.Jan2004 22.Jan2004 4,18 2,64 69,3 117,7 11,9 26,1 17,7 3,9
AZO 65 22 Jan2004 29.J3n2004 163 234 26,9 458 105 23,2 11,0 56
AZO 66 29.Jan2004 4 Feb2004 1,01 168 28,S 5,1
AZO 67 4.Feb2004 12.Feb2004 0,0 0,0
AZO 68 12.Feb2004 20.Feb2004 3,61 2,98 59,7 101,5 13,4 29,5 20,1 5,9
AZO 69 20.Feb2004 26.Feb2004 2,60 6,87 43,0 73,1 30,9 68,0 22,2 20,6

Page 19
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT AZORES Jul. 02 - Jul. 04

.. ~.",,,, ,,,~
~lt;~~:~:. (g~~~~
'i>t'-;t~: ~:--""'~~,:.;"~:;.'l:;~;:
Eh:]/'tI~&~fi'.
}.~.~~.~w~')':è~'.~r~~ t;~rf~~:~
:~!~~l~9fdt'.~~9,!.
~~~~~lB~'G~~-~~
(ddlmm/yyyy) (dd/mm/yyyy) [ng/m') [hg/rn')
:~'~~t%]:~1~~~'
lsmcike(OC)i
P.lilOfDebrls
:' .. ~'i"'!,~
[ng/m')STP
\'~1'."
. "~:;,,

[ng/m')STP
.~;i~~~mM}1~~
~~~~~~~ ~~)~~t(!iJ;Jg~-t
[ng/m'J STP
~ià'~r~.i~;i;
~:.:;'~}:"':":":':i'''~{~'~",
~~~<~~:~.<3°cti~1tt:~
isincike(OM)/OM'
,~;~M~!Q':1)[~.f!!!
:~:~~r~'~:i%)~'_~i\:~r
"\i.",:.';'{'/;)'k,,,i.~
[ng/m') STP
_;t~:i~\~~!~nt.A8:~;~'f

STP STP
AZO 70 26.Feb2004 4.Mär2004 461 396 76,3 129,6 17,9 39,3 28,0 8,5
AZO 71 4.Mär2004 13.Mär2004 0,58 9,7 16,4 6,5
AZO 73 26.Mär2004 1.Aor2004 2,44 40,3 68,S
AZO 74 1.Aor2004 7.Aor2004 5,83 12,83 96,4 163,9 57,8 127,2 199 15,5
AZO 75 7.Aor2004 15Apr2004 2,04 33,8 57,4
AZO 76 15.Apr2004 27.Aor2004 16,04 265,5 451,4 87,7
AZO 77 27.Aor2004 6.Mai2004 2,59 42,9 12,9
AZO 78 6.Mai2004 14.Mai2004 1,69 28,0 47,7 30,S
AZO 79 14.Mai2004 20.Mai2004 2,15 3,28 35,S 60,4 14,8 32,S 15,3 8,2
AZO 80 2O.Mai2004 27.Mai2004 0,48 8,0 13,6 3,4
AZO 81 27.Mai2004 3.Jun2004 3,33 55,1 93,7 13,1
AZO 82 3.Jun2004 11.Jun2004 285 473 80,3 151
AZO 83 11.Jun2004 22.Jun2004 074 8,59 12,3 20,9 38,7 85,1 2,8 11,5
AZO 84 22.Jun2004 2.Ju12004 5,72 94,7 161,0 36,0

Page 20
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT AVEIRO Jul. 02 • Jul. 04

1"--;~,.J.l~;t~:~...:.~l.:..~}~~" ,-~'-::~v~~fL'::~;
~'~'f.;t:;1:)}~:
"Sample.' :t""'.:!,c'" l.1c:'ïl;è~' i';'~Wood ~,~.:(~:f Wood",,'j
!Slartlng:ïlaleof
;."~jJ+-,~j'.C;: -Pr ..~,';'~:~~ :!r.";';.\.:~-!:;_~~
;'~~~If.'~
En:a: dale'o"H
.:!'t.~.T..~t~~j~': if",;"-."c:':.,!:Jl'~:"
PlantlOellrosPlanl'Oebrls ;',:o(-,k"""""O
~~':iPlant~.\ ..~..;
..~~
;,," :." :~•. ,- ....'.c'. ,:',
-'f.l\.t~;';;~
.......
.f ~~.: ::'~~":\Wöod '1~':';'';

~-~~fb.~,~~~i
~~r~~~iTP~,i;~AWt;~ lf;;l~~~:r.;~~
.~.~~~~[n~';'~~~~~~~ ~:fj~!!~.~:~[~~~~~~:~Rl ~~~8~:(9M-j. ;~~l.:~~I~~X.~~~~~~ :~~f~~:;~~)r-~1~~
~'.;'(~~~~l4~t~ ,~~~~.~~j~2m
(ddlmmlyyyy) (ddlmmlyyYy) lng/m')' [ng/m') (ng/m') STP (ng/m"] STP lng/m'] STP lng/m') STP [ng/m'] STP [ng/m') STP
STP STP
AVE 01 1.Ju12oo2 8.Ju12002 1130 12,62 187.1 318.1 56,8 125,0 11.3 4,4
AVE 02 8.Ju12002 15.Ju12002 1267 989 2097 3565 44.5 98.0 136 37
AVE 03 15.Ju12002 22.Ju12002 939 2396 1554 2641 1079 2375 4.0 36
AVE 04 22.Ju12oo2 29.Ju12002 11.49 25,39 190,2 3233 114,4 251,6 7.1 5.5
AVE 05 29.Ju12002 5AuQ2002 1075 2268 1779 3024 1022 2248 66 4.9
AVE 06 5.AuQ2002 12.Aua2oo2 2702 2421 447,3 7604 1091 2399 160 51
AVE 07 12.AuQ2002 19.AuQ2002 6,12 25.75 101,4 172,4 116,0 255,2 3,8 5.6
AVE 08 19.AuQ2002 26.Aua2oo2 3268 19,15 5410 9196 863 1898 145 3,0
AVE 09 26.AuQ2002 2.Sep2002 2934 34,11 4857 8256 1537 3381 6,3 2,6
AVE 1D 2.Se02002 9.Sep2oo2 46,39 1445 767,9 1305.4 65,1 143.2 19,0 2.1
AVE 11 9.Sep2002 16Sep2002 7957 995 13172 22392 448 986 23,2 1,0
AVE 12 18.5ep2oo2 23.Sep2oo2 2828 9.20 4681 7957 415 91.2 215 2.5
AVE 13 23Sep2002 30.Se02002 80.75 17,11 1336.7 2272,5 771 1695 24,3 1,8
AVE 14 30.Sep2002 70kt2002 10506 1463 17391 29565 659 1450 244 12
AVE 15 7.0kt2oo2 14.0kt2002 4349 1082 7200 12239 487 1072 18,8 1.6
AVE 16 14.0kt2oo2 21.0kt2002 12251 4850 2028,0 3447.6 218,5 480.6 73.2 10,2
AVE 17 21.0kt2oo2 28.0kt2002 9739 9,09 16122 27407 409 901 707 23
AVE 18 28.0kt2002 4.Nov2002 4177 1144 691,4 11754 515 1134 19,6 19
AVE 19 4.Nav2002 11.Nav2002 80,60 7,29 1334,2 2268 2 328 72.3 12,5 0,4
AVE 2D 11.Nov2002 18.Nov2002 15247 1144 25240 42908 516 1134 540 1,4
AVE 21 18 Nov2002 25.Nov2oo2 14653 2180 24256 41235 982 216.0 50,8 27
AVE 22 25Nav2002 2.Dez2002 8109 6,69 13424 22821 30.1 663 302 0.9
AVE 23 2.Dez2002 9.Dez2oo2 28881 28.34 47809 81276 1277 2809 35.9 1.2
AVE 24 9.Dez2oo2 16.Dez2oo2 22816 2114 37770 64209 952 209.5 47,6 16
AVE 25 16.Dez2002 23.Dez2oo2 84,82 2052 1404,1 23870 92.4 2034 32.1 27
AVE 26 23.0ez2002 26.Dez2002 12801 333 21191 36024 150 330 96,1 0,9
AVE 27 26.0ez2002 2.Jän2oo3 28075 1965 46475 7900 8 885 194.7 1125 28
AVE 28 2.Jän2003 9.Jän2003 276,72 8,91 45808 77874 40,1 88,3 105,6 12
AVE 29 9.Jän2003 16.Jän2003 55774 7297 9232,9 156959 3287 7232 583 27
AVE 3D 16 Jän2oo3 23.Jän2003 43546 94 45 72086 12254 6 4254 9360 791 6.0
AVE 31 23.Jän2oo3 30.Jän2oo3 656,28 23,65 10864.0 18468,8 106,5 234,4 640 0,8
AVE 32 30.Jän2003 6.Feb2003 33725 850 55828 94908 38.3 84.2 83.6 0.7
AVE 33 6.Feb2003 13.Feb2003 39966 7016 66160 112472 3160 6953 46,0 2,8
AVE 34 13.Feb2oo3 20.Feb2003 412.00 4056 6820,3 115944 182,7 402,0 64.5 2.2
AVE 35 20.Feb2oo3 27Feb2oo3 24756 1797 40982 69669 810 1781 1020 26
AVE 36 27.Feb2oo3 6.Mär2oo3 20191 1554 33424 56820 70.0 1540 97,9 2.7
AVE 37 6.Mär2003 13.Mär2003 447,24 26.95 7403.6 12586,1 1214 267.1 52,7 1 1
AVE 38 13.Mär2oo3 20 Mär2003 158 52 2051 26241 44610 92,4 2033 440 20
AVE 39 20.Mär2oo3 27.Mär2003 15552 3760 25744 43765 169,4 3726 424 3.6
AVE 40 27.Mär2003 3.Apr2oo3 8927 23,84 1477,7 2512,2 1074 236.3 38,8 3.6
AVE 41 3.Aor2oo3 10 Aor2003 2597 26.59 4299 7309 1198 2635 127 4.6
AVE 42 10.Apr2oo3 17Aor2oo3 2083 17 70 3447 5861 79,8 1755 212 63
AVE 43 17.Apr2oo3 24Aor2oo3 2903 24,42 4805 816,9 110.0 242,0 27.0 8,0
AVE 44 24.Apr2003 1.Mai2003 30 16 2603 499.3 848.9 117 3 2580 327 99
AVE 45 1.Mai2003 8.Ma12003 22,99 2454 380,5 6469 110,6 243,2 20,3 7,6
AVE 46 8.Mai2oo3 15 Mai2oo3 7,13 19.73 118,0 2006 88,9 1955 49 4,8
AVE 47 15.Ma12oo3 22.Mai2003 733 1481 1213 2062 667 1468 5,5 39
AVE 48 22.Mai2003 29.Mai2003 4,10 3241 679 115.4 146,0 3212 18 4,9
AVE 49 29.Ma12003 5.Jun2003 2,09 1428 347 589 643 141.6 1,7 4,1
AVE 50 5.Jun2003 12.Jun2003 078 1188 129 219 535 1177 07 37
AVE 51 12.Jun2oo3 19.Jun2003 15,22 1542 252,0 4284 695 152,9 7,2 2,6
AVE 52 19.Jun2oo3 26.Jun2003 387 1482 640 1088 668 1469 2.0 27
AVE 53 26.Jun2003 3.Ju12003 1804 582 2986 5077 26,2 576 183 21
AVE 54 3.Ju12oo3 10.Ju12003 20 28 11.35 3357 5707 51,1 1125 9,9 2,0
AVE 55 10.Ju12003 17.JuI2003 2503 1247 414,4 704 5 562 1236 210 37
AVE 56 17.Ju12003 24.Ju12003 1554 732 2572 4373 330 726 123 2.0
AVE 57 24.Ju12003 31.Ju12003 1878 9,54 3109 528,5 43,0 945 11,1 2.0
AVE 58 31.Ju12003 7.Aug2003 4013 17 72 664 3 11292 798 1756 84 13
AVE 59 7.AuQ2003 14.AuQ2003 1643 1484 272,0 4625 669 1471 62 20
AVE 60 14.Aug2003 21.Aug2003 1217 13,03 2014 3424 58,7 1291 10.8 4,1
AVE 61 21.AuQ2003 28.AuQ2003 2135 11.57 3534 6008 521 1147 17.2 3,3
AVE 62 28.AuQ2003 4.Sep2003 4630 764 766,4 13029 344 757 235 14
AVE 63 4.Sep2003 11.Sep2003 7143 14,32 1182,5 2010,2 64,5 1419 36,3 2,6
AVE 64 11.Sep2003 18.Sep2003 72,49 1979 12000 2039,9 891 1961 17,1 1,6
AVE 65 18.Sep2003 25.Sep2003 7082 1632 11723 1992.9 73.5 1618 31,5 2.6
AVE 66 25.Sep2003 2.0k12003 71.83 1094 1189,1 2021,5 49,3 108,4 32,9 1.8

Page 21
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT AVEIRO Jul. 02 • Jul. 04

tt~~~~~ft;~~;~
~t~t~t! r.äi!npiing ?lNif~
f::i!};;T{:.--".':,;':"'.('.:ti,i"
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11 :'1, ~ .,;';.'~I.";:
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7;:~'._~;1 : % ;i. '~~.t,;':

, ;~!lla.!:,l~'n

(ddJmmlyyyy) (dd/mm/yyyy) (ng/m'] lng/m'] (ng/m']STP Ing/m']STP [ng/rfI'J STP Ing/m')STP Ing/m')STP lng/m'] STP
STP STP
AVE 67 20kl2003 9.0k12003 7036 20,97 1164,7 19801 94.4 207.8 33,4 3,5
AVE 68 9.0k12003 16.0k12003 96,27 12,62 1593,6 2709,1 56,8 125,1 20,3 0,9
AVE 69 16.0k12003 23.0k12003 68,77 26,29 1138,4 1935,4 1184 260,5 20,7 2,8
AVE 70 23.0k12oo3 30.0k12003 102,23 17,09 16922 2876,8 77,0 169,3 520 3.1
AVE 71 30.0k12003 6 Nov2003 110,59 45,04 1830,8 3112,3 202,9 446,3 38,7 5,5
AVE 72 6.Nov2003 13.Nov2003 86,41 22,33 1430,S 24318 100,6 221,3 26,8 2,4
AVE 73 13.Nov2003 20.Nov2003 128,86 27,19 2133,2 3626,4 122,5 269,5 30,1 2,2
AVE 74 20.Nov2003 27.Nov2003 133,10 14,55 2203,3 3745,6 65,6 144,2 23,3 0,9
AVE 75 27.Nov2003 4Dez2003 139,22 8,72 2304,7 3918,0 39,3 86,4 17,2 04
AVE 76 4.Dez2003 11.Dez2003 156,49 34,66 2590,5 4403,8 156,1 343,5 36,S 2,8
AVE 77 11.Dez2003 18.Dez2003 140,93 32,66 23329 3965,9 147,1 323,6 38,5 3,1
AVE 78 18Dez2003 25Dez2003 485,80 5209 8042,0 13671,4 234,6 516,2 73,3 28
AVE 79 25Dez2003 31.Dez2003 190,75 33,82 3157,6 5367,9 152,3 335,1 66,5 4,2
AVE 80 31.Dez2003 8Jän2004 384,33 37,65 6362,3 10815,9 169,6 3731 55,0 1,9
AVE 81 8.Jän2004 15.Jän2004 18683 724 3092,8 5257,8 326 71,7 113,4 15
AVE 82 15.Jän2004 22.Jän2004 328,95 36,28 5445.4 9257,2 163,4 359,6 43,6 1,7
AVE 83 22.Jän2004 29.Jän2004 284,62 46,52 47116 8009,7 2095 461,0 42,1 2,4
AVE 84 29.Jän2004 5.Feb2004 228.22 38,46 3778,0 6422,6 173,3 381,2 31,8 1,9
AVE 85 5.Feb2004 12.Feb2004 22472 47,48 3720.0 6324,1 213.9 470,5 28,4 21
AVE 86 12Feb2004 19 Feb2004 219,25 51,72 36294 6170,0 233,0 5125 24,4 20
AVE 87 19.Feb2004 26.Feb2004 169,25 38,11 2801,8 4763,0 171,7 377,7 40,1 3,2
AVE 88 26.Feb2004 4.Mär2004 190,92 39,11 31605 5372,9 176,2 3876 38,7 2,8
AVE 89 4 Mär2004 11 Mär2004 21166 42,21 3503.8 5956,5 190,1 418,3 54,9 3,9
AVE 90 11.Mat2004 18.Mär2004 218,23 39,50 3612,6 6141,5 177,9 391,5 45,5 2,9
AVE 91 18.Mär2004 25.Mär2004 137,09 3738 2269,5 3858,1 168,4 370,5 44,2 4,2
AVE 92 25.Mär2004 1.A r2oo4 5370 15,68 889,0 1511,3 70,6 155,4 35,6 3,7
AVE 93 1.Apr2004 8.A 004 92,82 27,73 1536,6 2612,2 124,9 274,8 40,1 4,2
AVE 94 8Apr2004 15.A 004 76,11 3904 12600 21419 1759 3869 30,9 5,6
AVE 95 15 Apr2OO4 22.A 2004 29,35 7,27 485,8 825,8 32,8 72,1 33,9 3,0
AVE 96 22.Aor2004 29A 2004 4164 34,08 6893 1171,9 1535 3377 16,7 4,8
AVE 97 29.Apr2004 6.Mai2004 20,13 656 333,2 566,5 29,6 650 24,8 2,8
AVE 98 6.Mai2004 13.Mai2004 41,54 3,40 687,7 1169,1 15,3 33,7 54,0 1,6
AVE 99 13.Mai2004 20 Mai2004 3148 596 521 1 885,9 26,8 59,0 12,3 0,8
AVE 100 20.Mai2004 27.Mal2004 18,45 3054 5193 12,9
AVE 101 27.Mai2004 3.Jun2004 14,28 236 4 401,9 13,9
AVE 102 3.Jun2004 10.Jun2004 492 279 814 138,4 126 27,6 57 1,1
AVE 103 10.Jun2004 17.Jun2004 33,03 7,95 546,8 929,5 35,8 78,8 17,0 1,4

Page 22
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT PUY DE DOME Oct. 02 • Oct. 04

r~~i~~
~~itr&~i~~,~w~~*~~~W~~l
~~1f~~%~~~~
~;~~~~~~ ~i1~~lKm
;~~i,~~1
(ddlrnmlyyyy)
,
~*~~{~~tri~
!~1~~@~ &~~~~tfy.l~
(ddlrnrnlyyyy) [ng/rn']'
STP
[ng/ril']
~P
[ng/m']STP (ng/rn'] STP (ng/m'jSTP (ng/rn']STP [ng/m']STP [ng/m'j STP

HV.Pdd-Ol 25 Seo 2002 30kl2002 14,70 3770 243,3 4137 1698 373,6 15,1 13,7
HV.Pdd.02 30kl2002 100kl2oo2 1,29 12,82 21,3 36,2 57,7 127,0 2,6 8,9
HV.Pdd-03 100kl2oo2 160kl2002 5,74 9,33 951 161,6 42,0 92,S 13,7 7,8
HV.Pdd-04 160kl2002 240kl2oo2 629 1657 104,1 1770 747 164,2 37,2 34,S
HV-Pdd-05 240kl2002 310kl2002 7,80 511 1291 219,5 230 50,6 28,1 6,5
HV-Pdd-06 310kl2002 7 Ney 2002 457 75,6 128,6 13,5
HV-Pdd-07 7 Ney 2002 14 Ney 2002 2,57 3,95 42,6 72,4 178 39,1 10,3 5,6
HV.Pdd-08 14 Ney 2002 21 Nay 2002 14,15 443 234,2 398,1 20,0 43,9 89,6 9,9
HV.Pdd.09 21 Ney 2002 28 Ney 2002 3,66 60,6 103,1 222
HV.Pdd.10 28 Nay 2002 10 Dez 2002 353 58,4 99,3 54,7
HV.Pdd.11 10 Dez 2002 17 Dez 2002 584 967 164,3 29,4
HV.Pdd.12 17 Dez 2002 27 Dez 2002 545 90,2 153,3 26,9
HV-Pdd.13 27 Dez 2002 3 Jan 2003 125 20,7 35,2 25,7
HV.Pdd.14 3 Jan 2003 9 Jan 2003 21,41 354,5 602,6 84,9
HV.Pdd.15 9 Jan 2003 16 Jan 2003 2768 4582 779,0 42,1
HV.Pdd.16 16 Jan 2003 23 Jan 2003 8,14 134,8 229,1 50,6
HV.Pdd.17 23 Jan 2003 31 Jan 2003 6,30 104,3 177.3 38,9
HV-Pdd.18 31 Jan 2003 6 Feb 2003 3,45 3,43 57,1 97,1 15,4 340 30,7 10,7
HV.Pdd.19 6 Feb 2003 13 Feb 2003 8,18 135,4 230,1 44,0
HV-Pdd.20 13 Feb 2003 20 Feb 2003 2643 453 4376 743,9 204 44,9 25,1 1,5
HV-Pdd.21 20 Feb 2003 27 Feb 2003 14,06 10,67 2327 395,6 48,1 1057 11,6 3,1
HV.Pdd.22 27 Feb 2003 6 Mär 2003 1074 10,00 177.7 302,1 45,0 991 38,7 12,7
HV.Pdd.23 6 Mar 2003 13103/03 9hoo 27,28 31,90 451,5 767,6 143,7 316,1 SO,S 20,8
HV.Pdd-24 13/03/03 10h00 201031039h15 4754 959 787,1 1338,0 43,2 95,0 275 2,0
HV.Pdd.25 20 Mar 2003 27 Mar 2003 25,87 19,86 428,3 728,0 89,5 196,9 12,6 3,4
HV.Pdd.26 27 Mar 2003 3A1 2003 11,88 17 24 196,6 3343 77.7 170,9 8,3 4,2
HV.Pdd-28 3 ADf2003 lOA 2003 735 29 96 1217 206,9 135,0 296,9 9,5 13,6
HV.Pdd.29 10 Apr 2003 17A 2003 5,40 4054 89,4 151,9 1826 401,8 3,9 10,3
HV.Pdd-31 23Ap 2003 30A 2003 522 24,14 86,5 147,0 108,7 239,2 4,2 6,8
HV.Pdd.32 30Ap 2003 7 Mai 2003 7,61 4882 126,0 214,2 219,9 483,8 67 151
HV.Pdd.33 7 Mai 2003 15 Mal2003 13,53 50,70 224,0 3809 228,4 5024 8,5 11,3
HV-Pdd.34 15 Mal2oo3 22 Mal2oo3 440 29,51 728 123,8 1329 292,4 7,0 16,5
HV.Pdd.35 22 Mai 2003 28 Mal2oo3 731 1147 121,1 205,9 517 1137 7,7 4,3
HV.Pdd.36 28 Mai 2003 5 Jun 2003 26,28 6670 435,1 739,7 300,5 6610 11,2 10,0
HV.Pdd.37 5 Jun 2003 12 Jun 2003 3211 81,12 531,6 903,6 365,4 8039 14,8 13,2
HV.Pdd.39 17 Jun 2003 24 Jun 2003 54,73 100,30 906,1 1540,3 451,8 993,9 33,S 21,6
HV-Pdd-40 24 Jun 2003 1 Jul2oo3 3533 58,43 584,8 9942 263,2 579,0 14,5 8,4
HV.Pdd-41 1 Ju/2oo3 8 Jul2003 8872 4758 1468,6 2496 6 214,3 4715 56,9 10,7
HV-Pdd-42 8 Jul2003 15 Jul2oo3 7102 5590 1175,6 19986 251,8 554,0 16,3 4,5
HV.Pdd-43 15 Jul2003 28,85 2686 477,6 8118 1210 2662 14,4 4,7
HV.Pdd-44 22 Jul2003 28 Jul2003 12,61 38,23 208,7 3548 172,2 3788 7,4 79
HV.Pdd-45 2 Seo 2003 11 Seo 2003 30,64 25,90 507,3 862,4 116,7 2567 39,7 11,8
HV-Pdd-46 11 Sep 2003 18 Sep 2003 2167 2281 3586 609,7 102,7 226,0 15,5 5,7
HV.Pdd-47 18 Sep 2003 25 Sep 2003 19,39 15,25 320,9 545,6 68,7 1512 10,7 3,0
HV.Pdd-48 25 Sep 2003 20kl2003 12,89 16,68 2134 3628 75,1 1653 10,8 4,9
HV-Pdd-49 20kl2003 90kt2OO3 13,97 62,9 1385 8,5
HV.Pdd.50 90kl2003 160kl2oo3 17 39 24,72 2878 4893 111,4 245,0 24,S 123
HV-Pdd-51 160kl2oo3 290kl2oo3 18,02 1943 298,3 507,1 87,S 192,5 23,7 9,0
HV.Pdd.52 29 Okt 2003 6 Nay 2003 2592 1145 4291 7295 516 1135 34,2 5,3
HV.Pdd.53 6 Nay 2003 13 Nay 2003 6,37 105,4 1791 9,3
HV.Pdd.54 13 Nay 2003 15/11/2003 17 5,74 35,41 95,0 1614 1595 3509 45,0 97,7
HV-Pdd.55 20 Nay 2003 27 Nay 2003 22,51 18,02 372,6 633,4 812 178,6 55,3 15,6
HV.Pdd.56 27 Nay 2003 4 Dez2003 658 485 1089 1851 219 481 444 11,5
HV.Pdd.57 4 Dez 2003 11 Dez 2003 13,75 1103 2277 387,1 49,7 109,3 28,S 81
HV.Pdd.58 18 Dez 2003 2 Jan 2004 4,52 20,4 448 5,5
HV.Pdd.59 6 Jan 2004 13 Jan 2004 711 762 117,6 200,0 34,3 755 853 32,2
HV.Pdd-60 13 Jan 2004 19 Jan 2004 165 9,95 27,3 464 44,8 986 24,5 52,2
HV-Pdd-61 21 Jan 2004 29 Jan 2004 1,59 24,98 263 447 112,5 247,6 3,5 19,2
HV.Pdd-62 29 Jan 2004 5 Feb 2004 10,85 25,50 179,6 305,4 1149 2527 42,2 34,9
HV.Pdd-63 5 Feb 2004 11 Feb 2004 23,02 34,59 3812 648,0 1558 3428 56,0 29,6
HV-Pdd-64 11 Feb 2004 18 Feb 2004 1297 11,15 214,7 364 9 50,2 110,5 36,9 112
HV-Pdd-65 18 Feb 2004 25 Feb 2004 13,94 2,88 2308 392,3 13,0 28,5 90,5 66

Page 23
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT PUY DE DOME Ocl. 02. Ocl. 04

~~5~fiti;~;-;
~Sl~~ffirîJ 1ä:n-~:6f...~
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af;t:~~t~:~~,'\~~~;~:~;!
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'i:f~Jciiî~I~~t
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~;f:i~~l~~,9~'~;itt'1
ö'ê)~".-"""'il"(oM'1 ,tL;"('ÖC'»"!<- ~":.YoM"~'L'S!TIOke(OM)/OM DebfiS(OM)/OM
f,;i\~,~.;
,c~":~'

~:.1:.::f.~~~~:~~::-
~.t.~~~mp,
..:~",/:~~~::
~~~~:~~~~~:!?,~~.,:~~
,'~.:t:;~;lt.,f.+~i-'~~:?.è~~!f:i!
l:~.~~~;~~,~;.\-,_ ~~ .~~~~~~ ..f:;:,- :.•
#;_ .••• :t,l).~;,,~iW.l~\:.~,(,.J.~,!: ..~.~~::~;~;.,'j';'?:'?laj~l'~;~~;~~;
..:}~-:};~c;.~J,~?(o/.rh
(ddlmmlyyyy) (ddlmmlyyyy) (nglm'] [nglm') (nglm') STP [nglm') STP (nglm') STP (nglm'] STP (ng/m') STP [ng/m'] STl'
STP STP
HV.Pdd.66 25 Feb 2004 3 Mar 2004 2802 3026 463,8 788,5 136,3 299,8 32,9 12,5
HV.Pd~7 3Mar 2004 10 Mar 2004 5,88 S,51 973 165,4 24,8 546 23,S 7,8
HV.Pdd-68 la Mar 2004 14 Mar 2004 9,37 9,02 155,2 263,8 40,6 89,4 443 15,0
HV-Pdd.69 17 Mar 2004 24 Mar 2004 12,32 27,94 203,9 3467 125,9 276,9 44,9 35,8
HV.Pdd.70 24 Mar 2004 30 Mar 2004 18,48 7,48 305,9 520,1 33,7 74,1 207 2,9
HV.Pdd.71 30 Mar 2004 6ApI'2oo4 3,57 10,36 590 100,3 46,7 1027 8,8 90
HV.Pdd.72 6 ArJr 2004 13 ArJr 2004 11,18 4125 1851 314,7 185,8 4088 26,0 33,8
HV.Pdd.73 13 ADl' 2004 22 Aor 2004 14,42 33,57 238,7 405,8 151,2 332,7 455 37,3
HV.Pdd.74 22 Acr 2004 28 Apl' 2004 15,27 8644 252,7 429,7 369,4 856,6 149 29,7
HV.Pdd.75 26 Aor 2004 5 Mai 2004 10,25 29,33 169,7 288,4 132,1 290,6 240 24,1
HV. d 77
o 12 Mai 2004 19 Mal2004 13,59 3350 225,0 382,6 1509 3320 6,9 6,0
HVo dd.78 19 Mai 2004 26 Mai 2004 11,66 6057 193,0 326,1 272 9 600,3 57 10,4
HV. dd.79 26 Mal2004 2 Jun 2004 1465 34,02 242,5 4123 153,2 337,1 31,8 26,0
HV. dd-BO 2 Jun 2004 9 Jun 2004 2438 46,24 4037 686,2 206,3 458,2 185 12,3
HV. ddo81 9 Jun 2004 16 Jun 2004 21,19 43,97 350,8 596,4 198,1 435,7 9,9 7,2
HV.pdd.82 16 Jun 2004 23 Jun 2004 21,84 31,64 361,5 614,5 .142,5 313,5 18,0 9,2
HV.pdd-B3 23 Jun 2004 30 Jun 2004 44,86 27,15 7427 12625 122,3 269,0 36,S 7,8
HV. dd-84 30Jun 2004 7 Jul2004 31,54 15,30 5222 8877 66,9 1516 23,6 4,0
HV.ldd-B5 7 Jul2oo4 13 Jul2oo4 4012 11,65 664,1 1129,0 53,4 117 4 40,2 4,2
HV. dd-B8 13 Jul2004 21 Jul2004 8609 38,30 1425,2 2422,8 172,5 379,5 46,0 7,2
HV. dd-B7 21 Jul2004 27 Jul2004 14256 5016 2360,0 4011,9 225,9 497,1 55,0 68
HV.ldd.88 27 Jul2004 4 Auo 2004 77 53 59,45 1283,4 2181,8 267,8 589,1 25,7 69
HV.ldd.89 4 Au!! 2004 11 Au!! 2004 118,41 24,97 1960,2 3332,4 112,5 2474 111,6 B,3
HV. ddo91 26 Au!! 2004 6 Sec 2004 11,34 2,87 167,6 3190 12,9 285 21,6 1,9
HV. dd.92 6 Sec 2004 15 Sec 2004 29,10 4,58 4818 819,0 20,6 454 34,4 1,9

Page 24
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT SCHAUINSLAND Oct. 02- Oct. 04

.}~tsîfu~:i~t:::;-St~itit!.~d~l~~öf.
~~!~:"t~~~\jfJ~:i~ ~~t~~~~!( î~i~\V~6ii~~~i
If;~~;~J'g .~~r~~~â~; '~~-~(Ô~6~is f:I~'ntb~b~iä: }V!~"~-;~~.~,~lJ:.:.;.:~;:;;~;7~J'~.I~~~Xs"?~
AC~,,<~1!,t,.,.~,g'il''''~''l: """,: fi ";"f;'.!.f..'/} ~~eYoiC ,,}Cell.,ci '''''''''~k-':io8i' ,..", ~':''idM"j. '!{;:(ÔCi~~~;;""F](ÔMr-~1'" ;smake(OMI/OM Debrls(OM)/OM
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,,::~.~9.~~~:,:~:~.v ...:-.\~~.~lt~.f
';..~t~:' 1~~::~~.J".l.,%\i,
;\~f:,.:.:.-.\.::';}-~:!;:!f.'~::~t~}10~\i:t:~-IH :):::':~!.
(ddlmmlyyyy) (ddlmm/yYyy) (ng/rn'] [ng/m') [nglrn') STP (ng/m') STP [nglm') STP [ng/rn'J STP [ng/m']STP [ng/m'] STP
STP STP
SIL.()2/01 12 Sep 2002 18 Sep 2002 28,34 29,87 469,2 797,6 134,5 296,0 10,8 .,0
SIL.()2/02 150kl2002 220kl2002 13,72 2101 2271 386,1 94,6 208,2 23,9 12.9
SIL.()2/03 220kl2002 280kl2oo2 13,90 21,12 230,1 391,2 97,8 215,2 24,0 13,2
SIL.()2104 280kl2002 5 Nav 2002 12,66 10,54 209,5 356,2 47,S 104,4 16,5 .,8
SIL.()2105 5 Nav 2002 12 Nav 2002 1067 659 176,6 3003 29,7 65,3 313 6,8
SIL.()2/06 12 Nav 2002 21 Nav 2002 33,81 1692 5596 951,4 76,2 167,6 51,0 9.0
SIL.()2107 21 Nav 2002 28 Nav 2002 4,22 7,50 69,9 118,8 33,8 74,3 10,8 6,7
SIL.()2108 28 Nav 2002 5 Dez 2002 8,67 283 1435 243,9 12,8 28,1 22,5 2,6
SIL.()2/09 5 Dez 2002 9 Dez 2002 4,29 19,3 42,5 5,4
SIL.()2110 9 Dez 2002 12 Dez 2002 31,53 21,79 522,0 887,4 98,2 216,0 44,2 10,8
SIL.()2111 12 Dez 2002 19 Dez 2002 7.98 6,43 132,1 2246 29,0 63,7 23,6 6,7
SIL.()2/12 19 Dez 2002 26 Dez 2002 16,96 9,91 280,8 477,3 44,6 98,2 48,7 10,0
SIL.02/13 26 Dez 2002 2 Jan 2003 14,90 7,46 246,7 419,4 33,6 74,0 65,3 11,5
SIL.()3/01 2 Jan 2003 9 Jan 2003 51,98 1031 860,5 1462,9 46,S 102,2 69,2 4,8
SIL.()3/02 9 Jan 2003 16 Jan 2003 15,66 5,81 259,3 440,8 26,2 57,6 10,8 1,4
SIL.()3/03 16 Jan 2003 23 Jan 2003 17,13 3,79 283,6 482,1 17,1 37,5 44,5 3,5
SIL.()3/04 23 Jan 2003 30 Jan 2003 8,24 374 136,4 231,9 16,8 370 36,4 5,8
SIL.()3/05 30 Jan 2003 6 Feb 2003 25,37 3,23 419,9 713,9 14,6 32,1 84,0 3,8
SIL.()3/06 6 Feb 2003 13 Feb 2003 45,12 3,56 756,9 1286,6 16,0 35,3 46,6 1,3
SIL.()3/07 13 Feb 2003 20 Feb 2003 5599 5,88 926,8 1575,6 26,5 58,3 20.8 0,8
SIL.()3/08 20 Feb 2003 27 Feb 2003 33,97 5,13 562,3 955,9 23,1 50,8 23,2 1,2
SIL.()3/09 27 Feb 2003 6 Mar 2003 26,05 1681 431,3 733,2 75,7 166,6 23,6 5,4
SIL.()3/10 6 Mar 2003 13 Mar 2003 30,24 23,06 5006 851,0 1039 228,5 35,2 9,5
SIL.()3/11 13 Mar 2003 20 Mar 2003 40,53 14,49 670,9 1140,5 65,3 143,6 30,5 3,8
SIL.()3/12 20 Mar 2003 27 Mar2oo3 23,54 27,57 3897 662,5 124,2 273,3 12,4 5,1
SIL.()3/13 27 Mar 2003 3A r2oo3 13,77 10116 228,0 387,6 455,7 1002,5 6,8 177
SIL.()3/14 3 Apr 2003 lOA 2003 15,27 23,22 252,7 429,6 104,6 230,1 20,9 11,2
SIL.()3/15 10 Apr 2003 17A 2003 24,14 2756 3996 679,3 1241 273,1 15,9 6,4
SIL.()3/18 17 Apr 2003 24A 2003 17,40 38,43 288,1 489,8 173,1 3809 139 10,8
SIL.()3/17 24 Apr 2003 30A 2003 10,33 110,96 171,0 290,7 499,8 1099,6 8,1 30,7
SIL.()3/18 30Apr 2003 8 Mai2003 1010 88,44 167,3 2843 3984 8764 3,1 9,6
SIL.()3/19 8 Mai 2003 15 Mai 2003 19,82 15013 328,1 557,7 676,3 1487,8 11,6 31,1
SIL.()3120 15 Mai 2003 22 Mal2003 10,19 115,23 168,7 2867 519,1 1141,9 10,9 43,4
SIL.()3121 22 Mai 2003 28 Mai 2003 3,04 1911 50,4 85,6 861 189,3 2,0 4,4
SIL.()3122 28 Mal2oo3 5 Jun 2003 16,00 80,48 264,9 450,4 362,5 797,5 7,8 13,8
SIL.()3/23 5 Jun 2003 12 Jun 2003 688 100,86 114,0 193,7 454,3 999,6 2,9 15,1
SIL.()3124 12 Jun 2003 18 Jun 2003 8,43 14058 139,6 2373 633,2 1393,1 3,8 22,0
SIL.()3125 18 Jun 2003 25 Jun 2003 6,43 85,43 1064 180,8 384,8 846,6 3,1 14,6
SIL.()3126 25 Jun 2003 3 Jul2003 7,16 46,21 118,6 201,6 208,1 457,9 3,5 8,0
SIL.()3127 3 Jul2003 10 Jul2003 14,53 34,19 240,5 4089 1540 3388 8,4 6,9
SIL.()3128 10 Jul 2003 17 Jul2oo3 10,31 42,33 170,7 290,1 190,7 419,5 4,6 6,6
SIL.()3129 17 Jul2oo3 24 Jul2oo3 26,90 27,37 445,3 756,9 123,3 271,2 16,0 5,7
SIL.()3/30 24 Jul2003 31 Jul2oo3 31,46 141,7 311,7 6,6
SIL.03/31 31 Jul 2003 7 Aug 2003 62,90 63,42 1041,2 1770,0 285,7 628,5 21,4 7,6
SIL.()3/32 7 AU!l2003 14 Aug 2003 5078 46,43 840,6 1429 0 209,1 460,1 11,1 3,6
SIL.()3/33A 14 AU!l2003 21 Aug 2003 18,34 16,17 303,6 516,1 12,9 160,3 13,9 4,3
SIL.()3/34A 21 Au!l2003 28 Aug 2003 32,79 27,44 542,8 922,8 123,6 272,0 19,1 5,6
SIL.()3/35 28 AU!l2003 4 Sep 2003 1408 2417 233 1 396 3 108,9 239,5 7,9 4,8
SIL.()3/36 4 Sep 2003 11 SeP 2003 29,90 46,05 4950 8415 207,4 4563 10,4 56
SIL.()3/37 11 Sec 2003 18 Sep 2003 46,94 25,09 777,0 1321,0 113,0 248,7 28,6 5,4
SIL.()3/38 18 Sec 2003 25 Sec 2003 55,48 32,86 918,4 1561,4 1480 325,6 184 3,8
SIL.()3/39 25 Sep 2003 20kl2oo3 43,09 33,36 713,3 1212,6 150,3 330,6 30,4 8,3
SIL.()3/40 20kl2oo3 90kl2003 29,37 62,60 486,2 826,6 282,0 620,3 44,0 33,0
SIL.()3/41 90kl2003 160kl2oo3 5004 55,52 828,4 14083 250,1 5502 42,0 16,4
SIL.()3/42 160kl2oo3 230kl2003 2471 54,09 4091 6954 243,6 536,0 16,2 12,5
SIL.()3/43 230kl2003 30 Okt 2003 19,97 1938 330,7 562,1 87,3 192,0 20,8 7,1
SIL.03/44 300kl2003 5 Nay 2003 3204 26,79 530,4 9017 120,7 265,5 43,2 12,7
SIL.()3/45 5 Nav 2003 13 Nav 2003 583 4621 96,S 1640 208,1 457,9 4,2 11,7
SIL.()3/46 13 Nay 2003 20 Nav 2003 18,70 5,09 309,6 526,4 22,9 50,5 40,3 3,9
SIL.()3/47 20 Nav 2003 27 Nav 2003 4628 3041 7661 1302,3 137,0 301,3 55,1 12,8
SIL.()3/48 27 Nav 2003 4Dez2oo3 24,13 17,98 399,4 679,1 81,0 178,2 31,9 8,4
SIL.()3/49 4 Dez 2003 11 Dez 2003 37,28 15,30 617,2 1049,2 68,9 151,7 47,1 6,8
SIL.()3/50 11 Dez 2003 18 Dez 2003 9,30 9,15 154,0 261,7 41,2 907 31,1 10,8
SIL.()3/51 18 Dez 2003 26 Dez 2003 17,27 12,28 285,9 486,0 55,3 121,7 42,9 10,7
SIL.03/52 26 Dez 2003 30 Dez 2003 27,64 36,58 457,6 777,9 164,8 362,5 56,9 26,5
SIL.()4/01 2 Jan 2004 8 Jan 2004 1604 6,99 265,6 451,5 315 693 38,1 5,8
SIL.()4/02 8 Jan 2004 15 Jan 2004 15,92 45,43 263,5 448,0 204,6 450,2 47,6 47,8

Page 25
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT SCHAUINSLAND

Wood Plant
Sample Starting date of En.a. date of Wood Wood Plant Debris Plant Debris
Levo.c CeU.c smoke(OM)/OM Debrls(OM)/OM
Code sampling sampling smoke(OC) smoke (OM) (OC) (OM)
1%1 1%1
(ddlmmlyyyy) (ddlm mlyyyy) [ng/m'l [ng/m'l [ng/m'l STP [ng/m'l STP [ng/m'l STP [ng/m'l STP [ng/m'l STP [ng/m'l STP
STP STP
SIL.()4J03 15 Jan 2004 22 Jan 2004 24.90 31,08 412,1 700,6 140,0 308,0 78,3 34,4
SIL.(I4I04 22 Jan 2004 29 Jan 2004 19,88 14,05 329,0 559,4 63,3 139,2 48,4 12,1
SIL.(I4I05 29 Jan 2004 5 Feb 2004 19,57 20,77 324,0 550,8 93,6 205,9 40,2 15,0
SIL.()4J06 5 Feb 2004 12 Feb 2004 29,34 35,00 485,7 825,7 157,7 346,8 65,3 27,4
SIL.()4J07 12 Feb 2004 19 Feb 2004 19,26 17,84 318,8 542,0 80,3 176,8 21,2 6,9
SIL.(I4I08 19 Feb 2004 26 Feb 2004 24,69 21,13 408,7 694,7 95,2 209,4 23,3 7,0
SIL.(I4I09 26 Feb 2004 4 Mar2004 16,48 1379 272,7 463,7 62,1 136,7 12,7 3,7
SIL.(I4I10 4 Mar 2004 11 Mar 2004 18,82 7,73 311,6 529,7 34,8 76,6 14,2 2,1
SIL.(I4Ill 11 Mar 2004 19 Mar 2004 9,81 42,54 162,4 276,2 191,6 421,5 8,2 12,6
SIL.(I4I12 19 Mar 2004 25 Mar 2004 14,67 18,08 242,8 412,8 81,4 179,2 45,7 19,9
SILo()4113 25 Mar 2004 1J.pr 2004 25,47 37.00 421,6 716,7 166,7 366,7 12,6 6,5
SILo()4114 1 ADr 2004 8 r2OO4 21,14 163,95 350,0 595,0 738,5 1624,8 27,5 75,1
SILo()4115 8A r2004 15 .pr2004 29,93 31,58 495,5 842,4 142,2 312,9 17,4 6,5
SILo()4116 15 pr 2004 22 .pr2004 39,37 83,28 651,7 1107,9 375,1 825,3 31,0 23,1
SIL.(I4I17.1 22 pr 2004 23 .pr2004 22,33 144,82 369,6 628,3 652,3 1435,1 15,2 34,7
SIL.()4J17.11 23 pr 2004 29 >l>r2004 39,40 132,47 652,2 1108,7 596,7 1312,8 27,2 32,2
SIL.()4J18 29 pr 2004 6 Mai 2004 22,22 90,74 367,8 625,2 408,7 899,2 15,9 22,8
SIL.()4J19 6 Mai 2004 13 Mai 2004 17,79 34,03 2946 500,8 153,3 337,3 19,0 12,8
SIL-04I20 13 Mai 2004 19 Mai 2004 23,25 73,79 384,8 654,2 332,4 731,3 9,7 10,8
SIL-04I21 19 Mai 2004 27 Mai 2004 6,12 92,57 101,2 172,1 417,0 917,3 4,2 22,3
SIL.(I4I22 27 Mai 2004 3 Jun 2004 22,39 93,43 370,7 630,2 420,8 925,8 13,6 20,0
SIL-04I23 3 Jun 2004 9 Jun 2004 23,23 79,62 384,6 653,7 358,6 789,0 7,2 8,6
SIL-04I24 9 Jun 2004 17 Jun 2004 41,26 18,68 683,0 1161,1 84,2 185,2 11,0 1,8
SIL.(I4I25 17 Jun 2004 24 Jun 2004 3251 50,73 538,2 915,0 228,5 502,7 17,6 9,7
SIL-04I26 24 Jun 2004 1 Jul2004 6,96 138,67 115,2 195,8 6246 1374,2 2,7 19,0
SIL.(I4I27 1 Jul2OO4 8 Jul2004 36,98 85,30 612,2 1040,7 384.2 845,3 16,3 13,2
SIL.(I4I28 8 Jul2OO4 13 Jul2004 4,23 19,1 42,0 2,0
SILo()412811 14 Jul2oo4 15 Jul 2004 208,63 78,49 3453,6 5871,2 353,5 777,8 70,2 9,3
SIL.(I4I29 15 Jul2oo4 22 Jul2004 24,47 45,72 405,0 688,6 205,9 453,1 11,6 7,7
SILo()4130 22 Jul2OO4 29 Jul2004 29,56 30,49 489,3 831,8 137,3 302,1 5,5 2,0
SILo()4131 29 Jul2004 5Au02004 45,40 31,81 751,6 1277,7 143,3 315,2 10,0 2,5
SILo()4132 5 AUQ2004 12 AUQ2004 21,46 28,15 355,2 603,8 126,8 278,9 6,9 3,2
SIL.o4I33 12AuQ 2004 19 AUQ2004 34,30 37,72 5678 965,3 169,9 373,8 28,8 11,1
SIL.()4J34 19 AUQ2004 26 AUQ2004 13,99 26,07 231,5 393,6 117,4 258,3 9,6 6,3
SILo()4135 26Aull 2004 2 SeP 2004 25,75 17,61 426,3 724,6 79,3 174,5 29,0 7,0
SIL.()4J36 2 SeP 2004 9 SeP 2004 14,25 27,27 236,0 401,1 122,8 270,2 5,1 3,4
SIL.0413 7 9 SeP 2004 16 Sep 2004 10,44 47,82 1728 293,7 215,4 473,8 8,9 14,3

Page 26
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT SONNaLiCK

.i.:::~'~.ft.'t",:'" :- ::,;"~~~'r:"':';;'P::~'!.~,'\ :;!:
f-:'~i.~h'.~-~.ç.
~:~,: j::,~:':~.l~~~~;'~~~.s:-r
..... ~'~;t-';':~:~"'.->~ T~.;~"~'\r'~ .t;j);t;iJ~~_:,'r!:'~.:~\{~~~1~,:,.~.
.~h>:~':3 ~.".:;t:~tl'\:iti.~:t"-YI ~f=~.:'tWood
~....
;.,
~.~,,~~:H'::~Plarit~'::.j~~.
':~i''..':'~I~~ :~,~!!,,~g,:d~!!(a!~ ';t~v'ö~"
~,n,;~.;~,a.\e,~~th,\~ \~ëe'ii;ê},~~,~VI!'!t?''i!':)'': ~i;fr-'~",o.~8-',P,1~,n.tP~~n~ PI~~~lO!,,~rl~ :;.4\'O'j(iÎ(OM)ÎÖrx 'D~b;';(ÖMiibM
...
!tr\~~~~
..
~1;~:_~~.~~!..~!:
ll?~~t~~~
~~.TfJIr.~;~~_~'{:~~
~(':~i\~/~~ ~~~:~I~::~~.£l~:~;T~~~~~E).; \:JK~~9.!g~~
~~~y9:,~~;:~~~~ ~~:t?~!~~rt~~~
~~~':'~:~;:~~(OM'~~~;>:f{:
l',~_~~~.::-.~~(Oioù'r_t:~i
(ddlmmlyyyy) (dd/mm/yYyy) [ng/m') [ng/m'l '[,;g/m~] STP [ng/m')STP [ng/m'] STP Ing/m') STP [ng/m'] STP [ng/m~STP
STP STP
sao 05 3 Okt 2002 10 Okt 2002 268 24,56 44,3 754 110,6 243.4 1417,1 4575,6
SSO 04 10 Okt 2002 17 Okt 2002 3,94 13,62 65,1 110,7 613 134,9 44591 5433,6
sao 03 17 Okt 2002 24 Okt 2002 2,52 3,27 41 7 709 147 32.4 1290 9 5908
SSO 02 24 Okt 2002 31 Okt 2002 436 634 721 1226 28,6 62.8 906,2 464,3
sao 01 31 Okt 2002 19 Nay 2002 2,15 3,99 35,6 60.6 18,0 39,S 2900 7 1892.9
SSO 06 21 Nay 2002 30 Nay 2002
SSO 07 30 Noy 2002 5 Dez 2002 336 151 333
SSO 08 5 Dez 2002 12 Dez 2002 1,46 242 41 1
SSO 09 12 Dez 2002 19 Dez 2002 31.64 523,8 890,5 62103,6
sao 10 19 Dez 2002 26 Dez 2002 73,62 4,17 1218,8 20719 188 413 70432,0 14037
sao 11 26 Dez 2002 2 Jän 2003 983 328 162,8 2767 148 32,S 110567 13001
sao 12 2 Jän 2003 9 Jän 2003
sao 13 9 Jän 2003 16 Jän 2003 2,71 4,85 44.9 76,4 21,8 48,1
SSO 14 16 Jän 2003 24 Jän 2003 0,76 5,16 126 21.4 23,3 51.2 989,8 2369,6
SSO 15 24Jän 2003 30 Jän 2003 654 295 649 2111.7
sao 16 30 Jän 2003 14 Feb 2003 3,32 550 934 2281 7
sao 17 14 Feb 2003 20 Feb 2003 237 676 393 668 305 67,0 7535 7563
sao 18 20 Feb 2003 27 Feb 2003 1.26 6,71 209 355 302 665 883,7 16570
SSO 19 27 Feb 2003 6 Mär 2003 9,37 42,2 929 701.5
sa020 6 Mär 2003 13 Mär 2003 336 1105 557 946 498 109.5 9437 10922
sao 21 13 Mär 2003 20 Mär 2003 3,30 2.27 547 930 102 225 884 9 2141
sao 22 20 Mär 2003 27 Mär 2003 19,42 14,70 321.4 546.4 66,2 1457 2474,0 659,6
sa023 27 Mär 2003 4 ~ pr 2003 24,46 1378 404,9 6883 621 136,6 20466 406.1
Sa024 4Apr2003 11 \pr 2003 770 339 1274 216,6 153 336 21336 330,7
sao 25 11 Apr 2003 17 \Pr 2003 488 11,68 807 1372 526 1158 18255 15402
seo 26 17 Apr 2003 24 \pr 2003 3,10 13,23 51,4 87,3 59,6 1311 541,3 812.6
sao 27 24Apr 2003 2 Mal2003 597 13.11 98,9 1681 59,0 129.9 605,8 4679
sa028 2 Mal2003 8 Mal2003 1233 4016 2042 3471 1809 397,9 5499 630,4
sao 29 8 Mal2003 15 Mal2003 2910 2708 4817 818,9 1220 2683 972.6 3187
sao 30 15 Mal2003 22 Mal2003 3806 3985 630,0 1071 1 1795 394,9 3864,5 1424.9
sao 31 22 Mal2003 29 Mal2003 2,71 656 449 763 296 650 404,0 344,5
SSO 32 29 Mal2003 5 Jun 2003 314 1803 519 883 812 178,6 6351 12856
seo 33 5 Jun 2003 12 Jun 2003 288 1061 476 809 478 1051 658.5 8552
sao 34 12 Jun 2003 28 Jun 2003 830 1502 1374 2336 676 1488 9835 6265
seo 35 26 Jun 2003 3 Jul2003 459 20,72 76,0 129,2 93,3 205,3 463,7 736,9
sao 36 3 Jul2003 10 Jul2003 539 8,40 893 151.8 37,8 832 14370 788,1
sao 37 10 Jul2003 17 Jul2003 1051 1633 1740 295 8 736 161,9 3849 2106
sao 38 17 Jul2003 24Jul2003 374 5505 620 105 3 2480 5455 816 422,6
sao 39 24 Jul2003 31 Jul2003 7,61 36,21 126,0 214,1 163,1 358,9 3577 599,5
sa040 31 Jul2003 2 AUll2003 780 286 1292 219,6 129 28,3 388,6 50,2
sa041 2 Aug 2003 7 Aug 2003 4529 3361 7498 12747 151,4 333,0 7239 1891
sao 42 7 AUll2oo3 14Aull2003 2413 4202 3995 6791 189,3 416,4 8297 5087
SSO 43 14 AUll2003 21 Aug 2003 6,73 15,65 1114 189,3 705 155,1 347,0 284 2
sa045 28 Aug 2003 4 Sep 2003 7,29 39,53 1207 2051 1781 391,7 380,4 726,4
sao46 4 Sep 2003 11 Sep 2003 207 2801 342 581 1262 2776 1204 5749
seo 47 25 SeD 2003 2 Okt 2003 713 3012 1180 200 6 1357 2985 5489 816,7
sa048 2 Okt 2003 9 Okt 2003 3,55 9,36 58,8 100,0 42.2 92,8 1400,0 1299,2
SSO 49 9 Okt 2003 15 Okt 2003 5,14 52.02 851 144,6 2343 515,5 140.8 501,7
sao 50 15 Okt 2003 16 Okt 2003 620 1026 1744 3602
SSO 51 16 Okt 2003 23 Okt 2003 182 927 301 51,2 418 919 3714 6658
sao 52 230kt2003 31 Okt 2003 201 1613 333 566 727 1598 9513 26880
SSO 53 31 Okt 2003 6 Nay 2003 4,63 11,88 76,6 130,2 535 117,7 1041,6 941,6
sa054 6 Noy 2003 13 Nay 2003 2,57 1423 42,S 722 64,1 141,0 690.2 13471
SSO 55 13 Noy 2003 22 Nay 2003 105 921 173 295 415 91,3 4248 1315.4
seo 56 22 Noy 2003 27 Nay 2003 084 276 139 236 125 274 744 864
SSO 57 27 Nay 2003 4Dez 2003 649 292 64,3 945,1
SSO 58 4 Dez 2003 11 Dez 2003 267 1534 44,2 75,2 691 152,1 581,1 1175,S
seo 59 11 Dez 2003 18 Dez 2003 433 195 429 994.5
saD 60 18Dez2003 25 Dez 2003 227 825 376 64-.1} 372 818 6414 8203
SSO 61 25 Dez 2003 2 Jän 2004 2.45 40,S 68,9 1090,S
SSO 62 2 Jän 2004 8 Jän 2004 0,99 23.05 16,5 280 103,8 228.4 1863 1521,3
sao 63 8 Jän 2004 15 Jän 2004 183 1252 303 516 564 1241 18575 44678
seo 64 15 Jän 2004 22 Jän 2004 422 1402 698 1187 63,1 138.9
SSO 65 22 Jän 2004 29 Jän 2004 3.52 4,56 58,3 991 20.5 45,2 966,5 440.6
sao 66 29 Jän 2004 5 Feb 2004 4,44 21.16 73,4 124,8 95,3 209.7 925,5 1554,3

Page 27
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN CELLULOSE AT SONNBLICK

(i.~~~1!J.
~'JCode;
~h.!~:d;i:iN.~~~
{~~~~~:~~.~;~f.; n~~~f{ ~;B~~$'~
; i':;~samplln9""\;'.
\~~i{i~~Sé1
!';';r,-",'i m'ti,"'~~"';;i,'
;~~~rf~~~~H
N~~w~~,aI~1;~}~'~i:~:'~ri~
samplin9;,~~I<~
:;~~t!}6ß/@; i~t~~;6~'td~'
,::4-[.tl.,;,i'<" "':'ilhyl ~;t;:
i '''~) :smC!~~0C::)lslTlo.~el(O,M) ,1i<~(OC)(~r;t
~'6\.;.,..,.t.i~\~"1,~oe.;,'. ,.;.;"t,:lI.':"!:~"',:-~.Jr-i~ , 1, -....~,.JI\\ ...~.. ,.:'_;.\!-' ~
l
r.,~ ...\~ ..l.:_:. ~~:'~l~ •• ,:-'ll',-~ •.:.'._t.'1_ ..~Jo 'l;.;) 'I ......!.~ 'h.1.'''1 ".If"': ; 'rij,.(OM)it.!
.,~~'.v.-.t'.t~:. " ~~. r.;- :I.r~.,~.' ':'~o:-.'," 0/. )'}.\"'tl'~'
'1'''<
.... ,7'.:-,.~ % ;... r.'... "

(dd/mmJyyyy) (dd/mmlyyYy) [nglm') [nglm'] [nglm') STP [nglm')STP [nglm')STP [nglm') STP [nglm') STP (nglm'ISTP
, STP ~TP
S8067 5 Jän 2004 12 Feb 2004 6,08 14,56 1007 171,1 656 1443 1472,8 1242,1
S8069 19 Feb 2004 26 Feb 2004 2,21 6,89 36,7 623 31,0 683 15630 1712,5
S8070 26 Feb 2004 4 Mär 2004 9,16 874 151,6 257,8 39,4 86,6 4299,8 1445,1
S8071 4 Mär 2004 11 Mär 2004 5,21 9,44 86,3 146,6 42,5 93,5 1064,0 678,6
SB072 11 Mär 2004 18 Mär 2004 1,25 6,05 20,7 35,1 27,2 59,9 181,8 310,3
SB073 18 Mär 2004 25 Mär 2004 7,31 17 69 121,0 205,7 79,7 175,3 1031,4 878,9
S8074 25 Mär 2004 26 Mär 2004 2097 68,99 347,1 590 1 310,8 683,7 790,5 915,9
SB07S 26 Mär 2004 2 Apr 2004 1,82 12,09 30,2 513 54,5 1199 4324 1010,5
SBO 76 2 ADr 2004 8 Aar 2004 432 7,12 71,6 1216 321 70,6 9464 549,2
S8077 8 Aar2004 15 Apr 2004 1,84 6,45 30,4 51,7 29,1 64,0
SBO 78 15 ADr 2004 22 Apr 2004 2,06 478 34,1 58,0 21,5 47,4 566,2 462,6
SBO 79 22 ADr 2004 29 Apr 2004 7,83 10,11 129,6 220,4 45,5 100,2 1420,0 645,6
S8080 29 Apr2004 6 Mai 2004 2,18 5,64 36,1 61,4 25,4 55,9
Se081 13 Ma/2004 20 Mal2004 21,17 18,41 350,4 595,6 82,9 1824 7473,3 2289,1
SBO 82 20 Mai 2004 27 Mai 2004 38,25 9,00 633,2 1076,4 40,6 89,2 4622,6 3832
SBO 83 27 Mai 2004 3 Jun 2004 53,49 17,31 885,5 1505,3 780 171,6 52033,4 5930,8
SB084 3 Jun 2004 10 Jun 2004 12,59 14,11 208,5 354,4 63,6 139,9
SBO 85 10 Jun 2004 17 Jun 2004 22,41 24,82 371,0 630,7 111,8 246,0 8910,3 3475,3
SBO 86 22 Jun 2004 1 Jul2004 3,33 5,61 55,1 93,7 25,3 55,6 758,1 449,4
SBO 87 1 Jul2004 8 Jul2004 6,90 114,2 194,2 2569,9
SB088 8 Jul2004 15 Jul2004 079 1170 13,0 22,2 52,7 1160 194,4 1016,3
SBO 89 15 Jul2004 22 Jul2004 074 122 20,7 844
S8090 22 Jul2004 29 Jul2004 11,17 9,96 185,0 314,5 44,8 98,7 1212,7 380,5
SB091 29 Jul2004 5 Aug 2004 4,11 13,19 68,1 115,8 59,4 130,7 409,9 462,7
SB094 19 Aug 2004 26Aug 2004 3,32 6,29 54,9 93,3 28,3 62,3 453,1 302,4
seo 95 26 Aug 2004 2 Sep 2004 3,92 8,03 64,9 110,4 36,2 79,5 3072,2 2214,2
seo 96 2 Sep2004 9 Sep 2004 516 481 855 145,3 217 477 832,1 273,1
SB097 9 Sep 2004 16 Sep 2004 224 481 370 630 217 47,7 229,5 1738
SBO 98 16 SeD 2004 24Sep 2004 1,75 4,81 29,0 49,3 21,7 47,7 218,2 211,0
SBO 99 24 SeD 2004 30 SeD 2004 2,56 18,39 42,3 71,9 82,8 182,2 592,2 1500,S
SBO 100 30 Sep 2004 7 Old 2004 1,43 11,04 23,7 40,3 49,7 109,4 1096,7 2980,6

Page 28
 Allnex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT K.PUSZTA Jul. 02. Mav. 04

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(ngJm'] STP (ng/m'] STP [nglm')STP. [ngJm']STP [ngJm'J STP [ngJm') STP

HU 2002.07,04E. 07.11 4 Jul2002 11 Jul2002 26,81 86 30 443,9 754,6 388,7 855,2 95 10,8
HU 2002.07.11 '07.20 11 Jul2oo2 20 Jul2002 23,60 6600 390 7 664,1 297,3 654,1 9,8 9.7
HU 2002.07.20.07.24 20 Jul2oo2 24 Jul2002 36,83 119,34 609.6 1036,4 537,6 1182,7 15.7 17,9
HU 2002.08.05.08.12 SAu 2002 12 AUQ2002 12,31 53 99 2037 346,3 243,2 535,0 4,6 7,1
HU 2002.08.12.08.19 12Au 2002 19 AUQ2002 20,93 124,29 346,4 5B8,9 559,9 1231,7 7,9 16,5
HU 2002.08.27 • 09.03 27 Au 2002 3 Seo 2002 53,52 133,84 885,9 15061 602,9 1326,3 8,5 7.5
HU 2002.09.03 .09.10 3 Se 2002 10 Seo 2002 47,50 121,10 786.3 13367 545,5 12001 9,4 8,4
HU 2002.09.10 .09.17 10 Se 2002 17 Seo 2002 088 121,04 14,5 24,7 545,2 11995 0,2 8,1
HU 2002.10.28.11.05. 280kl2002 5 Nov 2002 98,08 1903 1623,7 2760,3 85,7 188,6 37,3 2,6
HU 2002.11.05.11.12. 5 Nov 2002 12 Nov 2002 138,21 31,76 2288,0 3889,5 1431 314,7 59,4 4,8
HU 2002.11.20-11.27. 20 Nov 2002 27 Nov 2002 158,40 44,09 2622,1 4457,6 1986 436,9 47,7 47
HU 2002.11.27.12.04 27 Nov 2002 4 Dez 2002 235,37 47,42 3896.4 6623.9 213,6 469,9 64,S 4,6
HU 2002.12.04 -12.11 4 Dez 2002 11 Dez 2002 214.94 49,99 3558 1 60487 2252 495.4 52,9 4.3
HU 2002.12.11.12.18 11 Dez 2002 18 Dez 2002 231,54 85,67 38329 6515,9 385.9 849.0 27.0 3.5
HU 2003.02.14.02.21 14 Feb 2003 21 Feb 2003 173,23 32,02 2867,7 4875,0 144,2 317,3 17,4 1,1
HU 2003.02.21 .02.28 21 Feb 2003 28 Feb 2003 193,92 14,71 3210,1 54572 66,3 145,8 21,9 0,6
HU 2003.02.28.03.07 28 Feb 2003 7 Mar2003 303.49 38,53 5023,9 8540,7 173,6 381,9 24.1 11
HU 2003.03.07 .03.14 7 Mar 2003 14 Mar 2003 121,64 38,36 20136 3423,2 172,8 380,1 28,0 3,1
HU 2003.03.14.03.21 14 Mär 2003 21 Mar 2003 8836 3183 1462,7 2486,S 143,4 3155 31,3 4,0
HU 2003.03.21 .03.27 21 Mar 2003 27 Mar2003 149,08 53,07 2467,9 4195,5 239,1 525,9 22,9 2,9
HU 2003.03.27 • 04.03 27 Mar 2003 3Aor 2003 58,71 6742 9718 1652,1 303,7 668,2 8.4 3,4
HU 2003.04.03.04.11 3 Dr 2003 11 ADr2003 49,46 57,59 818,8 1391,9 2594 570,7 14,7 6,0
HU 2003.04.11 - 04.18 11 \Dr2003 18 ADr2003 10352 55,08 1713,7 29132 24B,1 545,8 31,4 5,9
HU 2003.04.18 • 04.25 18 \Dr2003 25Aor 2003 23,83 7033 394,4 670,5 316,8 696,9 7,5 7,8
HU 2003.04.25 - 05.02 25 \Dr2oo3 2 Mai 2003 29,06 10978 481.0 817,7 494,5 1087,9 10,9 14,6
HU 2003.05.02 .05.11 2 MaI2003 11 Mai 2003 2232 8914 369,5 628,1 4015 883,4 4,6 6,5
HU 2003.05.12 .05.19 12 Mai 2003 19 Mai 2003 2290 64,80 379,2 6446 2919 642,1 7,9 7,9
HU 2003.05.19 • 05.26 19 Mai2oo3 26 Mai 2003 76,79 74,52 12712 21611 3357 738,5 33.9 11,6
HU 2003.05.28 .06.02 26 Mai 2003 2 Jun 2003 63,05 94 24 1043,8 1774,S 424,5 933,9 29,0 15,3
HU 2003.08.02 .06.09 2 Jun 2003 9 Jun 2003 5870 52,68 9717 1651,9 2373 522,1 24,0 7,6
HU 2003.06.09 - 08.16 9 Jun 2003 16Jun 2003 64,42 36,47 1066.4 18130 164,3 361,4 21,6 4,3
HU 2003.06.16.08.23 16 Jun 2003 23 Jun 2003 9605 48,69 15899 27029 2193 482,5 39,3 7,0
HU 2003.06.23 - 08.30 23 Jun 2003 30 Jun 2003 73,93 54,95 1223,9 2080,6 2475 544,5 347 9,1
HU 2003.06.30 .07.07 30 Jun 2003 7 Jul2003 101,99 73,03 1688,4 2B70,3 329,0 723,7 33,5 8,4
HU 2003.07.14.07.21 14 Jul2003 21 Jul2003 121,13 3302 2005,1 34087 14B,7 3272 62,1 6,0
HU 2003.08.04 .08.11 4 AUQ2003 11 AuQ2003 151,95 9138 2515,3 42761 411,6 905,6 48,2 10,2
HU 2003.08.11 .08.18 11 AuQ2003 18 AUQ2003 9828 47,85 1626,9 2765,7 215,6 474,2 337 5,8
HU 2003.08.18 .08.25 18 Aug 2003 25 Aug 2003 51,71 71,57 856,0 1455,1 322,4 709,2 26,1 12,7
HU 2003.08.25 .08.31 25 Aug 2003 31 Auo 2003 51,55 81,74 853 4 1450,8 368,2 810,0 12,9 7,2
HU 2003.09.01 - 09.08 1 Seo 2003 8 Seo 2003 78,66 56 55 1302,1 22136 254,7 5604 43,4 11,0
HU 2003.09.08- 09.15 8 Seo 2003 15 Seo 2003 9393 50,84 1554 9 2643,3 229.0 503,8 33,9 6,5
HU 2003.09.15 .09.22 15 Seo 2003 22 Seo 2003 104,65 66,26 1732,S 2945,2 298,5 656,6 30,7 6,8
HU 2003.09.22 .09.29 22 Seo 2003 29 Seo 2003 161,56 4244 2674,4 45465 191,2 4206 59,7 5,5
HU 2003.09.29 • 10.06 29 Seo 2003 60kl2003 133,65 45,93 2212,S 3761,2 2069 455,1 75,6 91
HU 2003.10.06 -10.13 60kl2003 130kl2003 6093 1658 1008,7 1714,8 74,7 164,3 45,9 4,4
HU 2003.10.13 -10.20 130kl2003 200kl2003 12211 33,61 20215 3436,5 151.4 333,1 45,3 4,4
HU 2003.10.20 .10.27 200kl2003 270kl2003 10596 16,21 1754.1 2981,9 73,0 160,7 32,1 1,7
HU 2003.10.27 • 11.03 27 OkI2003 3 Nov 2003 74,56 14.72 1234,3 20983 66,3 1459 36,6 2,5
HU 2003.11.03 .11.10 3 Nov 2003 10 Nov 2003 195,04 57,66 3228,7 54888 259,7 5714 765 B,O
HU 2003.11.10 '11.17 10 Nov 2003 17 Nov 2003 262,58 107,62 4346,7 73894 484,8 10665 32,3 4,7
HU 2003.11.17 .11.24 17 Nov 2003 24 Nov 2003 10043 24,65 1662,5 28263 1110 244 2 18,3 1,6
HU 2003.11.24- 12.01 24 Nav 2003 1 Dez2003 125,18 16,47 2072,2 3522,8 742 163,2 31,2 1,4
HU 2003.12.01 .12.08 1 Dez 2003 8 Dez 2003 130,23 2471 2155,8 3664 8 111,3 244,9 37,5 2,5
HU 2003.12.08 .12.15 8 Dez 2003 15 Dez 2003 163,03 72,11 2698,9 45881 3248 714,6 43,4 6,8
HU 2003.12.15 .12.22 15 Dez 2003 22 Dez 2003 222,55 77,72 3684,1 62630 350 1 770,2 39,9 4,9
HU 2003.12.22 .12.29 22 Dez 2003 29 Dez 2003 19431 74,66 32166 54682 336,3 739,8 367 5,0
HU 2003.12.29 .01.05 29 Dez 2003 5 Jan 2004 156,51 1959 25909 4404,5 88,3 194,2 31,4 1,4
HU 2004.01.05 .01.12 5 Jan 2004 12 Jan 2004 15542 40,42 2572,8 4373,8 182,1 4006 18,5 1,7
HU 2004.01.12 .01,19 12 Jan 2004 19 Jan 2004 111,21 990 1840,9 3129,6 446 98,2 38,S 1,2
HU 2004.01.19 .01.28 19 Jan 2004 26 Jän 2004 110,49 11,81 1829 1 31095 53,2 117,0 25.0 0,9
HU 2004.01.26 .02.02 26 Jan 2004 2 Feb 2004 135,80 12,06 2248,0 3821,6 54,3 119,5 22,6 0,7
HU 2004.02.02 .02.09 2 Feb 2004 9 Feb 2004 14545 37,90 24077 4093,1 170,7 375,6 44,2 4,1
HU 2004.02.09 .02.16 9 Feb 2004 16 Feb 2004 8114 20,55 1343,2 2283,4 92,6 203,6 36,6 3,3
HU 2004.02.16 .02.23 16 Feb 2004 23 Feb 2004 12257 2055 2029 0 3449,2 92,6 203,7 42.4 2,5
HU 2004.02.23 .03.01 23 Feb 2004 1 Mar2004 13383 21,91 2215,S 3766,3 98,7 2171 37.4 2,2

Page 29
 Annex

CONCENTRATION VALUES OF LEVOGLUCOSAN,CELLULOSE AT K-PUSZTA

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HU 2004.03.01 .o3.08 1 Mar2oo4 8 Mar 2004 125,50 11,21 2077,S 3531,8 50,S 111,1 272,2 8,6
HU 2004.03.08 .o3.16 8 Mar 2004 16 Mar 2004 155,41 22,18 2572,6 4373,4 99,9 219,8 84.4 4,2
HU 2004.03.16 .o3.22 16 Mar2004 22 Mar 2004 15400 17827 2549,3 4333,8 803,0 1766,7 30,8 12,5
HU 2004.03.22 .o3.29 22 Mar 2004 29 Mar 2004 62,18 15,74 1029 3 1749,8 709 156,0 447 4,0
HU 2004.03.29 .o4.0S 29 Mar 2004 5 or 2004 126,38 2862 2092,1 3556.5 128,9 283,6 27,1 2,2
HU 2004.04.05 .o4.12 5 r2004 12 \Dr 2004 70,41 29,69 1165,6 1981,S 1337 294,2 46,9 7,0
HU 2004.04.12 .o4.19 12 r2004 19 \Dr 2004 74,18 36,51 12280 20876 164 4 3618 374 6,5
HU 2004.04.19 .o4.26 19 r2004 26 \Dr 2004 55,08 56,84 911,7 1550,0 256,0 5633 27,9 10,1
HU 2004.04.26.()5.03 26 r 2004 3 Mai 2004 45,78 120,15 757,8 1288,3 541,2 1190,7 14,8 13,7
HU 2004.05.03 .oS.10 3 Mal2004 10 Mai 2004 62,71 118,93 1038,1 1764,7 5357 1178,6 39,5 26,4
HU 2004.05.10 .o5.17 10 Mai2oo4 17 Mal2004 55,58 154 97 920,0 1564,0 698,0 1535,7 17,1 16,8
HU 2004.05.17 .o5.23 17 Mai 2004 23 Mai 2004 49,38 193,61 817,5 1389,7 872,1 1918,7 14,8 20,4

Page 30