Artemev - 1996 - Geochemistry of Organic Matter in River-Sea Systems
Artemev - 1996 - Geochemistry of Organic Matter in River-Sea Systems
by
V. E. ARTEMYEV
Introduction IX
Abbreviations XIII
v
vi Table of Contents
REFERENCES 175
INDEX 187
INTRODUCTION
One of the basic concepts of ocean biogeochemistry is that of an ocean with extremely
active boundary zones and separation boundaries of extensive biochemical interactions.
The areas of these zones are characterized by a sharp decrease of element migration
intensity and consequently the decrease in their concentrations gave the boundaries for
the naming of the geochemical barriers (Perelman, 1972). For the purposes of biogeo-
chemistry the most important ones are the boundaries of separation between river-sea,
ocean-atmosphere, and water-ground (Lisitzin, 1983). The most complicated of them
is the river-sea boundary, where the biogeochemical processes are the most active and
complicated (Monin and Romankevich, 1979, 1984).
The necessity of studying organic matter in rivers, mouth regions and adjoining sea
aquatories has been repeatedly pointed out by v.I. Vernadsky (1934, 1960) who noted
both the importance of registration of solid and liquid run-off of rivers, coming into the
sea, and "the quality and the character of those elements, which are washed-down into the
sea", emphasizing that "wash-down of organic substances into the sea is of great value".
The interest in studying organic matter in natural waters, including river and sea waters,
has grown considerably over the last 30 years. During this period essential material was
collected on the content and composition of organic matter in various types of river waters
of the USSR, and this was published in papers by B.A Scopintzev, AD. Semenov, M.V.
Tarasov, M.P. Smirnov, AV. Maltzeva (see References), as well as on the largest rivers
of foreign countries (Degens et al., Transport of Carbon and Minerals in Major World
Rivers 1982, 1983, 1985, 1987, 1988). However, the majority of publications dedicated to
studying organic matter in natural water of the USSR contain information about the Corg
content in non-filtered water, where Corg is in both dissolved form and in the composition
of suspension particles (Maltzeva, 1980, 1984; Maksimova and Metreveli, 1984; Maltzeva
et al., 1984,1987).
Information about spatial distribution of organic matter in river mouths is extremely
limited (Scopintzev and Krylova, 1955; Skopintzev and Tzurikova, 1957). There is prac-
tically no data about Corg content in bottom river sediments of mouth regions, bordering
with sea.
Organic matter plays a fundamental role in all biogeochemical processes in the World
Ocean. The theoretical and practical value of organic matter study for revealing common
ix
x Introduction
geological past, contributing to more reliable estimations of the prospectives of oil content
of near-shore water areas.
The results of these studies were presented by the author at the All-Union seminars
on "Organic Substance of Modern and Fossil Sediments" (1970, 1976, 1979, 1982), AII-
Union Schools of Sea Geology (1978, 1980, 1982, 1984, 1986, 1990), VIIIthlnternational
Congress on "Organic Geochemistry" (Moscow, 1977), Ist-IIIrd All-Union Conference
of Oceanologists (1977, 1982, 1987), at the International Conference on "Biogeochemical
Cycles of Carbon and Sulphur" (Settlement Listvianka, 1988), 9th International Sympo-
sium on "The Environmental Biogeochemistry" (Moscow, 1989), as well as at colloquiums
of the ocean chemistry laboratory and meetings of the Working Group "Ocean Chemistry",
etc.
Personnel of the laboratories of the ocean chemistry and physico-geological researches,
the analytic laboratory of the Institute of Biochemistry and Physiology of Micro-Organisms
of the Academy of Sciences of Russia, central analytical laboratory of the V.1. Vernad-
sky Institute of Geochemistry and Analytic Chemistry of the Academy of Sciences of
Russia, laboratory of soil chemistry of the Soil Faculty of the Moscow State University,
laboratory of organic geochemistry of the Scientific and Research Institute of Oceanology
(St. Petersburg), as well as the personnel of the Centre for Control of Environmental
Pollution of the Northern Department of the State Committee for Hydrometeorology,
North Dvina and Pechora river mouth stations, Riga hydrometeo-observatory, Danube
hydrometeo-observatory, Dnieper-Bug, Don and Kuban mouth stations assisted in ob-
taining the material under expedition conditions, performance of chemical analyses, and
advised on some sections of the paper; the author is sincerely thankful to all.
The author is sincerely thankful to Prof.Dr. A.P. Lisitzin, and Prof.Dr. E.A. Romanke-
vich, for assistance in organizing expeditions, useful advices and recommendations during
discussions on the monograph sections.
ABBREVIATIONS
OM - organic matter
DOM - dissolved organic matter
POM - particulate organic matter
ROM - residual organic matter
C org - organic carbon
Cd - dissolved organic carbon
cP - particulate organic carbon
N org - organic nitrogen
N~rg - dissolved organic nitrogen
Ngrg - particulate organic nitrogen
DC - dissolved carbohydrates
PC - particulate carbohydrates
AA - amino acids
HA - humic acids
FA - fulvic acids
HS - humic substances
HC - hydrocarbons
C~ - dissolved carbohydrate carbon
C~ - particulate carbohydrate carbon
Act - chloroform bitumoid 'A'
Aa-b - alcohol-benzol bitumoid 'N
VA - vanillin aldehyde
PA - p-oxybenzaldehyde
SA - syringyl aldehyde
xiii
Chapter 1
Proceeding from the problems raised when choosing the region of work we were guided
by the following basic criteria: climatic zonality, river run-off value, type of rivers
(plain, mountain) and estuaries (see Chapter 3). The important role of climatic zonality
and formation of river organic matter composition was pointed out by Y.1. Vernadsky:
"Already it is possible to determine two separate types of fresh river waters, tightly bound
up with the certain climatic zones ... These are near-pole rivers with light brown water
and black rivers of tropical and subtropical regions. The chemical studying of the waters
of these rivers is urgently required" (Vernadsky, 1960). To compare the trends of organic
matter transformation processes in the line suspension-bottom sediments in estuaries of
northern and tropical rivers the following studies were performed in the southern part of
Dvinsky Bay on the section North Dvina-sea and the Amazon estuary.
To clarify the mechanism of transportation and the peculiarities of transformation of
dissolved and particulate organic matter of bottom sediments in the widest range of salinity
from 0.0 to 36.0%0 in tropical oceanic estuary at various stages of mixing river and ocean
water, estimation of distances of spread and scales of river organic matter effect on the
ocean medium we chose the estuary of the largest river of the world - the Amazon.
To determine the character of interconnection of dissolved and particulate organic
matter with primary products and micro-elements in sea estuaries of the moderate climatic
zone, the effect of water stratification on the organic matter behaviour in estuaries and
comparative analysis of this data with the behaviour of the same parameters in oceanic
tropical estuary, research was undertaken in Temryuk, Riga, Taganrog and Dvina bays.
The study of seasonal variations of organic matter behaviour in the river-sea system
would be useful in the estuary of northern latitudes with contrasting distributions of
meteorological, hydrochemical and geochemical indexes and liquid and solid run-off and
organic matter run-off values. Therefore, such research was performed in the White Sea,
on the section of "mouth of North Dvina-Mudiyug Island". To estimate organic matter
behaviour in the area of mixing in mountain rivers waters and sea waters, investigations
were performed on the section "mouth of Mzymta River-Black Sea".
2 Chapter 1
The basic areas of our investigations were river and sea water, suspension and bottom
sediments. Plankton, bacterial micro-flora and soils were studied to a comparatively lesser
degree.
The material for the study was taken during expeditions, organized by both the Institute
of Oceanology of the Academy of Sciences of Russia, together with other organizations.
To study the peculiarities of organic matter transportation by time in the river-sea system
and some mouths of rivers and estuaries, samples were taken during different seasons and
hydrological phases (flood, low water, tide, ebb tide) and at various times of day (at daily
and half-daily stations).
Sampling in mouths of rivers and the regions of mixing of sea and river waters can
be performed from various boats, from the research ships of ocean class ("Academik
Kurchatov", Professor Shtokman") to ships of such class as medium fishing trawlers,
small fishing trawlers, as well as from cutters, boats, and motor boats. In winter, samples
of water (in the mouth of North Dvina river) are taken from ice through a hole drilled with
an auger.
Samples of river water (salinity less than 1%0) are taken in mouths of rivers in front of
the conditional border with the region of mixing of river and sea waters, the salinity of
which is within the limits from 1%0 to the maximum salinity for this reservoir (sea, ocean).
Depending upon the width and the depth of the river, samples are taken either in one
point (on race) or in three points - near the right and left shores and at the middle of the river
from the surface (0-0.5 m),l bottom (1 m from the bottom)2 and, sometimes, intermediate
horizons. The principles of sampling and the number of water samples taken vertically
are predetermined by the supposed character of water stratification, expected thickness of
river and sea water layers and the bottom depth. Water and bottom sediment sampling in
the regions of river and sea water mixing is performed on river-sea sections, the number
of sections being determined by the size of the studied water area. Initial point (points) of
section (sections) is located in the river water, the final one is located in the sea water. The
length of river-sea section depends upon several factors: thickness and direction of river
run-off velocity and direction of wind (piling down, piling up, calm), tides and up-tides.
Therefore, these circumstances shall be taken into primary consideration when planning
and performing works in the river-sea system. To specify correctly the places (points) of
locations of stations for sampling on "river-sea" section and the distance between them it
is necessary to have the data on the horizontal and vertical distribution of salinity in this
region. This will give the possibility for uniform sampling of water on the section by the
change of salinity in the process of mixing of river and sea water. If the data on salinity
distribution is absent or doubtful it is necessary to measure the salinity of the water before
1Thickness of taken "surface" layer of water depends upon the height of hathometer. used for sampling.
2 It
is not recommended to lower the bathometer closer to bottom to avoid rolling on the surface layer of
bottom sediments
Materials and Methods of Study 3
sampling for analysis of organic matter. During our expeditions, samples of water were
taken on the "river-sea" cross-section in waters with salinity 0-10%0 through 1%0, in the
more saline waters (from 10 to 20%0) through 2-3%0, in waters with salinity more than
20%0 through 5%0.
To obtain more reliable results on the organic matter geochemistry in the studied area
of the river-sea system it is necessary to have the data not only of organic matter analysis
results but also the velocity and direction of wind and streams, bioproducts, optical
characteristics of water, biogenous elements, etc.
Water samples were taken by sterilized bathometers with capacities of 1, 5, 10 and 20 litres.
Suspension was obtained by means of water filtering through fibre glass filters GFIF and
GF/C. Bottom sediments were taken by means of a dredge.
During our explorations the water salinity was determined by the method of argento-
metric titration, as well as by means of salt meter GM-65, oxygen - by Vinkler method,
phosphates phosphorous - by Strickland and Parsons (1968), nitrogen of nitrates - by
Wood et at. (1967).
Dissolved and suspended organic carbon was determined by the method of sulphur-
chromium oxidation with subsequent culonometric determination of formed carbon diox-
ide (Lyutsarev and Smetankin, 1980a, 1980b). Organic carbon in bottom sediments was
determined by the Knopp method (Uspensky et at., 1966). Organic carbon in soils was
determined by the method offered by Tyurin (Orlov and Grishina, 1981). Organic nitrogen
in suspension was determined by means of the persulphate method (Konnov and Konnova,
1985), nitrogen in bottom sediments was determined by the method suggested by Kyel-
dal. The total sum of carbohydrates was determined by the phenol method (Artemyev et
at., 1971). Lignin in suspension and bottom sediments was determined by the means of
nitrobenzol oxidation in an alkaline medium with subsequent determination of oxidation
products by gas-liquid chromatography (Bobyleva, 1982; Peresypkin et ai., 1989).
Bituminological analyses of suspension and bottom sediments were performed by the
scheme published in the paper by Danyushevskaya (1985). The molecular composition
of n-alkanes of methano-naphthene fractions of bottom sediments bitumoids outlined by
uprising chromatography on silica gel (Silina, 1973) was analyzed by gas-liquid chro-
matography (Belyaeva, 1987).
Humic acids (HA) in bottom sediments were analyzed by the methods assumed in
bituminological researches (Uspensky et at., 1966). HA in soils were determined by the
pyrophosphate scheme suggested by Kononova-Bechikova (OrJov and Grishina, 1981).
The content and the composition of amino acids (AA) was determined by quantita-
tive chromatography on paper: "free": directly from suspensions, "bound": from the
hydrolysate of the bottom sediments amino acids (Danyushevskaya, 1985).
Dissolved and suspended forms of micro-elements were determined by the methods
described by Demina (1982).
Chapter 2
River and sea waters differ sharply in their chemical composition. Average concentrations
of some elements in river and sea waters are given in Tables 1 and 2 for comparative
purposes. Without any doubt the chemical compositions of some rivers, i.e. those rivers
of different water collecting basins (Table 3) may differ from the data given in Tables 1
and 2. It should be noted that our knowledge about chemical composition of water is far
from complete even for the large rivers of the world.
As it is seen from Table 4, river and sea waters and estuaries also differ sharply by the
content of Corg . The quantity of dissolved organic matter (DaM) of the majority of natural
waters is many times greater than the quantity of particulate organic matter (PaM); also,
these forms of organic matter are often present in rivers and estuaries in equal quantities.
The majority of river waters are acidic or neutral solutions of low ionic force.
Supply of dissolved substances to a territory of a river basin is provided by the fol-
lowing sources: soils, sedimentary and volcanic rocks, atmospherical precipitations, ash
suspension, products of mineralization or humification of organism remains. In this case
as V.I. Vernadsky noted (1960) "soil solutions of a river basin predetermine the main part
of the salt composition for river water".
Waters of the majority of the world rivers belong to the hydrocarbonatic class and by
composition of cations they are almost exclusively referred to the calcium group (Alekin,
1948, 1979).
Waters of sulphate and chloride class rivers are comparatively infrequent. Mineraliza-
tion of river waters differs during the period of summer low water and spring flood. The
water composition during low water time is essentially different from waters during flood
due to their supply from deeper horizons and artesian waters. The river water composition
depends upon the supply source: rain, snow, mountain snows, glaciers. The variety of
climatic conditions, predetermining different quantity of precipitation, their character, con-
ditions of accumulation, as well as combinations of other physico-geographical conditions
create differences in the water and consequently in the hydrochemical regime of rivers.
4
Organic Substance of River Run-Off 5
Table I. Average concentrations of some dissolved components in global river run-off and sea
waters (Livingstone, 1963).
Table 3. Elements of basic salt composition of rivers falling into ocean, mg/I (Martin and
Gordeev, 1985).
Atlantic 9.9 10.5 2.5 4.2 1.4 5.7 7.7 37.0 69.0 78.9
Indian 14.7 21.6 5.4 8.5 2.5 6.8 7.9 94.9 140.2 154.9
Arctic 5.1 16.1 1.3 8.8 1.2 11.8 15.9 63.5 118.6 123.7
Pacific 11.7 13.9 3.6 5.2 1.2 5.1 9.2 55.4 93.6 105.3
6 Chapter 2
The greatest part of river organic matter is of allochthonous genesis, coming from soils.
Emphasizing the important role of soils as the source of organic matter, supplied to rivers
and further on to sea, v.I. Vernadsky noted (1960): "We usually don't take into account
and understand the great value of soil mantle of our land for life and chemical reactions of
the ocean ... Soil and sea water are bound up chemically and genetically". It was shown
(Hedges et al., 1986) that soils may be a potential source of both dissolved and particulate
organic matter in rivers. The second terrigenous source of river organic matter may be
products of agricultural activities and finally comparatively small autochthonous fraction
of river organic matter is formed by products of in situ river plankton, consisting basically
of labile components (lttekkot et aI., 1986), as well as leaves, waste wood, grass, etc.
(Hedges et aI., 1986).
It is known that mineralization and chemical composition of surfacial waters depend
on processes of destruction of mountain rocks, minerals and organic residues in the soil
layer. The basic source of organic matter washed out by atmospheric precipitations are
residues of annually dying plants, and to a lesser degree the residues of animals, insects
and micro-organisms. Water-soluble organic matter run-out from drainage systems into
fluvial systems of rivers are formed in the thickness of soils by chemical decomposition
of vegetable residues as a result of microbial activities.
Organic Substance of River Run-Off 7
Ocean 2000
Soil 2100
Terrestrial biosphere
(except soil) 700
Fossil fuel: 4130
coal 3510
oil 230
gas 140
other 250
Organic matter created by living organisms of land, and first of all by plants during their
life activities, are finally supplied to the soil, forming its organic part or humus. Organic
residues (plants, micro-organisms, soil fauna) are subjected to various transformations
in the soil, as a result of which a part of the organic matter is broken down to simple
combinations (C0 2 , H 2 0, NH 3 , etc.). Another part of the organic matter is transformed
into more stable forms: peat, sapropels, etc.
Humus is formed from the layer of dead parts of trees, bushes, grass, soil fauna and
micro-organisms.
The character and the rate of transformation of organic residues during humus formation
are predetermined by the composition of these residues, chemical composition of soil,
moistening degree, etc.
The total content of Corg in the Earth soils is equal (Kobak and Kondrashova, 1986) to
2100 x 1015 g, i.e. soils are the largest reservoir of C org of our planet. The quantity of C org
contained in them is considerably larger than that in the biomass of ground ecosystems and
has a value in the same order with reserves of Corg in the ocean and fossil fuel (Table 5).
The zonality of nature, and that of climate was initially noted even in the ancient times.
The first scientific generalization in the field of geographical zonality (horizontal and
altitudinal) belongs to Gumboldt (beginning of 19th century). Division of earth surface
into geographical zones was first suggested by v.v. Dokuchaev in 1898. Dokuchaev was
the first one to determine zonality of climate, flora and fauna (Tziganenko, 1972) and
suggested the division of the northern hemisphere into seven zones: boreal (tundra), taiga,
forest-steppe, desert-steppe, areal (desert), subtropical and tropical forests.
Latitudinal variation of C org in soils is expressed in its growth from equator to poles,
the maximum being in the boreal zone (Figure 1). It was determined that boreal belt
soils accumulated the maximum quantity of C org - 35% of total reserves; soils of tropical
Organic Substance of River Run-Off 9
C, kg/m2
~
<
~
:I0
< ~
IC
~
32 r- ~
tJ
~
<
r.:l r-
<
~
c:I<
< ~ 0
-
0
...
tJ 0 c:I<
~ IC
r-
~
c:I< IC
0 IC =:>
~ =:> III
to; III
16 r-
~~
8 r
o 20 40 60 80°
Fig. 1. The content of Corg in soils of different climatic zones (Tziganenko, 1972).
belts - 27%; and so on. The lowest concentration of Corg was revealed in desert belt soils
(Table 6).
Fulvic acids (FA) differ essentially from humic acids by their elementary composition.
They contain considerably lower quantities of carbon and more oxygen (Table 8).
The richest of the humus are thick chernozems (Table 9), where a one metre layer
contains more than 700 tlha of humus and about 40 tlha of nitrogen. Reserves of humus
and nitrogen in soils are decreased both in regions characterized by increasing quantity of
precipitation and decrease of temperatures (leachable chernozems, grey forest and podzol
soils) and in the regions, being in arid conditions (southern chernozems, chestnut, brown,
desert-steppe soils).
From the standpoint of problems raised in this work, river flood plain soils are of the most
interest among soils as the source of organic matter in river waters. River flood plains are
parts of the river bottom covered with plants and submerged during flood (Tziganenko,
1972).
The climate, the relief and extent of mastering the territory in the river basin have a
great effect on the properties and the quantity of alluvial deposits. In the basins completely
covered with forest, for example in those of some northern rivers of the USSR, where
snow melts slowly under the forest cover, aqueous erosion is absent and does not supply
mud for flood plains. But, in such rivers as the Don, the basin of which is fully free
Organic Substance ofRiver Run-Off 11
Peaty-marshy soils,
peat bogs 40.2 41.0 16.8 2.0 1.0 0.4 20.1
Flood plain, meadow
soils 41.1 36.4 20.2 2.3 0.9 0.5 17.9
Dark colour soils 37.4 41.5 19.8 2.2 1.1 0.5 17.0
Dem-podsolic
soils, podsols 37.5 39.8 20.3 2.4 1.1 0.5 15.6
Brown, wood soils,
brown soils 37.4 42.2 17.9 2.5 1.1 0.5 14.9
Grey wood soils 38.1 40.3 19.2 2.4 1.1 0.5 15.9
Chemozems 42.5 35.2 19.9 2.4 0.8 0.5 17.7
Chestnut soils 37.7 42.1 17.4 2.8 1.1 0.5 13.5
Solonelz (salt
garden) 40.5 36.4 19.9 3.2 0.9 0.5 12.7
Grey soils 39.0 40.1 18.1 2.8 1.0 0.5 13.9
Termrossa 42.1 33.4 21.8 2.7 0.8 0.5 15.6
Mountain meadow
soils 42.7 32.0 22.3 3.0 0.7 0.5 14.2
Limits 37.4-42.7 32.0-42.2 16.8-22.3 2.0-3.2 0.7-1.1 0.4-0.5 12.7-17.9
Avemge 39.7 38.4 19.5 2.6 1.0 0.5 15.7
of forest, floods are usually very intensive, relatively short and bring a large quantity of
suspended deposits to river valleys.
Occupying the lowest areas of land, river plains accumulate various nutrient substances
and chemical elements for plants brought with river run-off from interfluves. The flood
plains are supplied with the most biologically active and most productive soils, washed
off with rain and melt waters. As for their potential productivity of the soils, which
are mostly spread in flood plains, exceed podsolic and chestnut soils but are second to
chernozems enriched with humus. A metre thick layer of grainy flood plain soils contains
up to 350-550 t and more humus per hectare, which exceeds that in podsolic soils by
5-7 times and that in chestnut ones by 3-4 times.
Genesis and properties of flood plain soils are different from those of watershed soils
which are bound with a great variety of natural factors effecting their formation. More
than 60% of the total area of flood plain soils of Russia are located within the boundaries
of the taiga-forest zone. Soils of river flood plains are marked by their productivity on the
background ofturf-podsolic zone soils (Sokolov et al., 1974). In central chernozem areas
and southern regions of the steppe zone (flood plains of the Don and the Kuban) flood
plain soils are very productive and are used intensively (Gorokhov, 1960). Their humus
content varies from 1 to 6%, averaging 3.2%.
12 Chapter 2
Podsolic, dern-
podsolic soils 33.4 39.8 25.3 2.0 1.2 0.8 16.6
Brown, wood soils 30.8 40.9 26.1 2.2 1.3 0.8 13.9
Grey wood soils 31.9 40.9 25.3 1.9 1.3 0.8 17.0
Chemozem,
chestnut soils 30.9 40.6 26.3 2.2 1.3 0.8 14.3
Grey soils 29.4 41.7 26.7 2.2 1.4 0.9 13.3
Brown soils 32.2 34.9 30.9 2.0 1.1 1.0 16.3
Terrarossa 36.6 33.4 27.9 2.1 0.9 0.8 17.6
Mountain-meadow
soils 30.2 42.1 25.4 2.3 1.4 0.8 13.2
Meadow soils 31.9 41.2 24.4 2.5 1.3 0.8 12.8
Dark colour soils 32.9 39.4 26.0 1.7 1.2 0.8 18.8
Limits 29.4-36.6 33.4-42.1 25.3-30.9 1.7-2.5 0.9-1.4 0.8-1.0 12.8-18.8
Average 32.0 39.4 26.4 2.1 1.2 0.8 15.4
Unfortunately, the data on content of humus (or Corg ) in flood plain soils of other large
rivers of the European part of Russia are absent at present. During the 9th expedition of
research vessel "Professor Shtokman" we sampled and later on studied, in the stationary
laboratory,) soils from the shores of the Amazon tributaries (Tables 10 and 11). Soils
of the Amazon basin are the source or river dissolved organic matter which is borne out
by the similarity of the composition of humic substances, found in the Amazon waters
and humic substances of podsolic and latosolic soils of the Amazon region (Leenheer,
1980). Humic substances get into river waters of the Amazon river either as a result
of drainage by underground waters of podsolic soils (Negru river) covered with a thick
layer of organic residues, or latosolic soils (for example, Topazhos river) which do not
have, like podsols, a layer enriched with organic matter (Table 5). At the same time,
passing latosolic soils, coloured solutions of humic substances are to a considerable extent
adsorbed at clay minerals, contained in latosols.
Content of Corg in the soils of the Amazon river varied from 0.63 to 3.30%, and equals
an average to 1.83%, which when converted to humus is equal to 1.1-5.7% or 3.2% as an
average. The maximum content of Corg was found in Negru river soils. In latosolic soils
taken from the shores of other investigated tributaries of the Amazon, the content of Corg
humic and fulvic acids is essentially lower.
As it is seen from Table 5 the basic part of the organic matter of soils consists of
"non-hydrolysed" or "residual" organic matter. Bitumoids in the composition of soils
organic matter play secondary roles, being equal to about 45% of the total content of
organic matter. In this case, there are no essential differences in content of bitumoid "N'
in various types of soils. More detailed studies of chlorophormic bitumoid "N' (bit. Ac\)
and hydrocarbons (HC) in soils of the Amazon (Table 11) gave a possibility to reveal
differences in the studied soils. Bitumoid Ac\ of Negru podsols is more "carbonic" than in
other soils. Resin components prevail in it. But latosolic soils are characterized by a higher
content of asphaltenes and asphaltenic acids. The main component of the hydrocarbons of
Negru river podsolic soil oils (more than 90%) consists of methano-naphthene and their
proportion amounts to 0.33% of organic matter (in latosolic soils 0.05%).
2.3. Role of River Run-Off for Organic Matter Delivery to Sea Medium
As it is known, continents are the area of preferable denudation, and oceans are the area
of preferable accumulation of substances, washed off the land. Dissolved and suspended
substances are delivered with river run-off from water collecting basins into oceans.
Even if the biogenic material, playing an important role in the sedimentation, originates
in ocean, organisms of plankton and benthos use mainly elements and compounds supplied
to ocean from river run-off (Table 12).
I Analyses of organic matter of soils were perfonned in the laboratory of soil chemistry of the Soil Faculty of
the Moscow State University and in the laboratory of organic geochemistry of the "Ocean-Geology" Research
Institute (St. Petersburg).
......
.j:.
<"'l
Table 10. Composition of organic substances in Amazon Basin soils.
~
Content in soils, % Content in OM of soils, %
tv
"....
Place of Bitumoid "~' Bitumoid "~'
sampling Corg Humus Chlor.' Eth.benz." CHA CFA Chlor.' Eth.benz." HA FA HAIFA ROM
Negru river 3.30 5.7 0.03 0.03 0.60 0.37 1.4 1.4 18.2 11.2 1.6 67.8
Topazhos river 1.60 2.8 0.03 0.03 0.13 0.13 1.4 1.4 8.1 8.1 1.0 80.9
Shingu river 2.69 4.6 0.09 0.10 0.43 0.26 1.9 2.1 15.9 9.6 1.7 70.3
Limits 1.60-3.30 2.8-5.7 0.03-0.09 0.03-0.10 0.13-0.60 0.13-0.37 1.4-1.9 1.4-2.1 8.1-18.2 8.1-18.2 1.0-1.7 67.8-80.9
Average 2.53 4.4 0.05 0.05 0.39 0.25 1.6 1.6 14.1 9.6 1.4 73.0
, Chloroform
"Ethanol-benzol
Shingu, 1006 72.4 10.6 17.0 6.8 1.76 5.6 41.1 51.7 50.0 50.0 1.0 0.005 0.11 0.05
Negro, 1030 76.6 11.1 12.3 6.9 1.74 25.5 60.9 5.4 90.4 9.6 9.4 0.008 0.36 0.33
Negro, 1031 75.1 11.6 13.3 6.5 1.85 9.4 76.0 14.5 0.002 0.12
Topazhos, 1039 73.5 11.4 15.1 6.4 1.86 9.7 63.2 26.9 90.4 9.6 0.003 0.14
Limits 72.4-76.6 10.6-11.6 12.3-17.0 6.4-{j.9 1.74-1.86 5.6-25.5 41.1-76.0 5.2-51.7 50.0-90.4 9.6-50.0 1.0-9.4 0.002...{).008 0.11"'{).36 0.05...{).33
Average 74.4 11.2 14.4 6.6 1.81 12.5 60.3 27.2 70.9 30.0 5.2 0.004 0.17 0.12
, Asphaltenes + Asphaltogenic
Organic Substance of River Run-Off 15
Terrigenous fragmentary
and shaly 22.6 77.2
Volcanic 2-3 8.8-10.3
Biogenic, plankton (dry) 110
including;
carbonaceous 1.36 4.7
siliceous 0.46 1.6
Cosmic 0.01...{J.08 0.03
From the data presented by Lisitzin (1974) it is clear that the mean role in delivery
of material from the continent to the ocean is played by rivers, suspended and dissolved
run-off of which totals respectively 18.53 mlrd tlyear and 3.2 mlrd tlyear. An exclusive
role of rivers as a binding link between land and ocean was noted by V.I. Vernadsky
(1960), who emphasized "what a great work is performed by river's water, washing off
continents and transporting huge quantities of substances to the sea".
The majority of high-water rivers of the Earth are rivers of tropical regions and the
greatest of them is the Amazon (Table 13).
The main part (more than 50%) of all suspended material is delivered into seas and
oceans by rivers of the equatorial humid zone. Even if river run-off in the northern
moderate zone is sufficiently great, the content of suspension in it is significantly lower
than in the equatorial zone (Table 13).
Holeman (1968) and later Milliman and Meade (1983) showed that about 70% of
suspension, delivered by rivers into oceans comes from 21 large rivers of the Earth.
However, only 5-10% of it reaches ocean depth (Postma, 1980; Eisma, 1981a; Milliman
and Meade, 1983). More than 90% of suspension remains on the shelf (including that in
estuaries, limans, deltas) and the continental slope.
The main part of dissolved and particulate organic matter, washed out from continents
to ocean is also delivered to ocean waters with river run-off, causing a noticeable effect
on the surrounding medium. Organic matter is the main regulator of all chemical, geo-
chemical and biogeochemical processes, going on in the volume of ocean waters and in
the bottom sediments. Run-off of dissolved and particulate organic matter is an impor-
tant geochemical factor, reflecting multiform processes of organic matter migration and
transformation in the studied region. In spite of the fact that river waters total only a
small part of surfacial waters on the planet (0.006% of world reserves of fresh water),
16 Chapter 2
Table 13. Entrance of organic matter to seas and oceans with river run-off (from the data presented by Lisitzin,
1974; Kemple, 1985; Spitzy et al., 1991 and the author).
their role in geochemical processes is great. V.I. Vernadsky wrote about the important role
of particulate organic matter (1960): " ... Mud of rivers is most closely bound up with
living substance, with geochemical energy of life. It is washed off into rivers in a form of
thinnest dust by winds and meteoric waters. Its quantity is most closely bound up with the
laminating work in soil, performed first of all by animals and mostly by human beings".
Organic Substance ofRiver Run-Off 17
Corg
of soils
3.10"g
0,003 . 10'" !!
Fig. 2. Organic carbon at continents and in the ocean (Degens et aL, 1984; Romankevich. 1990).
At present the ionic run-off of rivers as the main component of the general run-off of
dissolved substances is studied in the best way. Information about run-off of basic ions
from the Russian territory to seas and oceans, formation of ionic run-off, its connection
with geographical and geochemical factors is most detailly considered in works of Alekin
(1951, 1970) and Alekin and Brazhnikova (1961, 1984). Compared with ionic run-off
the run-off of organic matter is sparsely studied. The most complete information about
continental organic matter run-off from the Russian territory (without distinction between
dissolved and particulate organic matter) was published by Matseva et al. (1987). The
data from dissolved and particulate organic matter transfer with rivers of the world are
given in the collected articles Transport of Carbon and Minerals in Major World Rivers,
by Degens et aL (1982-1991), review articles by Degens and Ittekkot (1983, 1985);
Duce and Duursma (1977); Schleisinger and Melack (1981), and in the present work
(Tables 13-15).
The main reserves of Corg on land and in sea are shown in Figure 2. As it is seen here,
the basic mass of Corg on the Earth is accumulated in soils. Dissolved forms of Corg (Cd)
plays the main role in the ocean. The maximum quantity of Corg in ocean was found in
comparatively small volumes of water over shelves (Figures 3 and 4) which is first of all
bound up with the supply of Corg with river run-off, as well as with the production of Corg
in situ, due to the high content of nutritional salts in river run-off.
The biggest flows of both Cd and 0' are delivered by rivers to seas and oceans in the
equatorial humid zone - 75.8 and 90.2% respectively from global run-off. On the whole,
rivers deliver approximately equal quantities of cd and CP to waters of seas and oceans:
0.204 x 109 tlyear and 0.184 x 109 tJyear respectively.
The main flow of river waters (liquid run-oft) and Cd to ocean is from the territory of
South America and the maximum quantity of suspended material, and CP is supplied by
rivers of Asia (Figures 5-7, Table 13).
18 Chilpter 2
C'
Cd (>200.) .10'10 '5 g
860 '10 75 g Plankton
J'10 75 g
Water
volume, 10· km 3
r----------------,
5
J 6
Fig. 4. Water volumes and the amount of Co,g in waters above different depths of the ocean bottom (Degens
and Ittekkot, \984).
The run-off of Russian rivers amounts to 10% of the global river run-off. The river
run-off of the European part of Russia amounts to about 39% of the European total, and
the river run-off of the Asian part of Russia totals 42% of the Asian one.
Rivers, specified in Table 13 cover 37.1 % of the global river run-off, which amounts
to 37 400 km3/year (Spitzy et al., 1991). Extrapolating to 100% gives 204 x 106 t/year
(52.6%)for Cd, and 184 x 106 t/year (47.4%) for cP, C d+p totals to 388 x 106 t/year. If
it is accepted that 25% of river dissolved organic matter and 80% of particulate organic
Organic Substance of River Run-Off 19
100
D Liquid runoff
..>-
'"<I> ~ Solid runoff
"-
"e
flo
..'"
<I>
>-
0 50 ~
I:::
~
:::0
e
Q
:9 2=
,g-
::I :9
.... o
'"
0
Fig. 5. Solid and liquid run-offfrom continents (Degens and Ittekkot, 1985).
C P 106 t/year
JOO r - - - - - - - - - - - - - - - - - , ZOO
Fig. 6. Annual input of the river Corg from continents to the ocean (Degens et at., 1984; Degens and Ittekot,
1985).
20 Chapter 2
50~---------------z--------------------------'
~ ~5
55 555 5 5 - Sapcboppi
Z /;.- Obayo
b- ,~razas
Mu '.
M- Missouri
10 • - Mississippi
M
• - Neyse
+- Rivers of
U - Rivers of
z- Zair
A- Mazon'
o,q~ ________ __ ~ ~~~~~~~ .. .u~ __~~
1 10 100 1000 5000
PM ,.,gIl
Fig. 7. Dependence ofCP content in rivers from the particulate matter content (Meybeck, 1981 and the author).
Table 14. C org entrance to the Russian marginal seas with river run-off (Maltseva
et al., 1987).
Average
Run-off C org concentration Area
Sea km3/year 103 t/year of C org , mgll 103 km2
Barents Sea,
White Sea 417.7 5516.5 13.21 1250.0
Kara Sea 1337.2 12522.5 9.36 6200.0
Laptev Sea 789.6 8519.5 10.79 3670.0
East Siberian Sea 238.0 1696.5 7.13 1390.0
Chuckchee Sea 28.6 101.5 3.55 102.0
Bering Sea 220.4 1020.5 4.63 575.1
Okhotsk Sea 674.4 5388.5 7.99 2500.0
Japan Sea 43.5 226.5 5.21 135.0
Baltic Sea 168.3 1988.5 10.65 640.0
Black Sea, Azov Sea 146.3 937.0 6.40 1329.0
matter remains in river mouths during the mixing of river and sea water (see Chapter 3),
this will totalSI x 106 Uyear and 147 x 106 Uyear for Cd and CP, respectively.
The highest values of C org run-off in Russia are typical for rivers of Asian North, falling
into the Kara Sea and the Laptev Sea (Table 14). In accordance with the data (Maltseva
Organic Substance of River Run-Off 21
Table 15. Discharge of C org (Cd + CP) from the Russian territory to ocean basins
(Romankevich and Artemyev, 1985).
et ai., 1987) the total run-off of Corg from the Russian territory amounts approximately to
41 x 106 tJyear, but the run-off to ocean amounts to 38 x 106 tJyear or 92%. The main
mass of Corg , 28.3 x 106 t or 75% of summary run-off to the ocean, is delivered to the
Arctic Ocean (Table 15). The Pacific receives 6.6 x 106 tJyear of Corg or 17.0%, and the
Atlantic 2.7 x 106 tJyear or 7.2% of summary run-off from the Russian territory to the
ocean.
According to our data (Table 13) and the data of Meybeck (1982) the content of Cd in
world rivers averages 7 mg/!, and CP 2 mgn. Concentrations of CP in the suspension
composition varies from 0.5 to 40% (see Figure 7). Content of Corg in river waters and the
proportion of dissolved and suspended forms of organic matter depend upon many factors:
type of drained soils, products in situ, presence of anthropogenous pollutions, etc., which
on the whole is bound up with climatic and ecological peculiarities of the water catchment
basin. It was found, for example, that organic matter and some of its components in
mouths of plain rivers are mainly (60-70%) in the dissolved form, and particulate organic
matter prevails in mountain rivers (Artemyev, 1981). It was also shown that suspension of
mountain rivers contains 4-5 times fewer organic particles (converting into dry substance
of suspension) than plain one, which is bound up with relative enrichment of mountain
river suspension with terrigenous inorganic material.
Content of dissolved nitrogen and phosphorus in river waters is 1-2 orders lower than
the content of Corg and amounts, respectively, to 100-600 mgn and 1-35 mg/! (Meybeck,
1982).
Suspended nitrogen of river waters amounts to 0.1-1.3% of dry suspension. Ratio
CPJNP varies from 7 to 54 and average is equal to 25 (Artemyev, 1988; Subramanian and
Richey, 1985).
22 Chapter 2
Cd CP Cd +CP
Station May 1985 Febr. 1987 May 1985 Febr. 1987 May 1985 Febr. 1987
No. Horizon Spring Winter Spring Winter Spring Winter
Our investigations showed that the highest concentrations of Cd (11.2-33.7 mg/l, 20 mg/!
on average) of all the studied rivers were found in the mouth of the North Dvina river
(Tables 13 and 16). It is bound up with the fact that rivers of the Arctic Ocean basin
cross excessively moist taiga-forest, forest-tundra and tundra zones with podsolic, paludal
soils. Combination of natural conditions in these zones favours the formation of river
waters with high concentrations of organic matter of humus origin (Maltseva et at., 1987).
Largest rivers of the White Sea and the Barents Sea such as Pechora and North Dvina
deliver about 8 x 106 t of organic matter (Table 13) per year or 73% of the total quantity of
organic matter, run-off by rivers into these seas. It should be noted that concentrations of
Cd and CP in river waters change essentially in time and space depending upon the season,
time of day, place of sampling and depth of river. The detailed results of studying the
seasonal changes of Cd and CP concentrations in river waters are considered below. Since,
as a rule, the basic part of organic matter (up to 90%) is run-off by rivers into the final
reservoir of run-off during flood, calculation of dissolved and particulate organic matter
flows was performed on the basis of data, typical for this hydrological phase. Location
of sampling stations and the results of analyses of Cd and CP in the mouths of the North
Dvina and the Pechora are shown on Figures 8 and 9 and in Tables 16 and 17.
One of the typical peculiarities of the suspension of the studied northern rivers is the
higher content of organic substances they contain, which are bound up with climatic
peculiarities of the drained territory, when compared with rivers of other climatic zones.
Organic Substance of River Run-Off 23
.......... ::.......
Fig. 8. Sampling stations in the North Dvina mouth and southern part of Dvina Bay (1980-1987).
The maximum content of cP in the North Dvina mouth was observed within the period of
flood: more than 3 mgn (Table 16). During the rest of the year CP in the Pechora and the
North Dvina is equal to 0.3-1.0 mgn.
The prevalence of the dissolved form of organic matter over the suspended form in the
northern rivers is testified by high ratios of Cd/CP in the mouth of the North Dvina.
In the mouth of the North Dvina and in the Dvina Bay we have also studied organic
matter of bottom sediments, mainly sands, taken on the river-sea section (Figure 8,
Table 18). Content of Corg in bottom sediments of the North Dvina mouth varies from
0.07 to 1.41 % and on average is equal to 0.5%. Higher content of Corg was found in
aleurites (1.18 and 1.41 %), in sands contentofC org is considerably less (0.07-0.14%) and
is close to average values for bottom sediments of this type in the White Sea (Nevessky et
at., 1977). Low contents of Corg in sands is bound up with the presence of quartz, which
in contrast to other minerals of crystalline rocks does not contain metal ions in grid and is
characterized by low sorptional capacity.
24 Chapter 2
Content of nitrogen in sands and aleurites of the North Dvina mouth is extremely
low, 0.004-0.066%,0.03% on average, and the ratio CIN amounts to 17.5-24.0,21.3 on
average.
Rivers of moderate climatic zones are characterized by lower concentrations of Cd, than
that of rivers of northern latitudes (Table 13). Organic carbon is represented mainly by
the dissolved form, the quantity of which is however somewhat less than that of northern
rivers. Therefore, an increase of the relative content of particulate organic matter is
typically observed not only during flood but during other seasons in European rivers of
moderate climatic zones (Artemyev, 1981; Artemyev et aI., 1982). This is also testified
by lower values of the Cd/CP ratio when compared with northern rivers.
It was determined, using the example of rivers of the Black Sea and the Azov Sea
basin, that the vertical and horizontal distribution of organic matter in river mouths is
quite a complicated one (Table 19) specific for each river and therefore free of common
regularities. It is seen from Table 19 that concentrations of CP, even within the limits of
water layer of several metres, may change by 2-4 times with the maximum content either
in surfacial waters (S. Bug river) or in the bottom layer of water (Danube, Don). It is
possible to see in the example of vertical distribution of CP in the Don mouth how sharply
concentrations of CP may change at the same section of river channel (for example, near
left hand shore) over a distance of several kilometres.
Organic Substance of River Run-Off 25
The same inhomogenity is also typical for horizontal distribution of CP on the river
surface (Table 19). As it is seen. the content of organic matter on the cross-sections of
river beds may change by a factor of 1.5-1.6. In this case no regular connections of
extreme values to that or another section of river bed are noted.
Thus, to obtain accurate data on the concentrations of Cd and CP in the river mouth,
taking into account the inhomogeneity of the spatial distribution of Corg in river mouths,
it is necessary to take water samples for analyses in three points of cross-section of the
river bed: near the right and left shores and in the middle of the river from surfacial,
intermediate (when depth is more than 3 m) and bottom horizons. The average value of
all the obtained data will be the real value of Cd and CP concentration in the river mouth.
Mountain rivers of the Caucasian coast of the Black Sea are first of all characterized
by an abundance of suspension, exceeding its content in all other studied rivers by many
times (Artemyev, 1981). The absolute content of Corg .both Cd and cP is comparable to
that for plain rivers of the basin of the Black Sea and the Azov Sea. But, relative content
of CP in mountain river suspension is equal to only 2%.
26 Chapter 2
Content in sediment, %
Region of Station Si02
works No. Depth Type of sediment arnorph. Ccarb CaC03 C org OM
River 8.0 Sand, fine-grained, grey-brown 0.26 nJ. n.f. 0.07 0.13
2 7.0 Sand, fine-grained, grey-brown 0.25 0.04 0.33 0.14 0.25
3 14.0 Sand, fine-grained, grey-brown 0.25 0.04 0.33 0.12 0.22
4 6.5 Sand, fine-grained, grey-brown n.f. n.f. 0.08 0.15
5 2.1 Aleurite with interbeds of 0.44 0.20 1.67 1.182.15
shaly muds, dark brown
6 2.5 Aleurite with interbeds of 0.42 0.24 2.00 1.41 2.57
shaly muds, dark brown
Limits 0.25-0.26 0.04 0.33 0.07-0.14 0.013-0.25
Sands {
Average 0.25 0.04 0.33 0.10 0.19
Limits 0.42-0.44 0.20-0.24 1.67-2.00 1.18-1.41 2.15-2.57
Aleurites {
Average 0.43 0.22 1.83 1.30 2.36
Estuary 7 10.0 Sand, fine-grained with inter- 0.24 0.08 0.67 0.48 0.87
beds of shaly muds
8 12.0 Sand, medium-grained with 0.14 0.10 0.83 0.32 0.58
gravel
9 14.0 Gravel with aleurite interbeds 0.48 4.00 0.96 1.75
Limits 0.14-0.24 0.08-0.48 0.67-4.00 0.32-0.96 0.58-1.75
Average 0.19 0.22 1.80 0.59 1.07
Table 19. Distribution of organic matter on water surface in river mouths (Artemyev, 1981).
CP C~ mg/l
Left River Right Left River Right
River Horizon shore middle shore shore middle shore
Note: Numerator contains contents of organic matter in mg/l, denominator the same in %.
To clarify the nature of river organic compounds it is important to study their spacial
distribution in various sections of the river basin both in the main channel and in the main
tributaries. Especially important are such studies in the largest rivers of the Earth, the
waters of which have the greatest effect on wide water areas of the ocean. So the Amazon
river flow, coming into the Guiana stream is spread in northerly and easterly directions
and has an effect on the waters of the equatorial tropical Atlantic covering 107 km2 during
the maximum run-off.
One of the first summaries of hydro- and geochemical data of the Amazon was prepared
by Clarke (1924) and later on published by Livingstone (1963). Studies of the geochem-
istry of organic substance in the Amazon basin were started in the seventies and eighties,
mainly as a result of studies on the research ship "Alfa Helix" and other research ships
(Wissmar et al., 1981; Richey, 1981, 1982; Richey et aI., 1980, 1985; Furch and Junk,
1985). However, this data was insufficient for revealing the main regularities of spacial
distribution of dissolved and particulate organic matter in the river basin, since samples
were taken at a small number of stations and only from the river surface. Therefore, dur-
Organic Substance of River Run-Off 29
4'~--------------------~1~OO~O~1~OO~km~------~----------~
, ,
3"
Fig, \0, Sampling stations in the Amazon River Basin (March-April 1983),
ing the 9th cruise of research vessel "Professor Shtokman" to the Amazon (March-April,
1983), we carried out more detailed studies of peculiarities of Cd and CP distribution both
vertically and horizontally, Corg in bottom sediments, composition of organic matter in the
Amazon river from interflow of the Solimoins and the Negru rivers to the mouth and in its
main tributaries: Solimoins, Negru, Madeira, Topazhos, Trombetas, Shingu and Tokatins
(Artemyev, 1988), Figure 10 and Table 20,
The Amazon occupies first place among the world rivers by the value of river run-off,
5780 km3/year on average (Meade et at" 1979),
This huge run-off is explained by the size of the draining surface - 7 050 000 km2 -
and by the quantity of precipitations - 2500 mmlyear, The water velocity in the Amazon
varies from 0,5 to 1 mls during the dry season (June-December) and 1,0-2,0 mls during
the rainy season (January-June), Near Obidus (800 km from the river mouth) where
standard hydrological tests are carried out and in some parts of the Solimoins river the
velocity may be equal to 3-4 mis, The water temperature in the Amazon is relatively
stable (+29 0 throughout the year), The highest water (flood) is in the lower Amazon, in
May, the lowest is in November,
The Amazon is the final collector of a uniquely complicated draining system, with
numerous branches, tributaries, channels, flooded values, lakes, lagoons, etc, As a result
of geological development the Amazon draining surface is now limited at the west by the
Andes, at the north by Guiana and at the south by the Central Brazil massifs, The Amazon
draining waters are subdivided into three main categories: black, white and pure (Sioli,
w
0
\)
~
IV
"...
Table 20. Bioproduction, organic carbon and nitrogen in the waters of the Amazon and its main tributaries (according to data, presented by Artemyev, 1988).
Negru (above
Manaus) 13 5.1 5.1 5.0 1.1 30.7 0.09 15 8.1 7.0 0.20 31
Negru (below
Manaus) 7 5.4 20.1 0.48 20381 2.81 5.8 0.5 10.4 0.04 14 7.2 14.7 0.14 42
Solimoins 6 7.1 124.0 1.8 1.3 0.09 17 5.2 3.3 0.13 15
Madeira 3 6.9 0.85 2.09 272.0 2.3 0.8 0.14 14 4.5 2.2
Trombetas 4 7.2 22.5 0.72 335575 3.16 10.1 1.1 10.8 0.05 22
Topazhos 6 6.7 14.4 1.30 564137 1.73 5.4 0.8 16.7 0.08 22 4.5 7.0
Shingu 7 6.9 31.0 0.95 129670 2.43 8.4 0.8 15.5 0.04 17 5.3 11.2
Tokantins 4 7.4 48.0 8.30 24176280 3.19 26.5 2.5 9.2 0.09 39 5.8 2.5
Amazon 28 7.1 1.7 0.53 9000 1.58 121.0 2.0 1.7 0.10 20 5.1 2.5 0.14 25
1975). "Black" waters (Negru and Branku rivers) have their origin in the central part of
the Amazon river and are acidic (pH = 5) waters, which are exclusively poor in nutrients
and are of a reddish-black colour. The colour is caused, as it will be considered below, by
humic acids, produced in podsolic soils. The colour of solutions is explained by presence
of many chromofore groups, which may be aromatic nucleuses of free radical groups. In
spite of the low concentration of inorganic feeding salts black waters are characterized by
high concentrations of Cd (see below).
"White" waters (the Amazon river, Madeira river) are characterized by the presence
of large quantities of sedimentary material (suspensions) and contain more nutrients than
"black" waters. "Pure" waters (Shingu, Topazhos and Tokantins rivers) are typical for
northern and periphery zones and are predetermined by sedimentation of suspension in
large mouth bays of these rivers.
On the whole the Amazon waters are not rich in organic matter and may be compared with
distilled water, slightly polluted (Richey, 1982). Dissolved organic matter are supplied to
the Amazon waters mainly from underground and ground flows. The primary production
(PP) of macrophites and phytoplankton in the Amazon water is very low, due to the high
content of suspended material, supplied to river waters as a result of erosive processes in
the river head and insignificant concentrations of nutrients. The lowest values of primary
production were observed in the waters of the Amazon river (1.7 mgC/m 3/hour), the
highest - in the mouths of the Tokantins and the Shingu rivers - more than 30 mgC/m3/hour
(Table 20). The intermediate values of primary production are typical for the black waters
of Negru river - about 20 mgC/m3/hour. Similar types of distribution are observed on
the Amazon basin in such biological parameters as breathing, volume of phytoplankton
organisms and density of bacteria (Wissmar et al., 1981).
The year-round observations of p.rimary production value in the Negru river (15 km
above Manaus port) showed that primary production varies from 0.27 to 0.02 gC/m3/day
(Shmidt, 1976). As it was already noted, conditions for primary producing are not
favourable in "black" waters due to low pH, as well as extremely low concentration
and the non-balanced composition of biogenic elements and insufficient illumination (as a
result of selective absorption oflight by dissolved humic substances (HS) and the influence
of water muddiness).
The basic volume of river dissolved organic matter is represented by humic substances
originating from the organic matter of soils, formed in their turn from organic matter of
plants, animals and micro-organisms. Humic substances are represented by polymers -
humic acids (HA) and fulvic acids (FA) - products of reactions of extracellular conden-
sation of organic matter, released as a result of micro-biological degradation of ground
plants. Composition of dissolved organic matter may vary from river head to the lower
part of river due to differences in chemical composition of tributary waters, the sources
and the value of dissolved fractions. Dissolved organic matter, produced as a result of
humus destruction is supplied to the river water with underground waters.
32 Chapter 2
.c
:;
0
e:
.C~ ... 0
N
'" '"
.... ~
.0:" ;::
N 0
;:: 0
;:: ;:: c
.5" a; "
a; ."
0
.;
... "
I c N
;:: «'e:"
Z
'0 '"
N C; ;:: :a ;::
0 0
'"
0
'"
0
20
1;0
60
0
e 20
-
.s:5. 1;0
2' 60
Q 80
0
20
'10
60
80
Fig. 11. The distribution of particulate matter, Cd and CP in the Amazon river basin from Solimoins river
mouth to Amazon river mouth (March-April 1983).
The sources of particulate organic matter in the Amazon waters are phytoplankton,
periphyton, bacteria, moss, non-wood vegetable tissues and their residues, grass, macro-
phytes and timber. The Amazon basin is considered as a region which is not particularly
polluted with products of agricultural activities (Stallard and Edmond, 1983). Therefore,
it is possible to ignore anthropogenous sources of particulate organic matter (as well as
dissolved organic matter). Besides the enumerated sources the source of particulate and
dissolved organic matter in the Amazon basin water may be wood, floating on the main
surface.
According to existing estimates (Richey, 1982) the land surface products, drained by
the Amazon waters totals to 470 x 1013 gC/year, 8-16 x 1013 gC/year being supplied
to river waters from the drained land. Considerable quantities of Corg in the Amazon
basin are accumulated in so-called "Varsea", where the sources of carbon are macrophytes
Organic Substance of River Run-Off 33
R. Negro
10j2 1033 1030-31 mouth
0
10
20
30
~ 40
....Q,
,.d
Go>
~ 0
10
20
c~ . mg/I
30
40
Fig. 12. cJ and C~ in the Negro river (March 1983).
(about 5 x 1013 gC/year). In this case about 1 x 1013 gC/year of products of macrophytes
may be exported to river waters. As the studies show a considerable part of plankton
carbon is oxidized in situ (Richey, 1982).
Content of Cd in the Amazon basin water varies from 2.0 to 11.5 mg/l and average is
equal to 5.7 mgll for surfacial and bottom waters (Table 20 and Figure 11). The maximum
content of Cd is in waters of the Negro river (below Manaus), about 8 mgll, the lowest
one is in the Trombetas river (4.3 mgll).
Concentrations of ~ vary little with depth. Relatively high concentrations of Cd in
the Negru waters are predominated primarily by the delivery of organic matter from soil
humic acids, as well as by activity of primary products (Figure 12).
In the waters of the Amazon river, from the place of interftow of the Solimoins and
Negru rivers to the mouth, Cd concentration is within the limits of 5-7 mgll and the spacial
34 Chapter 2
distribution of dissolved organic matter is rather homogenous in both surfacial waters and
depth (Figure 11). In the Amazon mouth Cd content is approximately 5 mgll.
Content of CP in the studied waters varies from 0.3 to 4.3 mgll and on average is
1.6 mgll for surfacial waters and 1.2 mg/l for bottom waters (Artemyev, 1988). The
highest content of CP in both surfacial and bottom waters was found in the suspension of
the Tokantins river: 2.8 and 2.3 mg/l respectively, the lower is the surfacial waters of the
Topazhos river and in the Negru river below Manaus: 0.6 mgll.
In spite of close values of the average concentrations of CP in surfacial and bottom
waters of rivers of the Amazon basin, contents of cP in waters of surfacial and bottom
horizons at the separate stations differ by 1.5-4 times in the majority of studied rivers
(Negru, Solimoins, Shingu, Tokantins, Topazhos) (Artemyev, 1988). In this case there
is no regular connection of higher (or lower) concentrations of CP with the surfacial or
bottom horizons. This testifies that the basic factor, determining behaviour of suspension
and particulate organic matter in the Amazon basin waters is a windous or turbulent mix
of waters.
The highest content of CP in studied waters of the Tokantins river is bound up with the
activity of phytoplankton organisms. The highest (compared with other Amazon waters)
values of primary production and biomass of phytoplankton (Table 20) are obtained there
too.
The share of river CP in suspension varies from 0.5 to 31.5%, the average share in
surfacial waters amounts to 8.6%, in depth waters it is equal to 11.0% (Figure 13). The
richest suspension (by organic matter) is that in the Negru river above the port of Manaus,
where the content of CP in surfacial and bottom waters amounts to 23.9 and 30.7%
respectively. The lowest content of CP is in the suspension of the Madeira river (0.8%).
As a rule, CP equals to 10-20% of the Amazon suspension.
According to our investigations organic matter in the waters of the Amazon is mainly
in the dissolved form, which is illustrated, in particular, by the Cd/CP ratio (Table 20).
This value varies from 1.2 to 18.5 and amounts to 5.9 and 6.7 on average for surfacial and
bottom waters respectively.
Assuming (by our data) that the average contents of Cd and CP in the Amazon water is
equal to 5 and 2 mgll respectively (Artemyev, 1988, Table 20) and that the annual water
consumption is 183 000 m3/sec (Meade et ai., 1979a) we find that the river discharges
1.17 x 1013 g ofCP and 2.7 x 1013 g of Cd a year.
As it was shown as a result of investigations (Meybeck, 1981) nitrogen is available in
river waters mainly in the suspended form. This is nitrogen of protein-like material, as
well as that adsorbed in clays and other mineral particles. It was determined that nitrogen
of protein-like material is equal to 85-90% of the total Ngrg.
Content of Ngrg in the Amazon waters varies from 0.03 to 0.19 mg/l and averages
0.06 mg/l in surfacial waters and 0.08 mgll in bottom ones. As it follows from the data
given in Table 20, the results of determination of Ngrg in the Amazon waters, is obtained
by various authors with use of various methods and in different seasons, are as a rule,
of one order. And there are no essential differences in contents of surfacial and bottom
waters.
Annual flux of Worg of the Amazon amounts to 5.57 x 1011 g (lttekkot et ai., 1983).
Organic Substance of River Run-Off 35
c P, %
26.5
Q
20,5
20
1S
10
0
... ~~ ~:s ~
.... c::. t-- Z
~ ~~~
~ ~~~~ ~~ ~~ ~ ~
~
~ ~
1" c
~
~
~
Fig. 13. The distribution of cP in the Amazon basin and estuary (March-April 1983).
The CPfNP ratio in the studied waters varies from 7 to 80 and is equal on average to 27
for surfacial waters and to 16 in bottom waters. The highest value of CPfNP are typical
for the Tokantins river, where organic matter-containing compounds are represented in
minimum quantities. The highest quantity of nitrogen-containing compounds is in the
organic matter of the Negro rivers, where one of the lowest CPfNP (13-16) was found. An
increase of the relative content of nitrogenous organic matter in the Negro river waters
was caused by the fact that one of the main sources of organic matter in these waters are
soils - the main suppliers of nitrogen-containing organic matter in river waters (amino
acids, amino sugars). In the Tokantins river, where activity of primary producers is most
intensive (Table 20), delivery of organic matter from soils is of minor value.
In the Amazon river basin sediments are represented by terrigenous sands and muds and
differs essentially by content of Corg (Table 21). So in sands Corg amounts to 0.06-
0.30% (0.14% on average) and to 1.81-3.55% in muds (2.9% on average). The lowest
concentrations of Corg are in the bottom sediments of the Solimoins river (0.06%) and
36 Chapter 2
Content on sediment, %
Ord. Depth Sampling Si~
No. Station No., river m interval Type of sediment amorpb. Cc.rb CaC03 Corg
2 3 4 5 6 7 8 9
1002, Tokantins 30 0-5 sand, terrigenous, grey 0.52 0.01 0.08 0.09
2 1005, Amazon 13 0-5 sand, terrigenous, 0.46 0.03 0.25 0.19
dark grey
3 1006, Shingu 16 0-10 mud, petite, terrigenous 10.02 0.01 0.08 2.94
dark grey
4 1009, Amazon 11 0-10 sand, terrigenous, grey 0.32 0.01 0.33 0.30
5 1013, Topazhos 25 0-5 mud, petite, terrigenous, 4.96 0.03 0.25 2.76
grey
6 1015, Amazon near Obidos 68 0-5 sand, polymictic, grey 0.45 0.02 0.17 0.11
7 1017, Trombetas 7 0-5 mud, a1eurite-petite 0.38 0.03 0.25 3.41
terrigenous, grey with
remains of plants
8 1021, Madeira 17 0-5 sand, terrigenous 0.42 0.01 0.08 0.17
dark grey
9 1024, Sotimoins 23 0-5 sand, terrigenous 0.40 0.01 0.08 0.06
yellowish-grey
10 1028, Negru, above Manaus 23 0-5 mud, petite, terrigenous, 0.77 0.03 0.25 1.81
dark grey
11 1032, Negro, above Manaus 9 0-5 sand, quartz, greyish- 0.42 0.03 0.25 0.09
yellow
12 1034, Negro, below Manaus 30 0-5 mud, petite, terrigenous 0.43 0.03 0.25 3.55
13 Sands Limits 0.32--0.52 0.01--0.04 0.08--0.33 0.06--0.30
14 Average 0.43 0.02 0.18 0.14
15 Muds Limits 0.38-10.0 0.01--0.03 0.08--0.25 1.81-3.55
16 Average 3.31 0.03 0.22 2.90
ESTUARY
17 1044, estuary, section 13 0-5 mud, petite, terrigenous, 0.54 0.05 0.42 0.47
"Amazon mouth-ocean" with interbeds of sand
18 1050, section "Amazon 14 0-5 mud, a1eurite, petite, 0.44 0.03 0.25 0.29
mouth-ocean" terrigenous, grey
19 1055,northersection 11 0-5 mud, petite, terrigenous 0.80 0.03 0.25 0.67
"continent-ocean"
20 1061, estuary 13 0-5 mud, petite, terrigenous 0.33 0.01 0.08 0.46
Limits 0.33--0.80 0.01--0.05 0.08--0.42 0.29--0.67
Average 0.53 0.03 0.25 0.47
Organic Substance of River Run-Off 37
10 11 12 13 14 15 16 17 18 19
0.30 10.0 5.35 0.09 0.20 2.25 1.7 3.7 42.1 52.5
0.14 12.9 3.29 0.01 0.03 2.47 0.3 0.9 75.1 23.7
0.30 11.8 6.46 0.07 0.18 3.54 1.1 2.8 54.8 41.3
0.11-0.55 0.01-0.03 0.003-0.02 1.8-18.2 1.5-18.2 63.6-94.6
0.26 0.01 0.01 7.6 6.0 86.4
0.14-0.3 9.2-17.0 3.29-6.46 0.01-0.1D 0.03-0.20 1.71-3.54 0.3-2.0 0.9-3.7 27.5-75.1 23.7-68.8
0.25 12.2 5.27 0.07 0.13 2.39 1.3 2.4 47.7 48.6
ESTUARY
0.05 9.2 0.84 0.01 0.02 0.06 1.1 2.4 7.1 89.3
0.02-0.05 9.2-14.5 0.53-1.22 O.oI-O.Q2 O.oI-O.Q2 ??-O.06 \.3-2.3 1.6-2.4 4.1-22.3 73.1-96.2
0.035 11.85 0.86 0.02 0.02 0.04 1.75 2.05 8.37 87.8
38 Chapter 2
%
80 II t
_I
__ 2
____ 3
•
60 I
4
1\
"
I,
•
40
I,
I I
I , -
I,
II
I,
II
I
I I ,, I,
I
I
I
I
I
I , I I
,
, ,
20
:
: I
I I I, ~I "
I,
. .. ..f . .
I , I
• I
I .. ,
I l .. '
./
, \1 1/ \\ ,I
I, .
I /\
,,
0 I
, ""
It' I
0 0,2 0,4 0,6 0,8 1,0 2 4 10 20 30 60 70 Co.. ' %
Fig. 14. Corg content in soils, particulate matter and bottom sediments of the Amazon river basin (March-April
1983). 1. Sands, 2. muds, 3. soils, 4. suspension.
the highest ones in muds of the Negru river (3.55%), Figure 14 illustrates that the most
frequent concentrations of Corg in sands and muds amount to 0.1 and 3%, respectively.
Content of nitrogen in the Amazon muds varies from 0.14 to 0.30%, average 0.25%.
The CIN ratio values (9.2-17.0,12.2 average) give a possibility to suppose the combined,
mainly humus-like genesis of organic matter of studied river sediments. The role of
highest plants residues is, probably, the greatest one for sediments of the Negru and the
Trombetas rivers.
The content of amorphous silica and calcium carbonate in sediments of the Amazon
basin is, as a rule, a very low one (less than 1%), which testifies to the low propagation
of silica-containing and carbonate-containing organisms, and the presence of mineral and
inorganic particles in sediments.
Comparative analysis of organic matter concentration variation in the Amazon basin in
the case of passage from suspensions to bottom sediments signifies the character of organic
matter bottom sediments inherited from organic matter suspension. This is expressed in
connection with absolute contents of Corg of bottom sediments with Corg content in the
suspension (Figure 13). Lower contents of CP and Corg in bottom sediments, taken at
the same stations on the rivers Solimoins, Madeira and Amazon are determined by the
low bioproductivity, active hydrodynamics, as well as by the granulometric composition
of bottom sediments (medium-grained sands) which are not able to accumulate organic
matter supplied from the water mass.
Higher content of organic matter (Figure 13) (mainly humus genesis) was found in
suspension and bottom sediments of the rivers Negru, Topazhos, Trombetas and Shingu.
Influence of economic activities of human society (sewage discharge, etc.) on the con-
centration of organic matter is not excluded.
Organic Substance of River Run-Off 39
v.1. Vernadsky noted such variation of organic matter content of river waters as "variation
of chemical composition of dissolved and micro-dispersive substance, borne by rivers
... These variations are sharply expressed for each individual river. The rivers are ex-
tremely sensitive, balanced systems, which vary permanently ... It [the river] changes
perpetually, and this variation is different for each place of its course, varies every day
and night, by the seasons of the year and during long-term periods" (1960).
Seasonal variations of organic matter drainage depend, first of all, upon the climate and
ground plant development stages. During warm periods, activity of plants for extraction of
micro-elements from water is intensified, as is the decomposition of organic matter in soil.
All three main phases of drainage usually exist during this period of the year: underground,
river bed and slope-type drainage. During the period of maximum precipitations (spring,
autumn) the intensity of substance transfer is increased, as is their content in river waters. In
spring, when wash-off and transportation are performed mainly by the surfacial drainage-
slope and bed-type - the maximum drainage of colloidal, suspended particles is observed.
Most often the maximum quantity of mineral and organic substances is transported to
reservoirs in spring. In winter activity of plants connected with extraction of chemical
elements from river water is reduced to the minimum or stopped entirely. At this time
evacuation of mineral and organic substances to reservoirs with river drainage is decreased
owing to the decrease of temperature, slowing the rate of chemical reactions, decrease of
the absolute quantity of water in drainage, decrease of ground flow supply, almost complete
haiting of slope drainage and considerable decrease of river-bed drainage (Muraveisky,
1960).
The maximum drainage of water over most of the Russian territory is noted during
the spring flood period. The highest concentrations of organic matter in river waters
are observed during the same period (Table 16). Distribution of organic matter drainage
within the year depends, in particular, upon the type of water regime of the rivers. So the
rivers of the Barents, White and Kara Sea basins are related to the type of water regime,
with the prevalence of snow supply and spring drainage; therefore, the maximum drainage
of organic matter into these areas is typically during the spring flood (Table 22).
Different quantities of organic matter migrate in various seasons from water collecting
areas, their qualitative composition is also different (Voronkov, 1970). Various waters
ended their formation on the surface or in the thickness of soils-grounds prevalence in the
river bed network in various hydrological periods. The upper layer of forest zone soils
is enriched with movable forms of organic matter, entering the river bed during the flood
40 Chapter 2
Table 22. Organic matter run-off (in %) into the Russian seas by
seasons (Smimov. 1974).
1,2
10
.
c.
CII
1,0
~
8
..
J:l
o 0,8
:5
6 ~
o
Fig. 15. The seasonal distribution of organic matter run-off of some large U.S.S.R. rivers: 1. year; 2. spring;
3. summer-autumn; 4. winter (Maltzeva et aL. 1987).
period. Supply of rivers with ground waters containing considerably less organic matter
than surfacial-slope water is intensified in summer.
Variation of organic matter content in steppe waters in various seasons are usually
expressed less clearly (Figure 15). For the majority of northern and moderate humid zone
rivers, except for the rivers of the western European part of Russia, the Azov region and
Caucasus, with uniform distribution of organic matter drainage for the whole year, the
drainage of organic matter is typically prevalent during spring flood (Figure 15). Drainage
of organic matter during the spring flood in the basis of the North Dvina and the Pechora
rivers is equal to as much as 65% of the annual one (Maltseva et al., 1987).
Organic Substance of River Run-Off 41
PM CP Cd Cd/C p
19 70
.-. • PM
3,0 18 60 a ell
7 2,5 17 50
6 2,0 16 40
5 1,5 15 30
Ii 1,0 14- 20
3 0,5 13 10
2 0 12 0
...41
e
e
=
<I}
Fig. 16. The seasonal distribution of particulate matter, Cd and cP (mgll) in the North Ovina river mouth
(Artemyev et aI., 1984; Artemyev and Romankevich, 1988).
The results of determining Cd and cP content in the North Dvina mouth during various
seasons (Table 16, Figure 16) demonstrate essential differences of concentrations of both
Cd and cP in river waters. The highest content of Cd is typical in winter, which is
bound up with low rates of dissolved organic matter destruction under the conditions of
low water temperature. Higher concentrations of CP were noted during the spring flood
period in connection with the general increase of suspension content. Similar results were
obtained when studying seasonal peculiarities of distribution of Cd and CP, as well as that
of nitrogen in the mouth of the Mackenzie river (Telang, 1985), flowing like the North
Dvina river in the northern humid zone. Higher concentrations of Cd in the mouth of the
Mackenzie river (as well as in the mouth of the North Dvina river) were observed in the
winter months and the lower values in summer, when the higher concentrations of CP and
NP were noted within the period of flood and lower concentrations when the rivers were
frozen.
It may be considered that the essential seasonal variations of Cd and cP concentrations
in the mouths of rivers were observed everywhere, where we observe seasonal variations
of climate, determining both quantity and composition of river organic substance.
The cyclical character of organic matter distribution during the year is observed in the
mouths of some rivers; it is determined first of all by local climatic conditions (Figure 17).
42 Chapter 2
Cd, CPr
mg/I mrg~/I____________________________________________~
Fig. 17. The seasonal distribution of Cd and cP in the St. Lawrence river mouth (Pocklington, 1985).
C
mg/l 50
'"
,.,'
10 40 e PM
'0 my/l
8
30
:=0 - 160
I
-
6
e..= - 120
2 CII
20 .~
Ill:
4 80
10
2
1 40
L_-J
0
0 0
month
Fig. 18. The seasonal change of particulate matter content (I), cd (2) and cP (3) in the Orinoko river (Nemeth
et aI, 1982).
PM. mgtl
1000 t:""--------""I'T"----_t
/\
500 / tl.,
I ,
I ,
o o-,....-o--.d 'b
20
10
o
J F M A M In JI A SON D
month
Fig. 19. The seasonal change of particulate matter, cJ and CP concentrations in the Ganges river (Itte\ckot et
al., 1985).
were performed for the first time in the Amazon in the region of port Obidus (Kempe,
1982).
The study of seasonal distribution of Cd and CP in the Amazon itself was not carried
out. However, the studies carried out in the Solimoins river (Furch and Junk, 1985)
showed that the content of Cd is subjected to essential variations during the annual cycle
and coordinated with variation of water level in the river.
Time, H
6 10 12 14 16
i i i
300 P-PO t , mg/)
250
200
Si, mg/l 7.5
7.0
Fig. 20a. The change of biogenic elements, particulate matter. Cd, CP and trace elements in the Don river
mouth for a period of a day (October 1980).
Time, h
10
6,0 F---T-----,r----.------,----A---=;F-----'=n
4,0
2,0
0,0
-
7,0
4,0
CP, mgt)
2'O~
I,
40
20
0,
o
c"tC" 15,0
10,0
5,0
Fig.20b.
Cu Fe Mn
05 2fJ 5
J 0,3 100 3
2 0,2 50 2
1 1
T8ZG
~ 0,6 150 3
5
0,4 -100 1
1
0,2 50
6 8 10 12 1'1 16
Time, h
Fig. ZOe.
2.4.6. CONCLUSIONS
1. Organic matter is distributed in rivers of the world in accordance with climatic zonality
and is represented in river water mainly in dissolved forms. The highest concentrations
of Cd were found in rivers of the northern humid zone, which is bound up with the
supply of organic matter of mainly humus genesis from podsolic and swampy soils of
taiga-and-forest, forest-and-tundra and tundra zones.
2. The highest flows of both Cd and CP are supplied with rivers to seas and oceans in
the equatorial humid zone, respectively 75.8 and 90.2%. On the whole, rivers transport
approximately equal quantities of Cd and cP, 0.204 x 109 t/year and 0.184 x 109 t/year,
respectively.
3. The spatial distribution of CP in waters of river mouths vertically from the surface
to the bottom and horizontally from one shore to another one are of very complicated
character and are not characterized by any general regularities. Therefore, to obtain
correct data on the concentrations of Cd and CP in the river mouth it is necessary to take
samples of water for analyses in three points of lateral section through the river bed: near
48 Chapter 2
mgC/J
20
Daugava R.
. , IlIIlIlllIJ t-:-:Js
i§m2 ~* 06
15
10 Bailie Bea
2J2M
Corgo, ~~==*=~~~~~~==~
% 50M
I
50", 200", 232M I
100
I
I
I
50 I
I
I
I
I
Fig. 21. Corg in the particulate matter, colloidal and dissolved substance in the Daugava river and the Baltic Sea
(Lutzarev and Pashkova, 1984). 1. Particulate matter; 2-5. colloidal substance fractions; 6. dissolved organic
matter (molecular weight < 103).
the right, left shores and from the middle of the river from surfacial, intermediate (when
depth exceeds 3 m) and bottom horizons. The average value from all the obtained data
will be the proper value of concentration of Cd and CP in the river mouth.
Organic Substance of River Run-Off 49
2.5.1.1. DissoivedAminoAcids
Nearly all of the most important amino acids were found in river waters: glutamic and
aspartic acids, glycerine, alanine, leucine, arginine, serine being met most often (Semenov,
1967; Ittekkot et aI., 1982, 1986).
The predominance of "bound", i.e. unable for reaction, resistant to fracture, amino acids
testifies their presence in river waters in the form of mainly humic compounds (Seifert
and Ittekkot, 1985). The composition of free and bound amino acids in river waters varies
essentially depending upon the season and is rather sensitive to the change of production
process intensity, transformation, and consumption of organic matter (Semenov et ai.,
1966b). The study of proteins in the rivers of Latvia showed that high concentrations of
proteins in river waters are typical for summer, and the lowest are for winter (Table 24).
Such regularity is evidently bound up with the higher activity of phytoplankton which
produce the organic matter in the summer-autumn period, contributing to dissolved or-
ganic matter accumulation and, in particular, accumulation of proteins in river water.
The connection of the content of proteins in river water with the process of primary
production of organic matter by phytoplankton testifies to their autochthonous genesis.
The results of studying suspended free amino acids in the Amazon showed that they
amounted to 0.02-0.04% (0.03% on average) for calculation of dry mixture weight and
0.05-0.6 (average 0.2%) of organic matter (Tables 25 and 26).
Organic Substance of River Run-Off 51
Months Average Cd CP
River, point II IV V VII X XI XII per year mgll %
Gauya, above Sigulda 168* 580 630 604 537 400 - 502 11.9 4.2
56 192 210 202 180 133 168
Daugava, above Dkabpils 420 534 453 672 540 408 - 530 16.7 3.2
140 178 151 224 180 136 177
Lielupe, above 336 524 750 655 - 516 487 570 20.0 2.0
Kalntsiems 112 175 250 218 172 162 190
Neutral amino acids - 46.3-55.0% (average 49.9%) of the sum of amino acids -
prevailed essentially in the amino acids composition of the Amazon basin suspension.
Studying the individual composition of amino acids in the suspension of the Amazon
basin (Table 26) and other major rivers of the world (lttekkot et al., 1983) showed that
glutamic and aspartic acids and glycerine prevail in suspended amino acids as well as in
dissolved ones (Table 26).
Average contents of amino acids in bottom sediments of the Amazon basin river
total 0.11-0.14% (average 0.12%), converting into dry weight of sediment and 2.0-3.5%
(average 2.4%) of organic matter (Tables 27 and 28) which is 2-3 times higher than amino
acids content in modern ocean sediments (Romankevich, 1977). Neutral amino acids
(39.6%) prevail among amino acids groups in bottom sediments as in suspension also,
and aspartic and glutamic acids prevail among individual amino acids. The summary
content of amino acids in the bottom sediments of the Amazon basin is increased by 4-
5 times, compared with suspension, content of amino acids containing sulphur is increased
most intensively, by 16 times (Table 27). Similarity in the correlation of amino acids
groups and set of individual amino acids in suspension and bottom sediment testifies
their genetic relationship and the geochemical dependence of bottom sediments organic
matter upon particulate organic matter composition. An increase of amino acids content
in bottom sediments is bound up with the typical feature of organic matter transformation
in the process of sedimentation including an increase of humic acids in organic matter
composition.
2.5.2. CARBOHYDRATES
The results of analyses of carbohydrates in northern and southern rivers of the European
part of Russia (Artemyev, 1981; Artemyev et al., 1984) showed that carbon of particulate
and dissolved carbohydrates in the waters of the North Dvina river (C~ and C~ amount
respectively to 1.2 mgn and 0.04-0.14 mgn (average 0.09 mgn). Thus, the example of the
North Dvina river shows that carbohydrates in northern rivers are represented by mainly
VI
N
Table 25. Group composition of amino acids in particulate matter of the Amazon basin and its estuary. ~
'<;j
1. Trombetas (1017) 12.3 0.005 0.013 0.005 0.003 0.001 0.027 0.12 18.0 49.2 18.0 IJ.J 3.7
(22.4)
2. Shingu (1006-1008) 15.5 0.006 0.019 0.010 0.004 0.002 0.041 0.14 14.6 46.3 24.4 9.8 4.0
(28.2)
3. Topazhos (1013) 20.5 0.004 0.014. 0.004 0.002 0.001 0.025 0.06 16.0 56.0 16.0 8.0 4.0
(37.3)
4. Amazon (1015. 1020) 2.0 0.004 0.01l 0.005 0.002 0.001 0.023 0.64 17.4 47.8 21.7 8.7 4.4
(3.6)
5. Negru (1028. 1033. 1034) 26.1 0.004 0.13 0.005 0.003 0.001 0.026 0.05 15.4 50.0 19.2 11.5 3.9
(47.5)
Limits 2.0-26.1 0.~.006 0.011-0.019 0.~.01O 0.002-0.004 0.001-0.002 0.023-0.041 0.05-0.64 14.6-18.0 46.3-56.0 16.0-24.4 8.0-11.5 3.7-4.4
Average 15.3 0.005 0.014 0.006 0.003 0.001 0.028 0.20 16.3 49.9 19.9 9.8 4.0
(27.8)
Estuary: 1054 7.6 0.004 0.0011 0.005 0.002 0.001 0.023 0.17 17.4 47.8 21.8 8.7 4.3
(13.8)
1050 17.5 0.003 0.QJ5 0.005 0.003 0.001 0.027 0.08 IJ.J 55.5 18.5 11.1 3.8
(31.8)
1049 24.9 0.003 0.QJ5 0.005 0.003 0.002 0.027 0.06 IJ.J 55.5 18.5 IJ.J 3.8
(45.3)
1047.1048 40.2 0.003 0.017 0.006 0.003 0.001 0.04 10.0 56.7 20.0 10.0 3.3
(73.2)
1045 0.003 0.016 0.005 0.003 0.001 0.028 10.7 57.2 17.6 10.7 3.8
Limits 7.6-40.2 0.003-0.004 0.011-0.017 0.005-0.006 0.023-0.030 0.04-0.17 10.0-17.4 47.8-57.2 17.6-21.8 8.7-1J.J 3.3-4.3
Average 22.5 0.003 0.QJ5 0.005 0.003 0.001 0.027 0.09 12.1 54.5 19.3 10.3 3.8
&~ C
6 1054 7.6 19 20 39 19 15 21 15 4 18 15 107 23 27 50 18 18 9 223 13 ~
7 1050 17.5 11 17 28 29 23 32 18 5 20 19 146 21 25 46 10 16 26 9 255 14 §
8 1049 24.9 8 24 32 26 17 27 26 6 30 21 153 30 22 52 15 17 32 15 284 14 ~
9 1047.1048 40.2 10 20 30 26 20 30 29 7 29 26 167 28 31 59 15 18 33 11 300 14 So
10 1045 11 17 28 20 22 30 24 6 31 29 162 25 26 51 16 19 35 14 290 14 S
Average 22.5 12 0 20 31 24 19 28 22 6 26 22 147 25 26 52 11 18 29 12 270 14 ~
Table 27. Variation in the composition of amino acids in the system "particulate matter-sediment".
Table 28. Composition of bottom sediments amino acids in the Amazon basin.
"
3. 1017, Tromhcta~ 0-5 3.41 1.71 27.5 64 89 101 II!.S 91 82 104
4. 1028, Rio Negru, 0-5 1.81 2.47 75.1 ~ 63 40 72 15.1 77 82 60 96
ahuvc Manaus
5. 1034, Negru. 0-5 3.55 3.54 54.8 73 60 84 16.4 78 78 91 112
below Manaus
Limits 1.81-3.55 1.71-3.54 27.5-75.1 51-73 38-89 12-101 15.1-18.5 50-78 62-91 60--91 79-1I2
Average 2.9 2.4 47.7 64 ;8 87 17.1 66 78 76 95
..
3.
5.
26
24
28
89
73
63
65
56
98
37.5
40.'
41.4
179
147
120
136
120
98
22.9
23.0
16.4
39
79
57 70
56
88
9.2
8.1
12.6
85
85
99
69
69
76
13.3
13.3
13.2
3.5
3.5
2.1
Lim. 20-211 63-89 48-98 36.2---41.4 115-179 98-136 16.4-24.9 38-79 56-88 8.2-12.6 63-99 44-76 10.1-13.3 2.0-3.5
Av. 24 74 64 39.3 144 116 21.5 54 69 10.0 84 63 12.0 2.4
Organic Substance of River Run-Off 55
dissolved form (about 98%), C~ amounts to 11.7-20.0% (average 14.8% of CP), and C~
to 3.5-12.3% (average 8.9% of Cd).
About 115 of the dissolved organic matter in southern plain rivers is represented by
carbohydrates, a share of which amounts to 17.3-33.8% (average 21.7%). The total
content of carbohydrates in rivers of southern seas of Russia totals, on average, 1.2 mgll
for plain rivers and 2.8 mgll for mountain ones. In this case, if in plain rivers, carbohydrates
are present mainly in dissolved form (average 68.5% of carbohydrates sum), particulate
carbohydrates (70.1 %) prevail in mountain rivers.
Content of carbohydrates in particulate organic matter of southern plain rivers is ap-
proximately the same as in particulate organic matter of the North Dvina river: C~ equals,
on average, 15.5% of CPo The ratio freelbound sugars in river waters is essentially
higher than that in plankton organisms, which, as a result, contain negligible quantities
of simple sugars (Artemyev, 1976). This may be connected with a preference of simple
sugar formation rate in river waters over their consumption, as well as with excretion
of low-molecular carbohydrates by developing algae. As it was shown by the studies of
Semenov (1971) river waters differ essentially from each other by the composition of their
carbohydrates. These variations are caused by many factors, the most important of which
are the variation of composition of water organisms and the selectivity of consumption
of various carbohydrates by them. Thus, only the study of organic matter composition
and some of its components gives a possibility to estimate the trend and the intensity of
biogeochemical processes in river waters controlled by organisms inhibiting the water
medium. The data about relative content of labile components in river waters (amino
acids and carbohydrates) may give ideas about the potential ability of organic matter for
destruction. It was determined that the concentration of labile components in particulate
organic matter composition in the majority of large rivers of the world does not exceed
12% (Degens and Ittekkot, 1985), i.e. the predominating part of particulate organic matter
is represented by compounds which are resistant to degradation.
The proportion of labile and stable dissolved components in river and sea waters may
be studied using the example of the Visla river and neighbouring waters of the Baltic Sea
(Pempkowiak, 1985). It was shown that labile dissolved organic matter in river waters
amounts to 20-30% and in sea waters it is equal to 30-40%. In this case the share of
labile Cd in both river and sea waters during the seasons with lower average temperatures
of water is higher than in summer months.
Seasonal variations of concentrations and composition in river mouths are typical for
amino acids and carbohydrates as well as for other classes of organic matter, which testifies
irregularity of supply of various classes of river organic matter to sea water, their qualitative
variety being dependent upon the season. It was shown that variation of the share of amino
acids and carbohydrates in river organic matter composition may be used as indicators
of biogeochemical processes in river waters (Ittekkot et ai., 1985). Evidently, organic
matter fractured by micro-organisms will contain relatively low quantities of these labile
components. Investigation of seasonal variation of concentrations of amino acids and
carbohydrates in the mouth of the Ganges (Ittekkot et ai., 1985, 1986) gave a possibility
to determine that, in the case of an increase of river drainage, there is biodegradation
of river organic matter as a result of biogeochemical processes. This is also borne out
56 Chapter 2
by the decrease of content of labile components in it. The sequence of organic matter
biodegradation or change of source of organic matter in river water is caused by seasonal
variation in the composition of amino acids and carbohydrates (Ittekkot et at., 1986).
Concentration of humic substances in river waters varies from less than 10 to 1000 mgCn 3
(Table 29). One may observe the clear zonality in latitudinal distribution of humic acids
in river waters, determined by the influence of terrigenous material. The highest values
of humic acids content were found in coloured waters of northern and Siberian rivers
(Table 29), its supply being bound up with spring or autumn floods, i.e. supply of humic
substances from the water collection area. It is known that seasonal variations of huinic
substances concentration, which are also determined by supply of terrigenous humus to
rivers, have a connection with its water regime. All this is true for rivers, flowing in zones
of excessive precipitation with a high development of forest, plants, well-drained podsolic
soils, etc.
The results of the study of annual variation of concentrations of humic acids in the
Don river showed (Semenov, 1971) that in the winter low water period concentrations
of dissolved humic acids are low, and in spring flood and in autumn they reach their
maximum values. Thus the concentration of humic acids in river waters of the moderate
humid zone is determined mainly by organic matter supply from water drainage area and
not within reservoir processes (Semenov, 1971).
From Table 29 we notice that the content of humic acids in plain river waters is increased
regularly from the tundra group of landscape (Pechora river) to the taiga group (North
Dvina, Daugave rivers) where it reaches its maximum values, and further to the south in
the steppe zone it is decreased to the lowest values (Don, Kuban rivers).
Typical river of
Hydrological phase CHA CPA drainage system basin
TUNDRA
spring flood 339 2266 Pechora river
summer low water 236 1989
winter low water 130 1048
FOREST-TUNDRA
spring flood 435 3371
summer low water 180 2130
winter low water 87 1495
NORTHERN TAIGA
spring flood 1020 5438 North Dvina
summer low water 180 2218
winter low water 114 1572
STEPPE
spring flood 98 1046 Kuban
summer low water 17 602
winter low water 18 578
In spite of the fact that the largest part of coloured humic substances in river waters
consists of fulvic acids, reliable information about the concentration of these substances is
virtually absent in the literature. The few existing determinations of fulvic acids content in
rivers showed that their quantity exceeds content of humic acids in river waters by several
times (Tables 29 and 30). According to the data of Ertel et al. (1986) organic matter in
58 Chapter 2
River HA FA
the Amazon waters amounts to 60% of dissolved organic matter. The ratio FAlHA is, on
average equal to 4.7 ± 1. In the Solimoins river waters it is 5.4, in the Negru river waters
it is equal to 1.6. Dissolved humic substances, responsible for the colouring of the Negru
river waters, amount to about 112 of dissolved organic matter, the other part of dissolved
organic matter are represented by colourless organic acids (Leenheer, 1980). The data of
determining the elementary composition, infrared analysis, and other data show that the
majority of non-humic dissolved organic matter is supplied to "black" waters as a result
of drainage of the latosolic soils of the region.
Humic acids, found in "black", "white" and "pure" waters of the Amazon may be
compared with those supplied from podsolic and latosolic soils of the Amazon region
(Leenheer, 1980). The maximum quantity of organic matter of humic type were found
in "black" waters, where they are supplied as a result of underground waters drainage of
podsolic soils covered with a thick layer of organic residue, accumulated on the surface.
The study of the chemical composition of humic substances of Amazon "black" waters
showed that they are the final products of organic matter destruction as a result of the
humification process, which is carried on in tropical soils and waters more quickly than
at more moderate latitudes (Leenheer, 1980).
Considerably lower quantities of humic substances are delivered into "pure" waters,
passing through latosolic soils. These soils have no such layer as podsolic ones, which
are enriched with organic matter and, moreover, coloured solutions of humic substances
are adsorbed on clay minerals of latosolic soils.
Organic Substance of River Run-Off 59
Table 31. Bituminological characteristics of suspensions of the Amazon basin and estuary.
Estuary
6. 1054-1, 1054-2. 7.6 1.32 7.24 not found 0.20 9.6 52.5 37.9
1054-3
7. 1050 17.5 5.41 11.30 not found 0.50 17.0 35.5 47.5
8. 1049 24.9 3.39 13.40 not found 0.25 6.2 24.4 69.4
9. 1047. 1048 40.2 1.48 23.38 not found 0.06 2.7 42.6 54.7
10. 1045 2.39 13.60 not found 0.20 no data
Average 22.5 2.89 13.78 not found 0.20 8.9 37.7 52.4
2.5.3.2. Humic Substances and Bitumoids of Particulate Matter and Bottom Sediments.
Transformation of Organic Matter Composition in Line Soils-Suspension-Bottom
Sediments
As it was shown by the studies (Table 31), humic acids in river suspension are either
absent or are present in trace quantities. As a rule, more than 50% of river particulate
organic matter is represented by bitumoids. Alcohol-benzol bitumoid "N' (bit. Aal.b)
prevails in the Amazon suspension, content of that bitumoid tends to increase towards
the river mouth, reaching almost 50% of organic matter. The sum of alcohol-benzol and
chloroform bitumoid "N' (bit. AcI) amounts to 25-80% in suspension of the Amazon,
average 60% of organic matter. The remaining organic matter is represented by residual
organic matter (ROM).
The main components of river bottom sediments are humic acids and residual organic
matter. Humic acids are found in the terrigenous muds of the Amazon basin, where their
concentration amounts to 1.71-3.54%, average 2.39% converting into dry weight, and
27.5-75.1 %, average 47.7%, of the organic matter sum (Table 21). The high content of
humic acids (average of 65% of organic substances) is typical for bottom sediments of the
Negru river. According to the elementary composition of humic acids and other physico-
chemical characteristics (Table 32) humic acids of bottom sediments in the studied rivers
are formed by products of destruction of higher plants. Humic acids, found in aleurite-
60 Chapter 2
Table 32. Physico-chemical characteristics of humine acids of bottom sediments and soils in the Amazon
basin.
Content in HA, %
Corg HA HA,% Ash Moisture Combustible mass
Station number, river Type of sediment % % from OM C H N O+S
1006, Shingu mud, pelite, 2.9 2.3 42.1 10.0 7.2 58.3 6.1 4.0 31.6
terrigenous, grey
1006, Shingu soil 2.7 0.8 16.5 34.1 7.2 48.7 6.1 - 45.2
lOB, Topazhos mud, pelite, 2.9 2.0 39.2 14.9 10.0 57.4 5.8 4.3 32.5
terrigenous, grey
1013, Topazhos soil 1.2 0.6 29.2 24.3 6.0 not determined
1030, 1031, Negru soil 1.0 0.3 18.7 29.8 5.7 not determined
1028, 1034, Negru mud, pelite, 2.7 3.0 64.9 23.3 7.8 59.2 5.9 2.5 32.3
terrigenous
clay sediments of the North Dvina river amount, on average, to 20.4% of organic matter
(Table 28).
Content of humic acids in soils taken on the Amazon basin rivers shores is below that in
sediments (Table 32). Humic acids of soils are characterized by high ash-content, which
in a number of cases makes it difficult to carry out their analysis. Humic acids were
not found in terrigenous river sands in either the Amazon basin or the North Dvina river
mouth (Tables 18 and 21).
Content of bit. AcI and bit. Aal - b in both sands and muds of the Amazon basin decreases
compared with suspension and total respectively to 13.6 and 3.7%. The predominating
part of organic matter in sands is presented by residual organic matter: 86.4% on average.
The share of residual organic matter in muds is on average equal to 48.6% of the sum of
organic matter. Residual organic matter of aleurites in the North Dvina mouth is equal to
74.8%.
Variation of group composition of organic matter in sediments observed down the Ama-
zon stream is quite regular and is determined by peculiarities of distribution and genesis
of organic matter. So terrigenous sands of the Solimoins, Amazon and Tokantins rivers
which are poor in organic matter are at the same time characterized by high content of
bitumoids (up to 18%), typical for hydrobiontic organic matter (Artemyev and Danyu-
shevskaya, 1988) and with the absence of humic acids (Table 21). Muds of the Negru
river are characterized by the high level ofhumification of organic matter (up to 75%) and
low bitumoid content (about 2%).
The studied river sediments of the Amazon river are clearly divided into two genetic
groups. The first includes sediments enriched with organic matter pelite muds of the
Negru, Trombetas, Shingu rivers. The second one includes organic matter poor sands of
the Amazon, Solimoins, Madeira, Tokantins rivers. Evidently the basic source of organic
Organic Substance of River Run-Off 61
matter of the first group of sediments, which are characterized with high humification and
low bitumoid content, are products of destruction of higher plants.
Practically the whole soluble part of organic matter in sediments of the second group is
represented by bitumoid components, i.e. they are free of humic acids. Organic matter in
these sediments is more polymerized (average content of residual organic matter is 86.4%,
and 48.6% for sediments of the first group), and probably of hydrobionic type.
Bituminological studies are essentially supplemented by the results of physico-chemical
studies of sediments and soils from the Amazon river system (Table 33). Bitumoids of
river sediments, referred to by us as the first group, are characterized by high content of
hetero-elements (0, N, S), average 15.7%, and their main carriers - resins and asphaltenes.
The quantity of asphaltene components amounts, on average, to 25.0%, in the first group
of sediments and it is equal to 52.8% in the second one. Bitumoids of the first group
of sediments are poor in oils, in accordance with the enrichment of oxygen-containing
compounds, the extremely low content of hydrocarbons is found in the composition of
their organic matter (in 5-6 times less than that in the second group of sediments).
Thus, the data of element, group and hydrocarbon composition of bitumoids and their
molecular structure is completely in agreement with the bituminological characteristics
and reflect the presence of two basic types of organic matter in river sediments.
Comparison of physico-chemical characteristics of organic matter of sediments and
soils (Tables 33 and 34) gives a possibility to note the features of differences among
them. The data of element and hydrocarbons composition testify that soils contain higher
quantities of aromatic compounds. Evidently, there is an enrichment of soils with oxygen-
containing compounds, especially with asphaltenes and asphaltenic acids, the quantity of
which reaches 51.7%, which is 6 times more than that of bottom sediments. There is
no doubt that organic matter of soils is much poorer in the oil and hydrocarbons. The
observed differences in the structure ofbitumoids of soils and bottom sediments are related
to the original organic material, being the source of organic matter formation. For soils
these are mainly destructured vegitable residues, for bottom sediments it is hydrobionic
material together with residues of higher plants.
Aleurite muds and sands from the North Dvina mouth are identical to muds and sands
of the Amazon basin (Tables 18 -and 35) by composition of organic matter and bitumoid
Acl.
2.5.4. LIGNIN
Table 33. Comparative characteristics of organic matter of soils, suspensions and bottom sediments
from the Amazon basin and estuary.
Innumerous studies of lignin from the present day in river and sea bottom sediments
permitted us to determine that the content of lignin destruction products (phenolic alde-
hydes, ketones, acids) in organic matter of bottom sediments varies from hundredth parts
of a per cent to a several per cent. The total content of identified phenols in the studied
sediments of North Ovina river mouth varies from 5.3 to 35.2 pig of aerial dry sediment,
or from 0.06 to 2.88% of Corg (Figure 22).
High content of phenols was found in bottom sediments at four stations (4, 5, 6 and
2). High content of phenols in bottom sediments of station 4, remote from the sources
of technogenous pollutions, may be caused by the supply of lignin from wood, stored
at river shores as a result of washing out with rain waters. Higher content of lignin in
bottom sediments, taken at the other three stations is, first of all, related to the supply
of lignin-containing components with sewage waters of neighbouring plants. There is
a trend for a decrease in the quantity of phenols with increasing distance. The lowest
concentrations of phenols in bottom sediments were found at the stations remote from the
place of sewage discharge.
Among the products of lignin oxidation, vanillin aldehyde predominates, as well as
p-oxyacetophenone and p-oxybenzaldehyde. Their percentage in all the studied samples
of bottom sediments of the North Ovina river mouth is considerably higher than that of
other components. Higher content of vanillin aldehyde is bound up with its supply from
coniferous forests, growing on the shores of the North Ovina river as well as from sewage
products.
The source of p-oxybenzoic structures may be grass, as well as macrophytes. Higher
content of vanillin and syringyl aldehyde is typical for angiosperms (Manskaya and
Kudina, 1975). Vanillin prevails in lignin of monocotyledons and syringyl aldehyde
prevails in lignin of bicotyledons.
Low concentration of syringyl aldehyde in the studied sediments, compared with
vanillin aldehyde, may serve as the index of pollution of the studied region with industrial
Table 35. Physico-chemical characteristics of bonom sediments of the North Ovina river and Dvinsky Gulf.
North Ovina I sand, medium-grained n.f. nJ. n.f 56.3 39.9 3.7 89.5 10.5 8.5 0.006 4.33 3.87
river 2 sand. medium-grained nJ. nJ. nJ. 41.6 52.7 5.5 84.8 15.2 5.6 0.004 1.66 1.41
3 sand, medium-grained n.f. n.f. n.f. 43.4 48.6 6.0 80.3 19.2 4.2 0.004 1.95 1.57
4 sand, medium-grained 81.9 11.7 7.0 62.9 33.7 2.5 87.9 12.1 7.3 0.006 4.21 3.70
5 aleurite 79.3 10.8 7.3 23.1 60.7 11.0 80.2 19.8 4.1 0.009 0.44 0.35
6 aleurite 78.1 10.0 7.8 20.4 67.9 10.1 79.6 20.4 3.9 0.014 0.55 0.44
81.9 11.7 7.0 41.H2.9 33.7-52.7 2.5-6.0 80.8-89.5 10.5-19.2 4.2-8.5 0.~.0I4 1.66-4.33 1.41-3.86 <::>
Sand { Limits
Average 81.9 11.7 7.0 51.0 43.7 4.4 85.7 14.2 6.4 0.005 3.04 2.64
78.1-79.3 10.0-10.8 7.3-7.8 20.4-23.1 60.7-67.9 10.1-11.0 79.6-80.2 19.8-20.4 3.9-4.1 0.~.0I4 0.44-0.55 0.3H.44
Aleurite { Limits
~o·
Average 78.7 10.4 7.5 21.8 64.3 10.5 79.9 20.1 4.0 0.012 0.49 0.39
OvinskYGulf 7 sand with clay mud 81.3 12.1 6.7 49.2 45.3 S.3 86.S I3.S 6.4 0.010 1.13 0.98
8 sand 82.3 12.3 6.7 51.6 3S.4 12.8 84.3 15.7 S.4 0.10 1.7S 1.47
~
9 sand 79.6 12.0 6.6 61.3 34.1 2.8 86.3 13.1 6.6 0.024 1.41 1.22
§
~
nJ. = nOl found. ~
:.;,
~
..
:.;,
§
~
0'1
U\
_I
66 Chapter 2
16
~IJ
72 _IV
Bill
_VI
~v
Ol ~VlI
"::I..Ol 8
rn
o VIII
..
'0
1:1
.C1
II.
"
StaUon N
Fig. 22. The composition oflignin in bottom sediments at the profile "North Dvina river mouth-sea" (Peresypkin
et al., 1989). I. Benzoic acid, II. p-hydroxyacetophenon, III. p-hydroxyhenzaldehyde, IV. p-hydroxyhenzoic
acid, V. vanillin, VI. vanillic acid, VII. syrlngyl aldehyde, VIII. syringic acid.
waste since syringyl structures are destructed firstly in processes of biodegradation, then
vanillin ones.
Lignin is also supplied to river and estuary waters by the process of bark destruction
when rafting wood, and its storage on the water surface. When bark is leached, various
resin substances are also supplied into the surrounding water medium. The chromatogram
(Figure 23) illustrates these high-molecular components which are now difficult to identify.
Their content in the studied sediments, as it may be seen, considerably exceeds the
concentration of phenols in lignin destruction products.
The main pollutions are delivered to sewage during production of cellulose in process
of sulphite and sulphate boiling, washing, bleaching and processing of alkalies. Alkalies
after boiling sulphate cellulose contain 22-28% of lignin in the form of lignin-sulphonate
complex (Maksimov and Volf, 1969). The sulphate method of cellulose production prede-
termines the presence of dissolved sulphate alkaline lignin in sewage waters (Bogomolov,
1973; Nepenin, 1963). Thus, lignin sulphates and sulphate alkali lignin are supplied to
North Dvina waters with plant sewage, which in the process of purification are eliminated
from sewage waters only to a very insignificant extent (Maksimov and Volf, 1969). In
the process of destruction of these products, various phenols may be released into the
surrounding medium and be buried in bottom sediments (depending upon the type of
Organic Substance of River Run-Off 67
~'j . i In
1'-1.' . .I. .. , .
6
7 5
Fig. 23. Chromatogram of a1kali-nitrobenzol oxidation products of bottom sediments organic matter from
the Northern Dvina river mouth (Peresypkin et al., 1989). 1. Benzoic acid, 2. p-hydroxybenzaldehyde,
3. p-hydroxyacetophhenon, 4. vanillin, 5. p-hydroxybenzoic acid, 6. syringyl aldehyde, 7. vanillic acid, 8. sy-
ringyJ acid.
wood processing). High content of vanillin in the studied samples of bottom sediments
indicates that coniferous wood is mainly subjected to such processing.
Lower (comparing with vanillin aldehydes) concentrations of para-oxybenzaldehyde
in the studied samples testify the secondary role of grass for delivery of phenols to
North Dvina waters. The ratios p-oxybenzaldehyde/vanillin aldehyde and syringyl alde-
hyde/vanillin aldehyde in the studied samples vary respectively from 0.5 to 1.9 and from
0.04 to 0.18, which indicates the permanent source of vanillin structures (comparing with
p-oxybenzaldehydeand syringyl aldehyde) in waters of North Dvina river (st. 1-3). Low
values of p-oxybenzaldehyde/vanillin aldehyde and syringyl aldehyde/vanillin aldehyde
are related to bottom sediments, taken near CPP4 (Stations 1, 2). Aromatic acids (ex-
cluding syringic ones) were found in all samples, their concentrations being considerably
lower than those of aldehydes (Figure 22).
The total content of lignin in bottom sediments, including unidentified compounds,
may be determined by calculations, assuming that the vanillin aldehyde content is equal
to 6% of the total content of lignin in bottom sediments (Gardner and Menzel, 1974).
80
70 a
60
Station N
Fig. 24. Interrelation of lignin derivatives (phenols) in the particulate matter of the Amazon river basin and its
estuary. P = paraoxybenzaidehyde, V = vanillin aldehyde, S = syringyl aldehyde.
*- C',mg/l
0,8 ~p
~V
~S
_P+V+S
0/1
Station N
Fig. 25. Lignin derivatives (phenols) from particulate organic matter of the Amazon river basin and its estuary
(see Figure 24).
~P ~v ~s b
50
~
rG
'0
if'"
III
0
1031 1032 102* 1028 1030 1021 1009 1061 10** 1050 1055
Station N
Fig. 26. The interrelation of lignin derivatives (phenols) in bottom sediments of the Amazon river basin and its
estuary (see Figure 24).
phenols) in particulate organic matter composition in both the river and the estuary does
not exceed I % (Figure 25). The highest content of phenols was found in the mouth of the
Amazon, which is associated with the accumulation of lignin-containing natural objects
in the lower part of this river. High content of phenols was also found in suspension of the
Negru river, which is, to a considerable extent, formed on the account of lignin-containing
plants (Hedges et ai., 1986).
Comparing this with river suspension, the content of lignin in the composition of
particulate organic matter in Amazon estuary is somewhat increased primarily on account
of syringyl aldehyde.
p-Oxybenzaldehyde and vanillin aldehyde essentially predominate in the phenols of
bottom sediments, as well as in suspension, and total 85% on average.
Thus, compared with the suspension, the share of vanillin aldehyde increases in the
composition of lignin of bottom sediments of the Amazon basin and estuary. In this case,
the share of lilac aldehyde in muds is higher and that of p-oxybenzaldehyde is lower than
in sands (Figure 26).
Any essential changes in lignin composition of bottom sediments (muds) of the estuary
(compared with river muds) were not observed. Content of lignin in bottom sediments of
the Amazon is equal on average to 20 {lglg for sands, and to 90 {lg/g of dry sediment for
muds.
The absolute content of lignin in the estuary muds is less than in the river and is, on
average, equal to 40 {lg/g. The highest content oflignin among river sediments was found
in the Negru river (Figure 27). However, content of lignin in the organic matter of muds
is increased in the direction river-ocean (Figure 28), by average from 2 to 5%. Thus
the same trend is traced in bottom sediments as in suspension: accumulation of lignin
in the composition of organic matter in the direction river-estuary, testifying to genetic
relationship of lignines in bottom sediments and in suspension.
70 Chapter 2
Phenols, "gIg
~,25
100
77 §lI p
~V
~S
_ P+V+S
50
o
Station N
Fig. 27. The content of lignin derivatives (phenols) in bottom sediments of the Amazon river basin and its
estuary (see Figure 24).
Higher content of lignin in the organic matter of river sands (compared with muds) is
related to the fact that organic matter of sands is, on the whole, more stable, chemically
inert and that its composition keeps mainly compounds of lignin type which are resistant
to decomposition and mineralization.
2.5.5. CONCLUSIONS
Humic and fulvic acids predominate among organic matter of river waters, being equal
to 60-80% of dissolved organic matter. As a rule, the content of fulvic acids exceeds the
content of humic acids by an order. The highest content of humic substances is typical
for waters of northern rivers of Russia and "black" waters of the Negro river (the Amazon
basin). The remainder of river dissolved organic matter is represented by amino acids,
carbohydrates and other organic compounds - products of activity of organisms. The
content of labile components (amino acids + carbohydrates) in the majority of rivers of
the world is equal to 30% of dissolved organic matter and 15% of particulate organic
matter.
Organic Substance of River Run-Off 71
~p
~v
~s
10 _P+v+-S
o
Station N
Fig. 28. The content of lignin derivatives (phenols) in bottom sediments organic matter of the Amazon river
basin and its estuary (see Figure 24).
For river bottom sediments (the Amazon basin) amino acids amount to 2.4% of organic
matter, on average, which is 2-3 times more than the content of amino acids in the modern
ocean bottom sediments (Romankevich, 1977).
Summarizing the data of the study of organic matter of soils, suspension and river
bottom sediments one should note the following:
1. The nature of organic matter of soils and bottom sediments is different: in soils
they are preferably destructured 'vegetable residues; in bottom sediments they are plank-
tonogenous material (together with residues of higher plants). Consequently, organic
matter of river bottom sediments is formed to a considerable extent without noticeable
influence of soil organic matter.
2. Composition of river particulate organic matter differs from the composition of
organic matter of bottom sediments first of all by a higher content of bitumoids and
by the absence of humic acids. Thus one of the main peculiarities of organic matter
transformation in the line "river suspension-bottom sediments" is debituminization, the
utilization of bitumoid components in surfaciallayer of bottom sediments under the effect
of bottom fauna and micro-organisms. In this case bitumoids are transformed into non-
soluble complexes ("residual" organic matter) and may also form sorptional complexes
with humic acids (Romankevich, 1977). Absence of humic acids in suspension does not
allow the consideration of suspension as one of the sources of humic acids in river bottom
sediments. Consequently, humic acids are formed in river terrigenous muds in situ. It
72 Chapter 2
should also be noted that on the surface of river bottom sediments in the Amazon basin
we observe the result of actively passing or recently completed process of humification,
which is testified by the high content of humic acids in terrigenous muds (especially in
muds of the Negro river, Table 21).
Organic matter of North Dvina muds is characterized by considerably lower content of
humic acids, approximately by 3 times compared to muds of the Amazon (Table 18). This
testifies to the fact that the organic matter humification process in river bottom sediments
of northern humid zone passes far less actively than that under conditions of tropical
climates. In river muds of the equatorial humid zone, conditions for humification of
organic matter are more favourable than at northern latitudes due to the high temperature
of water (average 29°C during the whole year) and more intensive (in this connection)
activities of micro-organisms and bottom fauna on the transformation of organic matter
in the surfaciallayer of bottom sediments, leading to organic matter humification.
In spite of the fact that humic acids are mainly formed in the process of diagenetic
transformation of organic matter in the surfaciallayer of bottom sediments, humic acids
of soil genesis may also be buried in bottom sediments. As we known, soil humic acids
are transported to river water with rain flow, draining the soil, as well as directly from soils
during floods, and they are present in river water in the dissolved form. Under certain
conditions, dissolved humic acids may be a source offood for water organisms (Spitzy et
at., 1991), and consequently may get into the food chain and participate in the process of
biosedimentation, incoming, for example, in the composition of pellet lumps, etc.
3. Independently from the climatic conditions of organic matter formation in both
northern and southern humid zones, two types of bottom sediments shall be separated
among the river bottom sediments by organic matter composition: terrigenous sands and
terrigenous muds. River sands differ from muds by the absence of humic acids, higher
content of bitumoids and "residual" organic matter, as well as by the composition of
bitumoid AcJ (the content of oils is higher in bitumoid Acl of sands). Consequently, it
may be supposed that the organic matter of sands has passed the stage of humification
and is at the stage of progressing formation of organic matter complexes, resistant to
bio- and chemical degradation. Humic acids are evidently completely destroyed under
sharply oxidizing conditions of the medium, or were not formed at all. The differences
in composition of organic matter of sands and muds are bound up with differences in
the "medium of life" of micro-accumulations of organic matter in the surfacial layer of
bottom sediments, essentially differing from each other by granulometric composition.
It is known that micro-accumulations of organic matter are mainly associated with clay
sediments (Romankevich, 1977). The experimental studying of sorption of plankton de-
composition products, organic matter of soils and ancient rocks, showed that clay minerals
may adsorb 3-4 times more organic matter than they contain (Romankevich, 1977). The
predominating part of this organic matter is strongly bound up with clay minerals and is
not converted into dissolved form. This connection contributes to conservation of organic
matter in case of micro-biological attack at earlier stages of diagenesis. In sands, parti-
cles of organic matter are in a free state and not bound with the mineral part of bottom
sediments as strongly as in clay muds. As a consequence of this, organic matter particles
Organic Substance of River Run-Off 73
in sands are, to a higher extent, subjected to both mechanical destruction, moving under
action of bottom streams, turbulent motion of water, etc. and to biodegradation.
4. It was determined that vanillin aldehyde and p-oxybenzaldehydepredominate among
the products of lignin oxidation both in suspension and in river sediments. The sources
of them are sewage of CPP, as well as coniferous trees and grassy vegetation. Content of
lignin is increased in the direction of river-ocean (the Amazon estuary) in both suspension
and bottom sediments. This fact testifies to the lignin resistance to destruction and to its
selective preservation in the organic matter composition.
Chapter 3
3.1. The Region of Intermixture of River and Sea Waters as an Intermediate Link
in the "River-Sea" System
The region of river and sea water intermixture is, by definition, close to "estuary". The
word "estuary" originates from the Latin word "aestus" (tide). It is written in the English
explanatory dictionary that an estuary is "a wide mouth of a river where its stream meets
a sea and which is subjected to action of tides and ebb tides". The literature contains
various systems of classification of estuaries, depending on the base, chosen by authors,
for its creation (Fairbridge, 1980). The most widely spread are two classifications, based
respectively on geomorphological and hydrodynamic properties (Pritchard, 1987). The
classification based on geomorphological properties subdivides estuaries into: flooded
valleys of rivers (for example, Chesapic Bay on the Atlantic cost of U.S.A.), estuaries of
fjord type, estuaries limited by banks, estuaries formed as a result of tectonic processes,
and estuaries of river deltas (Odum, 1975).
As for the hydrodynamic classification, estuaries are subdivided into three basic types:
estuaries with a stable salinity wedge, where the river run-off almost suppresses circulation
completely (for example, the Mississippi estuary), estuaries with partial mixing of waters,
and estuaries with well-mixed waters and insignificant variation of salinity from the surface
to the bottom (Figure 29).
Thus an "estuary" is a wide definition which is traditionally applied to the mouth regions
of rivers, inshore bays, tide damps (marsh), limans, in fact to all water areas where the sea
water is mixed with fresh water, supplied from the continent. From these positions, the
most precise definition of estuary is the definition made by Pritchard (1952, 1967a): "An
estuary is a semiclosed inshore body of water, which has free communication with the
open sea and inside which sea water is measurably diluted with fresh water, supplied after
74
Geochemistry of Dissolved and Suspended Organic Carbon 75
-
Sea
- -
River
River water
~
ea~ __
-4- ~«<<<<<<<<(<Z\~
water ~«,«<<<<<<''''
Sea
B
o So
~n
.-
Sea
,-----~----
---- .....
- "'- -. --
- ,---,---#--
~
.....~,,«<-;.<:__~vJ(...~~
River
~""'w:«Z"""'"«%"
C 2-f- _~~----~: ~
Fig. 29. Types of water circulation in estuaries (Bowden, 1975). 1. Profile through the estuary; 2. salinity;
3. velocity; A-C. types of estuaries (see text).
land surface drainage". Taking this definition as the basis, we shall consider the definition
"region of river and sea water intermixture" as a special case of an estuary where sea
water is mixed with not the whole body of fresh water, supplied from the land, but river
only. In the present work we use both these definitions. However, the term "estuary" we
use only in relation to the water areas which are traditionally defined as "estuaries". As it
was noted by Odum (1975), estuaries may be considered as "transitive zones, or ecozones
between fresh water and sea places of life". It is believed that the important contribution
76 Chapter 3
of estuary productivity is made by river run-off. However, this is true only in the case
where the river run-off is enriched with biogenic elements. On the whole, rivers do not
"fertilize" estuaries. Actually, mouths of rivers are less productive than bays and lagoons
which have no large tributaries, but having a well-developed bottom flora.
According to the data obtained by Riley (1967) biogenic substances accumulated and
renewed in estuaries are initially supplied from the sea. At the same time, estuaries often
produce more than they may utilize. As a result, there is outwelling of biogenic substances
and organic detritus into the ocean (Odum, 1975).
The following typical peculiarities of estuaries should be noted:
1. High sedimentation rate, exceeding those for the ocean as a whole by 1000-10 000
times.
2. Estuaries are areas of complex and active chemical processes, where sea water
interacts with a large set ofmicro-elements and organic matter, delivered from huge
areas of continental drainage systems. Complex chemical transformations also take
place in bottom sediments.
3. Estuaries are subjected to active attack of such hydrodynamic factors as sea waves,
tide-like variations of water level, river drainage, density stratification of waters,
wind-generated currents, etc.
4. Estuaries occupy an area of 1.7 min km2 , which totals less than 0.4% of the ocean
surface. However, they deliver more than 5% of net primary production (PP) of the
ocean (Table 36). Estuaries have no equal to themselves among the sea localities on
the net PP concentration (Table 37). The total vegetable mass of estuaries is equal
to 0.63 x 109 t of organic carbon, which exceeds 113 of the total vegetable mass of
I World Ocean - totality of oceans and seas of the Earth (Stepanov, V.N., World Ocean. Dynamics and
Properties o/Waters, Moscow, Znaniye pub\., 1974,255 pp. [in Russian].
Geochemistry of Dissolved and Suspended Organic Carbon 77
Table 37. Net primary production in various zones of the ocean (McLusky, 1981).
the World Ocean. The density of distribution of vegetable mass of estuaries is 2-3
orders greater than the density of distribution of the vegetable mass of the open ocean.
Estimation of the variety of ocean life conditions and the relative probability of life
concentration showed that by this index estuaries exceed all the known ocean localities by
many times (Aizatullin et at., 1979). Unfortunately, for the last few years in the majority
of the world's regions, estuaries were subjected to such strong action of people that it
causes alarm for their future. The main hazard is the supply of various pollutants into
estuaries as a result of drainage from continents and due to their supply from the open sea
(Anikiev, 1987). "In the presently existing critical situation it is extremely important that
the unique properties of estuaries would be understood widely" (Odum, 1975).
The region of intermixture of river and sea waters is at the same time a boundary
of separation of river and sea waters in the river-sea system, characterized by scales
measured in both tens and hundreds of metres, and sometimes by hundreds of kilometres.
The regions of river and sea water mixture also have their own inner hydrodynamic,
physico-chemical and biological processes, characterized by wide variety in time and
space. The rhythm of variety of hydrodynamic regime in the river-sea system is predeter-
mined by tides, seasonal variations of river drainage and wind. In the region of the mixture
of river and sea waters, the gradients of physico-chemical parameters arise, which are an
integral part of the geochemical barrier in the river-sea system. The following parameters
are changed as a result of the transition from river water to sea: proportion of compo-
nents of basic salt composition, ionic force of solution, concentration and composition of
suspension, organic matter, etc.
A distinctive peculiarity of estuaries with partially mixed and well-mixed waters is the
presence of a so-called "turbidity maximum" or higher concentration of suspension in the
bottom layer of waters and its accumulation near the bottom, generally in the middle part
of an estuary. This is associated with the character of water circulation in the estuaries
of that type. Fresh water drainage forms a current directed to sea in the upper layer of
water and the lower layer of the water mass is occupied with sea water, the current of
which is directed towards the land. River particles, lowered into this layer are taken by the
current directed towards the land and deposited on the surface of estuary bottom sediments
(Martin and Gordeev, 1981).
78 Chapter 3
Integration of river and sea waters occur in different ways in each estuary, which causes
specific peculiarities of hydrological and hydrodynamic regimes of waters. However,
there are also properties of the waters' regime formation which are common for regions
of river and sea water mixture. The physical and chemical processes in the estuaries are
interlinked and it is impossible without serious study of the problems of hydrology and
hydrochemistry in these water areas to explain sufficiently the other phenomena (such as
biological, physical, geochemical, etc.) since the dynamics of waters is the energetic basis
oftransportation and interaction of dissolved substances (Semenov, 1969).
However, it would be a mistake to suppose that variations of dissolved substance
concentrations in the estuaries are predetermined only by the dynamics of water. Chemical
transformations in estuary waters are of great value, due to the extent of the saturation of
waters with carbonates, dependent on variations in salinity, mutual chemical adsorption
at the "water-suspension" boundary and deposition of the formed aggregates (Alekin and
Moricheva, 1959, 1961).
Therefore, the process of intermixture of fresh and sea waters is more complicated than
simple mechanical stirring of salts, dissolved in water.
The problem of chemical interaction of river and sea waters is closely bound up with
the problems of studying the sedimentation process under conditions of intermixture of
river and sea waters.
It was theoretically determined and confirmed by observations that "transformation"
of river water into sea water is going on in such a way that the basic qualitative jump
is performed within the salinity range of 1-2%0 when river water mineralization is up to
0.25 gIl. In this case it is important that the jump area is determined independently upon
the sea water salinity and is the common regularity.
The value of active reaction pH in the regions of sea and river water mixing varies
during that process from values typical for river water to higher values in sea water. Since
deep salt waters with high values of pH take part in the mixing process, the surface waters
of the mixing region are characterized by local extremes, predetermined by dynamic
properties.
The river and sea water mixing regions are characterized by transformation of salt
composition of continental waters. When mixing river hydrocarbonic water (composition
of ions: HC03 > S04 > Cl and Ca > Hg > Na + K) and sea water (composition of ions: Cl
+ Br > S04 > HC0 3 and Na + K> Mg > Ca ) in these regions and especially in large bays
and limans, it is possible to trace all the intermediate stages of ionic ratio (Figure 30).
As it is seen, transformation of hydrocarbon ate Don river waters into chloride-potassium
sea waters generally takes place when the salinity is equal to 1-2%0. Similar variations
of ionic composition in the case of the mixture of river and sea waters take place also
in other seas (Almazov, 1962, 1967; Pakhomova and Zatuchina, 1966). Therefore, an
isohaline of 2%0 is considered the hydrochemical boundary between river and sea water,
although transformation of ionic composition of water goes on actively up to 6%0, varying
to a lesser extent up to 10%0. Ionic composition of water of higher salinity is practically
not changed (Figures 30 and 31).
Geochemistry of Dissolved and Suspended Organic Carbon 79
CII
.lC
.....
CII
Q
~III 10
-;
.!:!
.eEI
..
'ii
0
"'"
0
Fig. 30. The change of ion composition of Taganrog Bay water at the mixing of river and sea waters (Tzurikova
and Shu1gina. 1964).
ions/Cl
810-------------.
• -1
.6-2
0-3
6
~~-4
o 5 70 15
ions. g/kg
Fig. 31. The interrelation of summary mineralization and its relation to chlorine in the Azov Sea (Tzurikova
and Shulgina, 1964). 1. Open sea; 2. near Kuban river waters; 3. Taganrog Bay; 4. the area of river and sea
water mixing.
Oxygen
Area rngll % pH
developed, the upper limits of oxygen content in water do not usually exceed 100%
saturation and the pH value does not exceed 8.6. In open Iimans, where phytoplankton
are sufficiently developed, the oxygen content reaches 190% of saturation as a result
Geochemistry of Dissolved and Suspended Organic Carbon 81
Behaviour of dissolved components in the case of mixture of fresh and sea waters may be
"conservative" when it is determined exclusively by dilution of waters of low and high
salinity with various concentrations of elements; it may be "non-conservative" when the
processes of elimination or addition of substances as a result of physico-chemical and/or
biological processes are observed (Figure 32).
If some component contained in river or sea water is conservative, i.e. its total concen-
tration is changed only as a result of physical stirring, its total concentration will depend
only linearly upon the salinity (or chlorine content). However, if the component is elim-
inated or added to the water medium as a result of some processes (physical, chemical,
biological) there will be a deviation from the theoretical curve of dilution (depending
upon the salinity). Thus variation of total concentration of the component as a function
of salinity will give a possibility to determine if its behaviour is conservative or not.
Large (more than 1-2 /-tm) particles supplied to the estuary maintain their dimensions,
and their deposition is controlled by hydrodynamic factors. As for particles of smaller
sizes and colloids, their behaviour is controlled by the processes causing coagulation and,
in some cases, subsequent disaggregation of flocculated material. It was determined that in
82 Chapter 3
Conclntratlon
Fig. 32. The scheme of dissolved organic matter behaviour at the mixing of river and sea waters (Eisma, 1988).
fresh water solid particles of 1-2 /-tm (mainly clays and colloids) are usually characterized
by an excessive negative surface charge, as a result of which repulsive forces prevail
between these particles. This change is balanced by a double layer of positive ions;
its thickness depends, first of all, upon the ionic force of water, as well as upon the
temperature and pH. When a charged particle is supplied to a solution of high ionic force,
the double electric layer is compressed and the surface negative charge is neutralized (due
to the sorption of cations of the double layer). Decrease of the repulsive barrier between
particles create closer contact between them and contributes to the formation of aggregates
(Eisma 1981) or new formations of suspended particles; the higher their concentration the
more frequent their collisions. Transition to positive charges is met in cases of salinities,
typical for early stages of mixing (2-10%0) (Martin et at., 1971).
The process of enlargement of particles in the dispersive systems, with liquid or gaseous
dispersive media is called flocculation. The main subject of flocculation is colloid organic
matter of river genesis. The process of flocculation is also typical for Fe hydroxides, when
they are eliminated from the solution together with organic matter and micro-elements
bound up with them (Sholkovitz, 1976, 1978). It was determined that flocculation is the
main mechanisms for extraction of dissolved elements during estuary mixing (Sholkovitz
et at., 1977, 1978; Sholkovitz and Coplang, 1981). The phenomenon of flocculation of
organic matter of river genesis in the presence of sea water was discovered as far back
as in the forties (Skopintsev, 1946, 1947), but it was studied in detail only considerably
later, and first of all Sholkovitz and his colleagues (1976,1978,1980,1981). Experiments
performed by Sholkovitz showed that flocculation takes place in water within the range
of salinity from 0 to 15-20%0 and that dissolved organic matter plays the important role
in controlling non-conservative behaviour of inorganic components. The study of the
Geochemistry of Dissolved and Suspended Organic Carbon 83
<:l
~
1\
...
~ r Atmospberic Prec:iPilaUO';;-lr- - - - - - -....
""
+ + l
River Estuary Sea
~pp~PbytOplaDJdol1~
10M ofmacroPhites~~ River OM
DOM-O,204 • 10' Lc/year Sea
OM
I M of icbtbyoplaIlJdOI1
!
nocculation deDocculation!
I
OM of bottom
I
sediments !
COl. NIl,
(pJIlto-, ....._10....... et aI.1
Fig. 33. Paths of organic matter input and transformation in the river-estuary-ocean system (Mantoura, 1986; Laane and Ruardij,
1988; and the author).
Geochemistry of Dissolved and Suspended Organic Carbon 85
The basic sources of organic matter and the processes of its transformation in estuaries are
shown in Figure 33. Estimation of the contribution from the atmospheric precipitations
to the delivery of organic matter into estuaries is unreliable due to an absence of reliable
information about the concentration of organic matter in rain (Laane and Ruardij, 1988).
It is practically impossible to measure the flow of organic matter in the section estuary-
sea. It can only be supposed that the flow of river organic matter into estuaries will not be
the same as the flow of organic matter from the estuary to the sea.
The concentration of organic matter in the estuary is permanently affected by hy-
drodynamic and hydrometeorological factors (streams, tides, ebb tides, wind), physical,
chemical and biological interactions between organic and inorganic material. On the
whole, estuaries contain more living organisms than any other region of the sea or ocean
(Wolff, 1980). Due to this reason, organisms affect estuary chemistry much more inten-
sively than in other parts of the sea. Many animals (fish, seals, whales, mollusks, etc.)
migrate actively between the sea and the neighbouring estuary. Some species of fish
spawn in fresh water, and adult individuals live in the estuary or in the sea (anadromous).
In contrast to this fact, other individuals of fish spawn in the sea and live in fresh water
(catadromous).
The basic ecological groups of photosynthesizing primary producers in estuaries are:
phytoplankton, phytobenthos and vascular plants (sea grass). Phytoplankton in estuaries
are usually a mixture of phytoplankton from adjacent seas and rivers entering the estuary.
Many species of phytoplankton are able to grow and breed in water with a rather wide
range of salinity; however, there are optimal typical conditions for normal functioning
(Wolff, 1980).
The value ofPP in estuaries depends upon the water residence time in them. The longer
it is, the more intensive is the development of autochthonous estuary plankton. If there
is insufficient residence time of water in the estuary, sea and fresh water plankton die,
resulting in low values of PP. Intensive atrophy of phytoplankton in estuaries with a short
residence time of water, as expected, is met in intermediate water salinities, which are
characterized by low values ofPP. These suppositions were confirmed during measurement
of PP in one of the estuaries of the Netherlands (Table 39).
Another reason for low PP in salty waters of estuaries may also be due to the high
turbidity of water. The factors restraining development and growth of phytoplankton may
also include the temperature of the water, shortage of light, biogenic elements, processes
86 Chapter 3
of mixing of the waters and interaction of all these factors. In this case, one should bear
in mind that various types of phytoplankton require different quantities and proportions
of biogenic elements. Nutrient salts, limiting the growth of some types, may be useful for
other types. Consumption (eating away) of phytoplankton by zooplankton and zoobenthos
may also limit the PP value.
Growth and development of phytoplankton is one of the main biological processes
acting on the estuary chemistry. The concentration of C02, phosphates, nitrates, ammonia
and sometimes silica may be decreased as a result of photosynthesis. At the same time,
the content of oxygen increases and often reaches oversaturation. As it was shown by
measurements, the value ofPP in estuaries varies within the limits of 10-400 gC/m2/year
(Table 40).
Phytobenthos forming in estuaries belong to various groups, including unicellular
and multicellular plants with lengths of several metres. The data concerning PP of
phytobenthos in estuaries is given in Table 41.
Sea grasses (macrophytes) are vascular plants, living under water in inshore waters and
estuaries. For example, Zostera, Thallassia and Cymodocea grow at high salinities and
Ruppia and Zannichellia are typical for salty waters. The biomass of sea grass may be
very high being up to 2000 gC/m2/year (Figure 34).
Mann (1972), in his review of the productivity of sea grass, indicates values of 58-
1500 gC/m2/year. The highest values of sea grass production are typical for tropical
and subtropical waters. High values of production make sea grass the main producer of
organic matter in some estuaries. So, for example, according to Barsdata et al. (1974),
90% of PP in the Aizembeck lagoon (Alaska) is produced by Zostera algae. At moderate
latitudes, the production is provided by macro-algae such as Macrocystis, Laminaria,
Fucus and Ascophyllum and sea grasses such as Spartina, Zostera and Thallassia. In
tropical estuaries mangroves predominate. Large quantities of dissolved and particulate
organic matter are discharged in waters of estuaries as a result of macrophyte vegetation
(Sieburth and Jensen, 1970). The quantity of CD discharged by macro-algae reaches
7-15 gC/m2/day.
Geochemistry of Dissolved and Suspended Organic Carbon 87
the heavy (rich) supply of mineral and organic substances with river run-off, as well as by
good aeration and heating of the water.
Living organisms change the biochemical parameters of estuary medium, discharging
into it the products of exchange of substances and various organic compounds, and
consuming macro- and micro-elements, leading to a change in the substance composition
of the suspension and bottom sediments.
Within the limits of the shore zone and shelf, the region of maximum sedimentation of
terrigenous material are the delta and mouth regions. The most intensive rates of present
day sedimentation are noted in deltas, and the thickness of sediments of ancient deltas often
exceed 10 km (delta ofIrravadi river, Bengal delta, etc.): see Chystyakov and Scherbakov
(1983). The processes of sedimentation in the regions of river and sea water mixing depend
upon the physico-geographical situation existing at the water drainage areas, as well as
upon the hydrodynamic regime predetermining directed motion of water masses of various
salt composition and salinity. Within the boundaries of avandelta, where the area of river
and sea water mixing is usually placed, the sudden decrease of the velocity of river streams
causes the accumulation of poorly sorted, mainly terrigenous bottom sediments with a
wide size range, from sand to clay mud. The intensity of sedimentation from suspended
and traction detrital deposits in deltas and foremouth shelfs is extremely non-uniform and
is determined by the distribution of solid and liquid run-off along branches, the character
of the underwater slope, other morphological peculiarities, and hydrodynamic regime
(Chystyakov, 1980).
The basic hydrodynamic parameters, determining the fate of terrigenous material, are
stream run-off, waveness, piling up and piling down. The areas of river and sea water
mixing are characterized by the large-scale accumulation and processing of the material
supplied by river drainage. Lisitzin (1982) referred mouth regions to the first global belt
of avalanche-type sedimentation. Avalanche-type sedimentation is the process of very
quick accumulation of sedimentary material at the bottoms of reservoirs, which leads to
the appearance of new properties of sedimentary formation. Such processes take place
in deltas, estuaries, limans and marginal seas which are traps for sedimentary substances
(Lisitzin, 1982).
Almost a quarter of a century ago, opinion held that about 80% of river run-off material
is deposited in river mouths and on the ocean periphery (Vinogradov, 1967).
Estimating the losses of suspended substances of rivers in deltas, the majority of
authors came to the conclusion that more than 50% of river suspension is deposited in
river mouths and does not penetrate into seas and oceans (Sokolov, 1980); according to
the data presented by Lisitzin it totals up to 92%.
Numerous data on the distribution of suspension in seas and oceans showed that its
concentration is at a maximum near the river mouth (Lisitzin, 1982).
The rate of sedimentation in these regions is 1-2 orders higher than that in the pelagic
zone and reaches tens of centimetres per thousand years. A very important feature is that in
the case of avalanche-like sedimentation, organic matter has no chance to be decomposed
Geochemistry of Dissolved and Suspended Organic Carbon 89
in the water thickness or in the surface layer of bottom sediments. Organic matter of sea
genesis is added to terrigenous organic matter near river mouths, that finally causes the
noticeable enrichment of deposit with various organic matter.
High rates of sedimentation, leading to quick accumulation of huge masses of material
in the regions of river and sea water mixing, results in isostatic sinking of sedimentary
formations and an increase in their temperature. Thermobaric transformation of organic
matter, thermocatalysis, takes place and at a certain combination of temperature (60-
200°C) and depth (more than 1.5 km) oil- (and then gas-) formation is started within the
sedimentary column (Vassoevich et al., 1970, 1972; Sokolov, 1980).
The regions of avalanche-like sedimentation in a number of cases become oil-and-gas-
bearing zones that warranted significant activity in studying them for the last few years
(Lisitzin, 1982).
Propagation of the Amazon water stream, entering the Atlantic is predetermined mainly by
two factors; firstly, by the Guyana current, moving to the north-west over the continental
slope and external shelf; secondly, by tides.
According to data from Meade et al. (1979), the average current velocity decreases to
the north-west from the Amazon mouth, from 1.8 mlsec to 0.4 mlsec at 4ON.
The tidal currents are directed mainly across the shelf, especially in the upper layer.
They are most intensive near the mouth, 1.2 mlsec, the velocity of the tidal currents
decreasing to the north-west. To study the effect of tide on the changeability of various
characteristics in the Amazon estuary, a daily station (Figure 35) was arranged during
the period of Russian expedition investigations in 1983 in the Amazon and its estuary
(March-April 1983). At that time the tide was syzygeous, the level difference being equal
to 3.5 m.
It is clearly illustrated in Figure 36 that during the overwhelming part of time the whole
mass of water is occupied by river waters (salinity less than 1%0). Only at moments of
maximum water level freshened waters (salinity 6--7%0) arrive from the ocean side, and
they exist on the surface for 1.5 hours. Change of salinity proceeds in jumps and the front,
differing by colour, salinity and other characteristics, comes at the very end of the water
lift from the ocean side.
The maps - diagrams of salinity distribution on the surface for high and low water
seasons - are shown in Figure 37. During the high water season, 35%0 isohaline is at a
distance of 270 km from the river mouth. During the low water season the area of mixed
waters (salinity from 1 to 30%0) moves towards the river for approximately 50 km due to
decrease of river run-off, but salt waters do not penetrate into the river mouth. Figure 38
illustrates the distribution of salinity and standard density on the main section river-
90 Chapter 3
1il1il1058
1057 1062
t045.,
1046.,
1il'049
1050
',05'
@'054
it'052
1il'053
it 1il'044
1061
,rJ.:3
..•~~
48
Fig. 35. Sampling stations in the Amazon river estuary (March-April 1983).
:;tvSZl
H,M.--_________---.
TLDI
o 6 12
Time, H
18 2"
Fig. 36. The daily change of water level and salinity in the surfacial and deep waters at 1044 station (see
Figure 35) (Gordeev et aL, 1988)
Geochemistry of Dissolved and Suspended Organic Carbon 91
Fig. 37. The distribution of salinity (%0) at the surface of waters in the Amazon river estuary in a high water
(left) and low water season (Monin e/ al.. 1986).
ocean in the Amazon estuary during the high water season. Near the mouth, inclination of
isohaline is considerably less than those far away from it. In this area we observe intensive
turbulent mixing, caused by interaction of river water streams and powerful tidal currents.
Here we registered the minimal vertical gradients of salinity and relative density. The
maximum values of both vertical and horizontal gradients at the considered section were
registered near stations 1049 and 1050 in the medium part of the section. The vertical
gradients of salinity and relative density are distributed here almost uniformly through
the whole 20 m thickness of water, and amount to approximately 1%0 and 0.8 of relative
density unit per 1 m.
Complex processes of water mixing is well illustrated in Figure 39. This process
is characterized by alternation of waters which are weakly and strongly saturated with
oxygen. Moving from the shore, river waters are incrementally saturated with oxygen, up
to 100% at a distance of 250 km from the mouth. The zone of water oversaturated with
oxygen (up to 110%), associated with high bioproductivity, is observed in waters with
salinities of 15%0.
Horizontal gradients of salinity are insignificantly in the Amazon estuary waters, remote
from the mouth, but at the same time vertical gradients (Figure 40) increase sharply. Their
maximum values for salinity and relative density are equal to 3% and 1 unit of relative
density per 1 m.
The temperature of water in the Amazon and neighbouring regions of the Atlantic is
equal to 29 ± 1°C. The values of pH in the Amazon mouth are equal to 7.4 and vary within
the limits of 7.4-8.2 in the whole area of mixing of river and sea waters.
The Amazon transports 1.2 x 109 t of sedimentary material per year to the Atlantic
(Meade et ai., 1985)). Distribution of suspension in the surface layer of the Amazon
92 Chapter 3
Station N
20
a 40
..ci
....
Q.
Go)
60
Q
80
0 100 200 JOO
-
~
"
0
a
..ci
....
Q. 40
Go)
Q
80
0 100 200 300
Distance from the mouth, km
Fig. 38. The distribution of salinity (a) and density (b) at the profile "Amazon river mouth-sea" (see Figure 35)
(March-April 1983).
estuary water during the high water period is shown in Figure 41. The principal character
of suspension distribution is not changed during the period of low water (Gibbs, 1973).
The typical feature of distribution is the elongation of isolines along the shore to the
north-west, just like salinity isolines.
In the area of inshore shelf over the near-mouth bar, attention is drawn to the zone of
high concentrations of suspension, with values on the water surface equal to 200-400 mg/l
and in the bottom layer equal to 1500-4000 mg/l, which far exceeds the concentration of
Geochemistry of Dissolved and Suspended Organic Carbon 93
station N
ti ~~~" i1; -~ ~
~i ....
10
~
~ ....... ~ ~:s
......... ~ .... " ~ ~
a
:S 40
s:
8
80
0 100 200 JOO
Distance from tbe moutb, km
Fig. 39. Vertical distribution of oxygen (%) at the profile "Amazon river mouth-ocean" (March-April 1983).
80
0 50 100 150 a 50
Distance from the mouth, km
Fig. 40. The distribution of salinity (a) and density (b) at the profile land-ocean in the north-western part of
the Amazon river estuary (see Figure 35) (March-April 1983).
suspension in the Amazon moth (110 mgn). In accordance with optical characteristics,
these waters may be characterized as exclusively turbid ones. It may be supposed that the
reason for their originating is the rolling of bottom sediments by strong turbulent motions
during the interaction of the river water stream and powerful tidal currents.
The processes of rolling bottom sediments are clearly traced on the daily station (1044,
Figure 35). Variations of the suspension concentration is surfacial and bottom layers
of water due to the variation of the water level during tide/ebb tide cycle are shown in
Figure 42. We may see that the concentration of suspension is changed by more than two
times on the surface, and by more than an order near the bottom, depending upon the tide
phase.
94 Chapter 3
Fig.41. The distribution of particulate matter (mg/I) in surfacial (left) and near-bottom waters in a period of
high water in the Amazon estuary (Monin et al., 1986).
l-------l
1500
8 812 ::::::
."" "..'.
1000 ~
Q -
~~-----
.!:8
v:::
- .
QI Q
lii ,810 .. -
"l -- i
'. .
" .......--.~
, ,,' .~ 500 Q,.
...
'" .1:1
QI , ,
t:I .. 11"
8 ''Z1 0
~
0 5 10 15 20 Time. H
""
Fig. 42. The daily change of particulate matter concentration in the Amazon estuary. 1. Ocean water level;
2. particulate matter concentration at the surface of water; 3. same at 1 m from bottom surface (Gordeev et al.,
1988).
The Amazon estuary waters may be subdivided into four groups by colour (Monin
and Kopelevich, 1983): yellow-brown, yellow, green and blue. Yellow-brown waters are
located over the inner part of near-mouth bar and are characterized by the maximum values
of suspension concentration and optical characteristics. The salinity of these waters does
not exceed 1%0. In the case of transition to yellow waters, the salinity is increased stepwise
to 5-6%0 and the values of optical characteristics are lower. The boundary between yellow
and green waters is a sharp one, its position corresponding to the end of the near-mouth
bar and to the beginning of an increase in depth.
Geochemistry of Dissolved and Suspended Organic Carbon 95
station N
.... ~
~~ :g
~ ...,.... <::.
~
t-..
.;,. "" ...
.;,.
...,
...
~ ~
..... ~ ~ .... ~ ~
.... ~ ~ ~ ~ ~
0
20
a
-
..a
Q
g.
CII
40
•
60 •
80
a 50 100 150 200 250 JOO
Distance from tbe moutb, km
Fig. 43. Vertical distribution of particulate matter (mgll) at the profile "Amazon river mouth-ocean"
(March-April 1983).
It should be noted that we are speaking about the average position of boundaries and
zones, which may vary depending upon the tide phase and may move by tens of kilometres.
At the boundary between yellow and green waters we observe the nest stepwise change
of optical characteristics with decreasing values. The green water zones are characterized
by the further decreasing of suspension concentration and optical indexes (slackening,
dispersion, adsorption). Transition from green to blue waters is a smooth one.
Vertical distribution of the suspension on the section "Amazon mouth-ocean" is shown
in Figure 43. Comparing this data with the distribution of salinity (Figure 38), one may
note that the concentration of suspension in the surface increases from the values of
100-150 mg/l near the Amazon mouth to 300-700 mg/l in the zone of strong rolling of
bottom sediments, and then drops to 5-10 mg/l in waters with a salinity of 10%0. On
further increasing of salinity, concentration of suspension is gradually reduced to 1 mg/l
and lower. It is also obvious from Figure 43 that the bottom layer of water on the section
"Amazon mouth-ocean" is much more turbid than the surfacial one, which is bound up
with both rolling the surfacial layers of bottom sediments and with the deposition of
suspension from the surfaciallayer of waters.
Variations of suspension concentration in the Amazon estuary are, to a considerable
extent, bound up with processes of mechanical and mineralogical differentiation of sus-
pended material. The comparison of results of river and ocean water suspension granu-
lometric composition analyses shows that the Amazon suspension corresponds to pelite
and aleurite-pelite muds (Table 42).
The granulometric spectrum of oceanic suspension is characterized by the high content
of pelite fraction (less than 0.01 mm); content of subcolloid substances (particles less than
96 Chapter 3
Table 42. Granulometric composition of river and ocean suspension in the Amazon basin and estuary (Monin
et ai., 1986).
Granulometric type
Station Content offractions, in % (by Bezrukov's and
Location of stations number >0.1 mm 0.1-0.05 mm <0.01 mm <0.001 mm Lisitzin's
classification)
0.001 mm) is higher than that in river suspension, and the quantity of aleurite particles in
it is less than in rivers.
The main part of the suspension consists of clay minerals, kaolinite and montmoril-
lonite prevailing. The share of heavy fractions (sp. gravity exceeding 2.9) is very low.
In the Amazon they are represented by amphibole-pyroxene-epidote-zirconium associ-
ations; there are also black non-transparent minerals. The quantity of heavy metals is
sharply decreased in the Amazon suspension. Such minerals as zircon, epidote, pyroxene,
hornblende, garnet, rutile and tourmaline were met in the form of single grains, and the
recorded quantities of black ore minerals were more impressive (Monin et at., 1986).
The distribution of nitrates in the Amazon estuary is characterized by the following
peculiarities: considerable variations in fresh waters, maximum at a water salinity of
5%0, a sharp drop of concentration in the salinity range of 10-15%0 (as a result of active
assimilation by phytoplankton) and comparatively low and non-varying concentrations at
salinities of 15%0 and more (Figure 44).
The behaviour of phosphates in the Amazon estuary is in many cases similar to that of
nitrates, but it is characterized by a great spread of data on the diagram for their relation-
ship with salinity (Figure 45), as well as a relative enrichment of salt edge waters with
phosphates. The balance between dissolved and suspended material showed that almost
all phosphorus, evidently, passes into solution in salt wedge waters or on bottom sediment
surfaces (Edmond et at., 1981). Suspended phosphorus was found in high concentrations
when salinity is about 10%0 and enrichment of the suspension with phosphorus is the
greatest compared to other macro-components (Sholkovitz and Price, 1986).
Geochemistry of Dissolved and Suspended Organic Carbon 97
.
..
12 •
f •
8
•
{ 4 ••
u
a a •
• • •••• !A
•
I .;, :n===~==~~===~
~ 12
...t··.· •
8
.
•
•~ •• :•
o ....... :. :.. :.:••
o 10 20 30 5,%0
Fig. 44. Dependence of nitrates content from salinity in the Amazon estuary (data of Institute of Oceanology
expedition in 1983 and Edmond etal., 1981 (lower)).
1,0
• •
0,8 • ••
,.
I
." 0,6
...
.....
: -'
• ••
... ••
•
• •
J,; 0,* r·
~
• •
.... • •
One of the aims of our investigations in the Amazon estuary and neighbouring regions of
the Atlantic was to determine the regularities of dissolved and particulate organic matter
behaviour as a function of the salinity of the waters. As it was already noted, deviations
from simple dilution of river organic matter with oceanic waters may be caused by both
physico-chemical and biological processes.
98 Chapter 3
Cd, mg/I
c P, mg/I
5
o
z
o 20 30 5,%0
Fig. 46. Dependence of Cd and CP concentrations on salinity in Amazon estuary (Artemyev and Shapiro.
1987). 1. Field (natural) data; 2. experimental data.
Table 43. Organic carbon in samples for the experiment on mixing of the Amazon and Atlantic waters
(Artemyev and Lazareva, 1986).
Table 44. Variations of concentrations of dissolved organic carbon (ct), "stable" ct (~t), "labile" ct (ct)
and humic acids carbon (CHA ) in the case of mixing of the Visla river and the BaItic Sea waters (Pempkowiak,
1985).
Salinity ct ~t ct CHA
Object of research %. mgll % mgll % mgll % mgll %
River water 8.6 100 6.1 100 2.5 100 3.8 100
River + sea water 3 2.6 104 3.5 92
River + sea water 5 7.4 86 5.0 82 2.4 96 3.0 80
River + sea water 7 2.3 91 2.5 66
River + sea water 9 6.6 77 4.2 70 2.2 88 2.3 60
0.0-27.7%, average 10.8%, of the total content of organic carbon in the sample. Since the
experiment data correlates satisfactory with the results of natural observations (coefficient
of correlation is 0.7-0.8) one may prove that the process of floccule formation takes place
not only in the case of artificial mixture between fresh and salt waters, but also under
natural conditions.
Our experimental data on the mixture of waters of the Amazon and the Atlantic cor-
relate well with the results of the experiment on mixing waters of the Visla river and the
Baltic Sea (Table 44), where it was shown that more than 20% of Cd of mixed water
100 Chapter 3
and sea waters are transformed into CP (basically into humic substances). Labile organic
matter and "non-humic" organic matter, resistant to decomposition and mineralization,
flocculate in small quantities, 12 and 7% respectively (Pempkowiak, 1985).
3.2.2.2. Peculiarities ofcJ and cP Behaviour under Natural Conditions and "Losses"
of River Organic Matter in the Estuary
To estimate the reliability of the character of Cd and CP behaviour in the case of mixing
of river and sea waters ("conservative", "non-conservative") the data, obtained during
natural observations, was subjected to "smoothing" by means of the method of "moving
average" by 3 and 5 points (Artemyev and Shapiro, 1987). It is obvious from Figure 46
that the resulting curve of Cd distribution against salinity in the studied waters does not
correspond to the line of simple dilution, the equation of which, obtained by the method
of least squares, has the form Cd = 4.46 - 0.0788.
To prove the significance of deviations, we performed statistic estimations of zero-
hypothesis about the fact that natural data lie on the straight line of sample dilution.
Calculations, performed by the method of Livovsky (1982), showed that the hypothesis
on simple dilution may be rejected with 95% confidence probability. Thus, ideas of
"conservative" behaviour of dissolved organic matter in the regions of river and sea water
mixture (Sholkovitz, 1978; Fox, 1983; Mantoura, 1986; Mantoura and Woodward, 1983;
Michaelis et at., 1986) are not confirmed. In addition, the analysis of actual data, included
in the above-mentioned papers, does not permit us to agree with the authors' conclusions
completely, due to a whole number of reasons (unequal study of river-sea sections, absence
of definitions of CP parallel to those for Cd, insufficient sampling for reliable interpretation
of the obtained data, quantity of taken samples of water on sections, etc.). As it was shown
by our investigations, as well as by the data obtained by a number of foreign researchers,
conservative behaviour of dissolved organic matter in estuaries may take place, but this,
more likely, is an exception, and not a rule. Content of Cd and CP as the distance from
the Amazon mouth to the ocean generally decreases on average from 5.0 to 2.0 mgll and
from 6.7 to 0.4 mgn respectively (Figure 46).
At the initial stage of mixing of waters (within the range of salinity of less than 1%0
to 12%0) higher and lower concentrations of Cd and CP alternate. In this case, as a rule,
an increase of Cd concentration is accompanied by a CP concentration decrease, and vice
versa. To quantitatively estimate the observed fluctuations in organic matter behaviour at
different stages of water mixing and to clarify their nature, we performed calculations of
"losses" and "new formations,,2 of dissolved and particulate organic matter under natural
conditions, and compared the obtained data with the results of laboratory experiments.
Existing individual data on calculations of "losses" of dissolved substances, transported
by river run-off to the ocean are based on the one-dimensional model (Boyle et al., 1974;
Officer, 1979), suitable for the estuary, in which diffusion flow of substances is considered
to be directed by axial currents. Such a model is unlikely for the Amazon estuary waters
2Conventional terms, actually meaning ttansition of organic matter from one form into another one under
the action of physical, chemical and biological processes [V.A.].
Geochemistry of Dissolved and Suspended Organic Carbon 101
Table 45. Integral losses of dissolved (cd) and particulate (CP) organic carbon in the region
of mixing waters of the Amazon and the ocean, depending upon their salinity.
0.05 8 0.05 10
2 0.12 0.12 0
3 0.37 18 0.35 17
4 0.62 25 0.52 31
5 0.90 21 0.70 46
6 1.38 10 0.93 54
7 2.18 II 4 1.39 61
8 2.92 0 2.18 II 68
9 3.77 0 2.92 71
10 4.48 2 3.77 78
11 5.11 5 4.48 77
12 6.05 III 16 5.47 III 73
13 7.38 27 7.09 73
14 8.58 36 8.99 75
15 10.04 34 11.59 IV 79
16 11.40 30 14.14 79
17 12.88 IV 21 19.03 75
18 14.88 12 19.03 75
19 16.68 16 21.10 V 78
20 12.50 18 23.34 82
21 20.17 V 23 25.52 83
22 21.74 21
23 23.65 23
24 25.59 25
as Guyana Current results in an "elongation" of the mixed water plume along the shore
(Gibbs, 1970) and, consequently, the transverse diffusion intensity will considerably
exceed that of the longitudinal one.
We proposed the stationary quasi-one-dimensional model, taking into account the
advective streams, and streams predetermined by turbulent diffusion transversed to the
current (Artemyev and Shapiro, 1987).
Integral "losses" of river dissolved and particulate organic matter depending upon the
salinity are shown in Table 45 and in Figure 47. Figure 48 contains "differential losses"
of organic matter. It is obvious that "losses" for dissolved and particulate organic matter
(positive values Q) alternate with the "new formation" of organic matter.
Depending upon the direction of these processes, five zones may be separated in the
area of the Amazon and the ocean water mixing. The first zone (waters with salinity of
102 Chapter3
o I ! II !5 III 1f! IV 1~ V 20 5, %0
Fig. 47. Integral "losses" of river organic matter (I) and particulate organic matter (2) in a process of mixing
of Amazon river and ocean waters (Artemyev and Shapiro, 1987).
1,2
1,0 '9
·
0,8 •
"
••
..
~ o
rij
"- 0,6
0
·•••
o
0,4 •
~ 1 2
<,,"... ::'~;'t===o4-!h~~.","-"
0,2
0
IIV 8 ~ 16 20" 2115.%0
-qz
Fig. 48. The intensity of differential "losses" of dissolved organic matter (I) and particniate organic matter (2)
in the Amazon estuary (Artemyev and Shapiro, 1987).
0.01-1 %0) is characterized by "losses" of both dissolved and particulate organic matter (as
a result of transformation into suspended form in processes of flocculation, deposition on
the bottom, etc.) reaching respectively 25% (first maximum of dissolved organic matter
"losses") and 54% from the initial river organic matter. 3
3Here and subsequently the quantity of relative losses (%) calculated following Boyle et al. (1979) is shown.
Geochemistry of Dissolved and Suspended Organic Carbon 103
Fig. 49. The distribution of chlorophyll (mglm3) at the surface of Amazon estuary waters in a season of high
water (Monin et a/., 1986).
The second zone (waters with salinity of 1-4%0) is characterized by "new formations" of
dissolved organic matter ("losses" decrease to zero) also in this case "losses" of particulate
organic matter are still increasing to 78% in waters with salinity of 4%0. The main
source of dissolved organic matter in this zone is, evidently, organic matter supplied from
suspension during desorption. Additional sources of organic matter for dissolved and
particulate organic matter in the waters, studied by us, might be the primary production
of phytoplankton. However, as it was shown by optical studies carried out during our
expedition (Monin and Kopelevich, 1983), the favourable conditions for development of
phytoplankton in the Amazon estuary are created in transparent ("green") waters with
salinities exceeding 15%0, where the maximum of chlorophyll "a" consumption was
determined (Figure 49).
In the third zone, from 4 to 10%0, "losses" of dissolved organic matter increase again
(to 36%), but at the same time losses of particulate organic matter decrease. As it was
shown by comparing the data of natural observations and experiments, one of the sources
of particulate organic matter in this case is the flocculation of dissolved organic matter. As
is obvious, the process of forming organic floccules proceeds at all stages of mixing, from
104 Chapter 3
slightly saline to oceanic waters, but it proceeds most intensively in waters with salinities
of7-8%0.
Since the data of the experiment correlate satisfactory with the results of natural ob-
servations, it is possible to prove that the process of forming of floccules takes place not
only in the case of artificial mixing between fresh and salt waters, but also under natural
conditions.
Suspended organic particles, formed as a result of flocculation, may total up to 60% of
particulate organic matter. It is obvious from Figure 47 that "losses" of dissolved organic
matter in the third zone are not completely compensated by new formation of particulate
organic matter. Evidently, part of the suspended particles formed as a result of flocculation
are lowered to the bottom and buried in bottom sediments.
In the fourth zone (waters with salinity from 10-15%0) we observed again an increase of
dissolved and a decrease of particulate organic matter, probably as a result of desorption
processes. Finally, in the fifth zone (water salinity exceeding 15%0) the processes of
transformation of organic matter are practically completely levelled.
Calculations of losses of river organic matter in the area of mixing of the Amazon and
the Atlantic waters show that 75% of river dissolved organic matter and 20% of particulate
organic matter are finally supplied to the ocean.
CP, mg/I
Chi, JI.gll
1 <1
0
0 •
20
0<1
-
"0 ~1-J
1IIlIIIlII3-5
60
80 _>70
Fig. 50. Vertical distribution of cd, cP and chlorophyll at the profile "Amazon river mouth-river" (Monin et
al., 1986).
(Monin and Kopelevich, 1983). Evidently, the high content ofed in "green" waters of the
Amazon estuary is bound up with development of phytoplankton (Figure 46).
Thus, the favourable conditions for the development of phytoplankton in the estuary of
one of the largest rivers of the world, i.e. the Amazon, are possible only at a considerable
distance from the river mouth. Near the river mouth under conditions of quick and
intensive mixing of waters, plankton communities have no time for growth and therefore
are forced to breed only far away from the river mouth, where mixing of waters decreases
(Eisma, 1988).
106 Chapter 3
o~
-20 ,.... -1 Amazon R
• 2 tributaries
.3 bottom
0
00,
i
00.
•
0'" surface •••
-25 f-
-
~
.~~
-30 -... ...
• •• •
I I I ... I
PP/PPmax
1;.---
o 10 20 30 S, "I""
Fig. 52. Dependence of the relation PP/PPmax on salinity in estuaries (Eisma, 1988; Cadee. 1982).
Figure 51 illustrates the variation of 613 C for CP from the main bed and tributaries
of the Amazon. where these values average 29.3%0. to the Amazon estuary where the
values 613 C increase to 18%0 which is typical for sea plankton. The estuarine waters
which are most favourable for the development of phytoplanktonic organisms may be
located at varying distances from the river mouth. In this case, the determining factor is
the transparency of waters, their accessibility for penetration of sun light, but not high
concentrations of biogenous elements (Eisma, 1988). As it is obvious from Figure 52,
high values of primary production may be met in both the medium part of the estuary (the
Amazon) and at its periphery (Zaire river) and outside its boundaries (Ems river, Rhine
river).
Geochemistry of Dissolved and Suspended Organic Carbon 107
11,0-
_15
~M
.l' '---.,.
/"-
10,0
Fig. 53. Sampling stations and salinity in the area of Kuban river and sea waters mixing (April-May 1979)
(Artemyev et al., 1982).
3.2.3. CONCLUSIONS
The results of experiments in the mixing of the Amazon and ocean waters and data of
natural observations in the Amazon estuary showed that the process of dissolved and
particulate organic matter formation as a result of flocculation is present at all stages of
water mixing, but most actively in waters with salinities of 5-10%0.
Calculations showed that Cd behaviour in the studied waters depending upon the salinity
does not correspond to the line of sample dilution, and is of a "non-conservative" character
as a result of its transformation into the suspended form and back into dissolved one at
various stages of river and ocean water mixing the under effect of physico-chemical
processes (flocculation, adsorption-desorption).
By means of the model worked out by us we made an estimation of "losses" of river
organic matter in the case of mixing of river and ocean waters: for dissolved organic
matter 25% and for particulate organic matter 80%.
108 Chapter 3
30
O.r-----------------t-----------~~~~
Temryuk Bay
~
...
....
• :.-: 2
D•
o
o.
••
00
a
Fig. 54. Distribution of particulate matter at the area of Kuban river and sea waters mixing under south-eastern
(up) and north-western (down) winds (Shulgina, 1955). 1. River water; 2. mixed river and sea water; 3. sea
water.
During our investigations in the Temryuk Bay in the region of mixing of the Kuban river
and sea waters (Artemyev et al., 1982) we observed clear change from fresh (less than
1%0), to mixed (1-11 %0) and salt waters (11 %0 and more) on the surface of the water area
studied (Figure 53). Such a distribution of salinity in the surface water (Figure 54) of the
studied region was observed in the case of south and south-eastern winds. In this case
waters of the Kuban river are moved towards the bay for 1-2 km (Figures 53 and 54).
The distribution of nitrates and phosphates in the studied area, dependent upon the
salinity, is characterized by the decrease of their content by passage from river to sea
waters (from 50 to 5 mg/I). High concentrations of nutrient salts in the Kuban mouth
might stimulate active growth of organic matter by organisms such as phytoplankton as
was observed in the Temryuk Bay (see next section). But the activity of phytoplankton in
the Temryuk Bay at the early stages of mixing of river and sea waters (as in the Amazon
estuary) is prevented by the water turbidity (Figures 55 and 56). Due to this fact the
primary production value does not reach high values here, but shows maximum values in
the middle part of the river and sea water mixing area, when the water salinity is equal to
7%0. Concentration of suspension in these waters is essentially lower by a factor of three
in comparison to the near-mouth region when the waters become more transparent and
accessible for penetration of sun light.
The value of primary production decreases noticeably with an increase of the distance
from the shore, which may be caused by the deficit of nutrient salts, but as the boundary
with sea waters this value sharply increases. The increase of phytoplankton primary
production at the boundary of river and sea waters is related to the mass development of
phytoplankton, observed in the region of hydrofronts. In the same boundary waters an
increase of "production" of bacteria was discovered (Ivanov, 1967).
Content of suspension in waters studied change from 11 to 66 mg/l and averages
27 mg/l, decreasing towards river mouth-sea. The leading factor of terrigenous material
sedimentation at the premouth shelf of the Kuban river is the wind regime. The quantity
and propagation area of suspended material of the river depend upon the intensity and
direction of wind (Figure 54). A considerable part of suspension (about 60%) is deposited
in the mouth area of the Kuban (Table 46), 10-20% of terrigenous pelite material being
deposited as a result of coagulation (Simonov, 1969).
110 ChapterJ
a n
·ZI
20~
11
zoo
flo
;,
Fig. 55. Distribution of primary production (mgCJllday) in the area of Kuban river and sea waters mixing
(April-May 1979).
Table 46. Sedimentation of terrigenous material fractions (min t) into delta and
in the coastal waters near Kuban R. (Kbrustalev, 1989).
•17
80.0----~i/.
Ie
..
--......;;;~------'
I ~4ii.O .,
....
---~.1
Fig. 56. Distribution of particulate matter in the area of Kuban river and sea waters mixing (mgll) (April-May
1979).
Content of organic matter in the area of mixing of the Kuban river and Temryuk Bay waters
varies from 0.23 to 1.62 mgn and averages 0.74 mg/I. The share of particulate organic
matter in suspension is equal to 1.6-10.7%, average 4.9%, i.e. suspension is represented
mainly by mineral components. Distribution of organic matter depending upon the salinity
is characterized by three maxima: a near-mouth maximum, a maximum in the central part
of the river and sea water mixing region, and a maximum at the boundary with sea waters.
As it is obvious from Figures 55 and 57, distribution of CP and primary production is
similar, which indicates the determining contribution of phytoplankton to the delivery of
particulate organic matter to the studied waters.
112 Chapter3
• 12
.11 I!i~' 1:';:'
\:.::J~
.19
Fig. 57. Distribution of cP (mgll) in the area of Kuban river and sea waters mixing (April-May 1979).
One of the important problems of estuarine biogeochemistry, which has been a subject
of attention over the last few years, is the behaviour and interaction of organic matter and
micro-elements in the river-sea system. There is a lot of evidence for the deposition of
dissolved and colloid micro-elements during the process of water mixing in estuaries in
cases of both low salinity and salinity of 20%0 (Gordeev, 1983; Anikeev, 1987; Anikeev
et al., 1985; Martin et al., 1993). The preferable mechanism of transition of organic
matter and micro-elements from the dissolved into the suspended state is the formation
of floccules "iron oxide-organic matter" and connection with such aggregates of other .
micro-elements (Boyle et al., 1977; Bewers and Yeats, 1981). A number of works proves
similarity in behaviour of metals and organic matter, especially humic substances, in areas
of mixing of river and sea waters, where it has been shown that flocculation of metals and
humic substances takes place (Boyle et al., 1977; Eckert and Sholkovitz, 1976; Sholkovitz,
1976, 1978;Sholkovitzetal., 1977, 1978).
Geochemistry of Dissolved and Suspended Organic Carbon 113
a ·27
.,&
·,1
Fig. 58. Distribution of particulate Cu (mgll) in the area of Kuban river and sea waters mixing (May 1979).
• 28
.16
.12
.18
.19
.10
.s
Fig. 59. Distribution of particulate Ni (mgll) in the area of Kuban river and sea waters mixing (May 1979).
(Artemyev et at., 1982) and the southern part of the Riga Bay (Artemyev and Gorshkov,
1982; Demina and Artemyev, 1984).
The study of micro-elements in suspension at the section "mouth of Kuban river-
Ternryuk Bay" showed that their concentration, as well as CP and primary production,
decreases in direction of the river-sea. However, on the background of the general trend
to decreasing content of micro-elements, the maximum concentration of copper, nickel
and cadmium is clearly separated in the central part of water intermixture area at the
salinity of 5.5-7.0%0, i.e. in the area where high values of primary production and CP
(Figures 58 and 59) were found. If we suppose that the enrichment of suspension with the
above-mentioned micro-elements is bound up only with the activity of primary producers,
concentrating micro-elements in their tissues in process of their development, one should
expect an increase of concentration of suspended micro.-elements at the boundary of river
and sea water intermixture area. Just here we noted the maximum (third one) of primary
production value. However, the content of micro-elements is steadily decreasing seawards
Geochemistry of Dissolved and Suspended Organic Carbon 115
after the maximum concentrations in the central part of the waters intermixture region.
Thus, the residues of tissues dying or dead phytoplankton organisms are not the only
reason for high concentrations of micro-elements in suspension in the central part of
water mixing areas. Since the noted maximum content of micro-elements in suspension
is located several kilometres from the river mouth (where their concentration is lower),
the river run-off also cannot be the reason for that extreme.
As it was noted earlier (Demina et at., 1973; Sholkovitz et ai., 1976, 1978), in the case
of intermixture of river and sea waters micro-elements are removed from the dissolved
into the suspended state as a result of flocculation of colloid particles. Apparently, extreme
concentrations of micro-elements in the area of intermixture of waters of the Kuban river
and Azov Sea area also primarily caused by flocculation.
The contribution of phytoplankton primary production to the deliver of micro-elements
into suspension of water intermixture area takes place too, although it plays a secondary
role in the studied waters.
3.3.3. CONCLUSIONS
I. While water salinity is increased, the content of phosphates and nitrates is progressively
decreased from 50 and 25 mg/l respectively in the Kuban river mouth to 20 and 5 mg/l in
sea waters.
2. Distribution of primary production of phytoplankton in the area of river and sea
water intermixture is characterized by the presence of 2 maxima: in the central part of the
river and sea water intermixture area (waters with salinity of 5-6%0) and on the boundary
with sea waters, in the region of hydrofront (waters with salinity of 11 %0).
3. Content of CP and suspended micro-elements (copper, nickel) is increased in the
direction river-sea but it is characterized by the presence of a number of maxima and
minima, bound up with the physico-chemical (flocculation, adsorption-desorption) and
biological processes (primary production of organic matter by phytoplankton). The sharp
increase of content of CP and micro-elements in the central part of the water intermixture
area is caused by activity of primary producers, as well as by flocculation of dissolved
organic matter and micro-elements bound up with it.
4. Behaviour of particulate organic matter and micro-elements of suspension (copper,
nickel) dependent upon the salinity in the studied waters is of similar character, which
testifies to their migration in a form of organic matter-metal complexes.
3.4. Dissolved and Suspended Organic Carbon and Primary Production in Non-
Stratified Estuary (The Taganrog Bay)
In October 1980 we performed biochemical studies at the section "Don river mouth-
Taganrog Bay" (Figures 60 and 61). One of the typical peculiarities of waters in the
studied region was the absence of any kind of stratification along the whole section river-
116 Chapted
~:~~~ ~==~::--
o '" 5 6
- - - . Surface layer (0 - 0.5 m)
7 8 9 10 11 5,%0
- - - 0 Bottom Layer (0.5 m from bottom)
Fig. 61a. Hydrochemical and biogeochemical components at the profile "Don river mouth-sea" (October
1980).
Geochemistry of Dissolved and Suspended Organic Carbon 117
::::en
Cj
is
:;,.
0
Po
I
Po
::::en
1
Cj
S
M
I
~I
Z
-~
0 5 6 7 8 9 10 11$,%0
Fig.6lb.
sea (Figure 61). Good intermixture of the whole water mass caused practically the same
distribution of the majority of considered components in surface and bottom waters.
The values of pH in the direction river-sea increase from 7.9 to 8.1. The distribution
of oxygen and biogenic elements (phosphorus, nitrogen and silica) is characterized by the
peculiarities, typical for the mouth shelf of the Don river and Taganrog Bay (Simonov,
1969): a decrease in concentrations by the transition from fresh to salt waters, sharpest
in waters with salinities of 0.5 to 4%0. Activation of processes of primary production of
organic matter by phytoplankton organisms takes place in the same waters in the early
stages of mixture of river and sea waters at relatively low turbidity of waters (concentration
of suspension is about 10 mgll). Using the data from Khrustalev (1989), it is seen that
diatomic complexes are mainly developed in October in the Taganrog Bay. This causes
a sharp increase of primary production value, by more than an order compared with river
waters, in waters with a salinity of about 4%0 (Figure 61). Thus, a decrease of concentration
of nutrient salts in the area of contact of river and sea water is caused to a considerable
extent by their consumption by phytoplankton. The further decrease in the intensity
of organic matter produced by algae towards the sea (from 750 to 70 mgC/m3/day) is
bound up with the shortage of biogenic nutrient salts, and an increase of concentration
of suspended particles in water, which nevertheless allows for the upkeep of primary
118 Chapter 3
Si. /1g/l
7000~'
5000
3000 ..... 1
1°°°L~_ J
.oorA
500 I'
500
400
1
100~/
~
~~.
•~
0 11 5 5 7 8 9 10 S,%o
Fig.61c.
..
6 ~_C_d_._~__m_g/~.~
! . --.......--.~
J
2
1
o 1 2 J If 5 6 7 8 10 115, o/c,o
Fig.61d.
production at the level of70-100 mgC/m 3/day. When approaching the boundary with sea
waters, the primary production value decreases to 50 mgClm3 /day.
Geochemistry of Dissolved and Suspended Organic Carbon 119
,t . '
25
io ....···........
JO·
~.
~'
POM, 20
1,0 _
05
_. • •• :;:.-:-..........- .
••• , ", 15
, CP .......... -!--C P
I: - . . . . . .___ -.Ill 10
L_--o-~~ 5
o ~~~~--~--~~~~--~--~~--~~o
10 Cd/cp
...
~~
8 ~ "' .. ..."", ....
6 ~ ~
.~
...._____ .... _- ••.-...... 'A-._"l6,
"o
~
2
1 2 5 6 7 8 9 10 71 12 S,%o
J "
Fig. 61e.
18
cg. % CP
12
6
C~. % Cd
35
25
15
0
" 5
Fig.6lf.
6 7 8 9 5,%0
As it is obvious from the example of the Taganrog Bay, the river run-off may have a
fundamental effect on the primary production value in the area of intermixture of river
and sea waters, and is one of the factors controlling primary production in these waters.
The concentration of suspension within the studied period in the Taganrog Bay varied
from 11 to 53 mgll with an average of 25 mgll. When moving from the river mouth to
the sea the content of suspension was increased step by step, from less than 4 mgll in the
river mouth to several tens of mgll in the sea part of section. An increase of the content
120 ChapterJ
Suspension, 106 t
Month Inorganic Organic' Sum total
of suspension in the area of intermixture of the waters of the Don river and Taganrog Bay
(compared with river waters) within the studied period is bound up with its supply to the
water as a result of rolling of the surfaciallayer of bottom sediments under conditions of
intensive wind mixing of the whole 3~ m thick water mass. The share of organic matter
in the composition of suspension is equal to 5.9-21.5%, averaging 11.2%, which is also
confirmed by the data presented by Khrustalev (Table 47).
Content of Cd and CP in the studied waters is equal respectively to 3.22-8.5 mgll, average
5.4 mg/l and 0.7-2.3 mg/l, average 1.3 mg/l (converting into particulate organic matter
- 1.3~.2 mgll, average 2.4 mgll, Figure 61). The dissolved form of organic matter
predominates in waters of the Taganrog Bay (74.0-88.6%, average 80.9%). The basic and
most labile component of particulate organic matter in the Taganrog Bay and the Azov
Sea is detritus, represented by residues of planktonic plants (Table 48).
A specific group is formed by organic-mineral aggregates, consisting of clay minerals
and products of heavy decomposition of vegetable residues. The content of living organ-
isms in particulate organic matter is extremely low. As it is obvious from Table 48, the
particulate organic matter concentration is usually at a maximum in regions adjoining the
Don mouth. The effect of river run-off is revealed in the. increase of allochthonous genesis
vegetable detritus content in the suspension, as well as in high concentrations of nutrient
salts (Figure 61).
Geochemistry of Dissolved and Suspended Organic Carbon 121
Table 48. Seasonal variation of particulate organic marter composition in the Taganrog Bay of the Azov
Sea in 1911, mg/l (Khrustalev et ai., 1982).
Taganrog Bay:
'2 eastern 0.14 1.21 1.41 0.04 0.04 3.41 4.96
0..
< central 0.04 1.48 1.52 0.03 0.00 1.29 2.84
western 0.03 0.16 0.19 0.03 0.00 0.96 1.18
sea 0.01 0.38 0.39 0.05 0.01 1.10 1.55
Taganrog Bay:
eastern 0.45 2.64 3.09 0.11 0.02 0.12 10.00
.E:-
~ central 0.36 0.81 1.11 0.10 0.00 5.22 6.49
western 0.01 1.45 1.46 0.08 0.01 3.54 5.09
sea 0.03 0.63 0.66 0.11 0.03 2.08 2.88
Taganrog Bay:
-I
~
eastern
central
0.81
0.24
1.32
0.63
2.13
0.81
0.01
0.03
0.04
0.01
2.68
1.92
4.86
2.83
0
western 0.05 0.62 0.61 0.02 0.00 0.80 1.49
sea 0.04 0.18 0.82 0.04 1.09 1.95
However, behaviour of organic matter in the Taganrog Bay may be of different character,
since concentrations of dissolved and particulate organic matter in surface and bottom
layers of water, and distribution of these components by the section river-sea are influenced
by water hydrodynamics. So, during the period of our investigations when the whole
thickness of water from the surface to the bottom was mixed well, i.e. under conditions
of "non-stratified" estuary distribution of Cd and CP on the section "river mouth-sea" was
of "calm" type in the Taganrog Bay, without clearly expressed extremes. Nevertheless,
in the case of passage from fresh waters to waters of intermixture, CP more than doubled.
Evidently (Figure 61), this is bound up with a sharp increase of primary production value
in these waters.
It is obvious from Figure 62, that the content of particulate organic matter, as well as
the suspension and biomass of phytoplankton is subjected to noticeable variations within
24 hours. As is obvious, there is no direct connection between organic matter and biomass
of phytoplankton, which can be explained by the fact that the majority of particulate
organic matter is presented by "mineralized" organic matter (Table 48).
Behaviour of Cd and CP in the near-mouth section ofthe area of intermixture ofthe Don
river and Taganrog Bay waters are mutually opposite: the increase of CP is followed by
122 Chapted
Surface layer
1 2 J 1 2 3 123
75 25 15 r-:::--:--...... 75 25 15'-s""u-m-m-er--' 75 25 15 r-"7A-u t:""u-m-n--'
60 20 12 60 20 12 60 20 12
45 15 9 "-5 15 9 liS 15
JO 10 6 30 10 6 30 10
15 5 3 15 5 3 15 5
o o o
Bottom layer
Fig. 62. The daily dynamics of particulate matter (I) content (mg!l), phytoplankton biomass (2), glm 3 , and
particulate organic matter (mg!l) in Taganrog Bay waters (Khrustalev, 1989).
Cd decrease. This is also testified by the character of variation of Cd/CP ratio at the section
river-sea: in waters with salinity of 0.5-4%0 the ratio Cd/CP more than halves, from 9.5
to 4.5, while in waters with higher salinity this value does not vary with an increase in
distance from the shore (Figure 61).
The most probable reason for Cd concentration decrease at the initial stage of mixture of
river and sea waters, in waters with salinity of 0-4%0, is flocculation of dissolved organic
matter and its transformation into the suspended form. In this case the decrease of Cd
content cannot be bound up in any way with the activity of primary producers. On the
contrary, in these waters, as it was noted earlier, the processes of organic matter production
by phytoplankton, were activated, as well as processes of discharging of dissolved organic
matter into water.
Composition of organic matter (dissolved and particulate organic matter) in waters of
the Taganrog Bay is noticeably changed when moving away from the Don mouth to the
sea, which was very noticeable in the curves of the distribution of dissolved and particulate
carbohydrates on the section river-sea.
Since the main source of natural organic matter in the studied waters over the entire
length of the section river-sea is diatomic plankton, changes in composition of dissolved
and particulate organic matter may be, primarily, bound up with vital activity of planktonic
organisms. It follows from Figure 61 that at the early stage of intermixture of waters in the
Geochemistry of Dissolved and Suspended Organic Carbon 123
Taganrog Bay during the period of active production of organic matter by phytoplankton,
the content of carbohydrates in dissolved organic matter composition is increased consid-
erably, from 17.5% in fresh waters to 38% in waters with a salinity of about 4%0. Their
content decreases again with the increase of distance from the shore.
It is necessary to pay attention to the fact that the character of variation of relative
content of dissolved carbohydrates in the composition of dissolved organic matter (cg,
% of Cd) and primary production on the section river-sea coincide almost completely.
Consequently, primary production is the main source of dissolved carbohydrates in the
studied waters. As for the variation in the dissolved and particulate organic matter compo-
sition on the section "Don river-Taganrog Bay", the content of dissolved carbohydrates in
dissolved organic matter varies from the particulate carbohydrates content in particulate
organic matter in a contrasting way. The obtained results of studying the carbohydrates
in the area of intermixture of waters of the Don river and the Taganrog Bay correlate with
the data (Laane and Ittekkot, 1985) of dissolved carbohydrates concentration (of the same
order) in the Ems river (average 18.4% of dissolved organic matter).
3.4.3. CONCLUSIONS
Content of Cd and CP in the studied waters average respectively 5.4 and 1.3 mgn. Dissolved
forms of organic matter prevail and total 74.0-88.6%, with an average 80.9% of the sum
of dissolved and particulate organic matter. The share of particulate organic matter in the
suspension composition is equal to 5.9-21.5%, average 11.2%.
Under conditions of good stratification of waters in the bay (as a rule in summer
and autumn seasons) increased concentrations of particulate organic matter are seen in
the waters adjacent to the Don mouth and bound up with the delivery of particulate
organic matter with river run-off. In the case of intensive mixing of waters by wind,
and the absence of water mass stratification, the behaviour of dissolved and particulate
organic matter is determined by physico-chemical (flocculation) and biological (primary
production of organic matter by phytoplankton) processes in the area of intermixture of
river and sea waters.
Variety of dissolved and particulate organic matter composition on the section river-sea
is bound up with the functioning of phytoplankton, which play the main role in delivery
of dissolved carbohydrates into water.
The main feature of the hydrochemical regime of the southern part of the Riga Bay is the
essential refreshing of sea waters with river run-off. The Riga Bay includes four groups
of sea water classified by the degree of refreshing: highly refreshed (salinity up to 3%0),
124 ChapterJ
a b
.5,72
• •
•
Fig. 63. Distribution of salinity in a surfacial (a) and near-bottom (b) layer of Riga Bay waters (Artemyev et
al., 1981).
-15,0
.1.,D
10,0
5,0
2,$
/f0 ,.. ;: -. &~2,O
ob ',0_ >
~2V~-'- b,O [
~ i·
eli ::. ~
1;;'
/f0 ~
.Q.,
"U s,o
I
~
~
{;j
g
~
C
~
§
1)'
t !f0 ~
Fig. 64. Vertical distribution of TO, salinity, Cd and CP at profiles river-sea in the southern part of the Riga Bay in July 1978
t
(Artemyev et aI., 1981), tv
Ul
....
~
Cd, bottom CP, bottom PP
~
~
....~
• ""
•
•
I I
1111
,.. UI CJ\ v
I'" I
I II
~~~i
PM Cd, surface CP, surface
Fig. 65. Primary production (mgCIm3/day), cP, Cd and particulate matter (e), mg/l, in a surfacial and near-bottom layer of the southern part of the
Riga Bay waters (Artemyev et ai., 1981; Dyomina and Artemyev, 1984).
Geochemistry of Dissolved and Suspended Organic Carbon 127
Organic carbon in the studied waters is mainly in dissolved form (85-98%, average 94%
of the sum of Cd and CP). Content of Cd varies from 3.1 to 18.1 mg/l and averages
7.2 mg/1. The highest content of Cd was found in refreshed waters in the Daugava river
mouth and bound up with the supply of organic matter by river run-off (Figure 65). The
area of propagation of refreshed waters, enriched to the maximum extent with organic
matter of river origin is limited within a narrow area, propagating from the Daugava river
mouth mainly to the north-west (Figure 63). It should be noted that a spot of higher
concentrations of Cd (10-15 mg/l), due evidently to contamination, was found in the
north-east part of the studied water area on the background of low Cd concentrations and
outside the zone of river run-off effect.
Cd is distributed vertically in accordance with the water stratification (Figure 64). So,
for example, in the Daugava river mouth the thickness of the upper layers of water with
high concentrations of Cd (more than 7 mg/l) regularly decreases in the direction from
the shore towards the bay, edging towards water surface approximately in the same places
where the boundary of poorly refreshed waters pass. On section IV, where the effect of
river run-off is practically absent and all the studied thickness of waters is represented by
the most saline waters of the bay, Cd vertical distribution is, on the whole, characterized
by slightly varying values.
High concentrations of Cd as well as cP in the waters of the southern part of the Riga
Bay, some distance from the Daugava river mouth are bound up with the processes of
primary production of organic matter by phytoplankton organisms (Figure 65).
The study of dissolved organic "yellow" substance in the Daugava river mouth and in
the open part of the Riga Bay showed (Pelevina, 1980) that its relative concentrations are
equal to 3.6-6 m- I and 0.4-1.5 m- I respectively.
Evidently, the main source of these organic compounds is the river run-off. By the data
of Yurkovsky and Rugaine (1985) the highest concentration of dissolved coloured organic
matter (DCOM) (and Cd, by our data) was found in the region ofthe Daugava river mouth
(6.3 mg/I). For comparison, the bottom waters ofthe bay and surface waters ofthe Baltic
Sea contain about 1 mg/l of dissolved coloured organic matter. Dissolved and suspended
coloured organic matter are equal to 17-41 % of dissolved organic matter and 2-14% of
particulate organic matter respectively.
The composition of studied suspension includes 1.9-42.1 % of cP, average 15.3%, or 3.5-
76.6%, average 27.8% of organic matter. Thus, in the majority of samples a considerable
part of suspension is represented by mineral particles, mainly terrigenous (Pustelnikov,
1976). Distribution of particulate organic matter on the surface of the studied water
surface is similar to the distribution of primary production of phytoplankton (Figure 65).
The similarity of areas of high concentrations of Cd and primary production on the surface
of studied water area in the zone of transition from refreshed waters to sea water, testifies
128 Chapted
to the fact that considerable parts of CP in the area of mixture are characterized by
phytoplankton genesis. High concentrations of cP in surface waters in the region of the
Lielupe and Gauya rivers are bound up with the delivery of particulate organic matter with
river run-off.
Content of CP is, as a rule, decreasing with increasing depth (Figures 64 and 65).
However, high concentrations of CP were noted in some bottom samples of suspension,
which were not found in respective surfaciallayers of water. The source of this suspension
are waters, propagated from the open part of the bay towards the Daugava river mouth
(Figure 64). On the other hand, the high content of cP in surface waters of the region of
river and sea water intermixture is not accompanied by the same high concentrations of
CP in bottom layers (Figure 65).
This is bound up with the fact that processes of sedimentation in the stratified estuary,
which is the studied water area of the northern part of the Riga Bay, are subjected to
influence not only of hydrological factors (direction and velocity of currents, wind, etc.)
but also by different genesis of surface mainly refreshed waters, and bottom, mainly sea
waters. These peculiarities of the waters of the southern part of the Riga Bay determine
the direction of transportation and place of deposition of suspended organic particles on
the surface of bottom sediments.
High concentrations of CP in the zone of transition from refreshed (mixed) waters to
sea waters of the bay are accompanied with low concentrations of Cd (Figure 65). It is
possible to suppose that a part of the dissolved (colloid) organic matter coagulates during
mixture of refreshed and sea waters, increasing the content of particulate organic matter
with the formation of floccules. As it was obvious from Figure 65 there is a principal
difference in the behaviour of Cd in surfacial and bottom waters: maxima of Cd content in
surface waters corresponds to minima of concentrations of CP in bottom waters and vice
versa. This fact may also serve as indirect evidence of the presence of dissolved organic
matter flocculation process and its transformation into the suspended form during sea and
river water intermixture.
"Non-conservative" character of dissolved organic matter behaviour on the section
"Daugava river mouth-Riga Bay" is testified by the results of studying of dissolved
"coloured" dissolved and particulate organic matter (Figure 66). In this case, as considered
by Yurkovsky and Rugaine (1986), only a part of these components may be eliminated
from solution by flocculation. In the opinion of some authors, the character of the
behaviour of "coloured" dissolved and suspended organic matter dependency upon salinity
is determined by the concentration of organic matter in river water. Under comparatively
low concentrations of organic matter the relationship between dissolved coloured organic
matter and salinity is represented by a line which is virtually straight and dissolved organic
matter behaviour depends upon the law of simple dilution during mixing between river
and sea waters.
According to the data of Yurkovsky and Rugaine (1986) "losses" of dissolved organic
matter brought from the land totals up to 10% in the southern part of the Riga Bay.
Geochemistry of Dissolved and Suspended Organic Carbon 129
A 211-26.011.60
0,16 • 6-10.05.80
o 21-211.05.80
0,12
::::: o
en
e
,,; 0.08
u
0.011
6 '\ .6-10.05.80
~ 0 21-21#.05.80
~
::::::
2 '-;~~
Cl
6 0
-=U
~
6 • 111-18.10.82
0
2 J 5 6 S,o/••
Fig. 66. The content of particulate and dissolved "coloured" substances in surfacial waters of the Riga Bay
plotted against salinity (Yurkovsky and Rugayne. 1986),
a b
Fig. 67. Distribution of salinity (%0) in surfacial (a) and near-bottom (b) waters of the southern part of the Riga
Bay (Artemyev and Gorshkov, 1982).
Fig. 68. Particulate organic carbon in the southern part of the Riga Bay (Artemyev and Gorshkov, 1982).
Cut ppm
Fig. 69. Particulate Cu in the southern part of the Riga Bay (Arternyev and Gorshkov, 1982).
measurement of phytoplankton primary production value. But the data obtained earlier of
seasonal measurements of biomass, phytoplankton production and their distribution in the
southern part of the Riga Bay (Zute, 1974; Rudzroga, 1974, 1987) show that in September
the values of primary production are very low; they were not changed practically within the
boundaries of water area, studied by us, and consequently are not able to have a significant
effect on the concentration and behaviour of organic matter and micro-elements. Thus,
the main reasons for fluctuation of these components are the physico-chemical processes:
Geochemistry of Dissolved and Suspended Organic Carbon 133
Zn, ppm
~:>600
Fig. 70. Particulate Zn in the southern part of the Riga Bay (Artemyev and Gorshkov, 1982).
flocculation and adsorption-desOlption. which may affect the behaviour of organic matter
and micro-elements at various stages of water mixture. It also follows from Figures 68-70
that the behaviour of CP, copper and zinc in surface waters of the Daugava river and the
Riga Bay are similar. This proves their interrelation and migration in the form of organic
matter-metal complexes or adsorptional complexes.
The analysis of behaviour of iron and organic matter forms in the southern part of the
Riga Bay showed that in the initial stage of intermixture of the Daugava waters and sea
.....
(;l
-I:>
(J
:§
(;;
...
""
Table 49. Average content and forms of Fe, Zn and Cu (in I"gIl) and Cd (in mgll) in waters of the Riga Bay (Demina and Artemyev, 1984).
Fe Zn Cu Cd
Water mass II III IV II III IV II III IV
Surfacia! content 1.6 2.0 3.6 ill 12.7 1.9 14.6 5.1 2.0 1.3 3.3 .L.Q 6.55
(d = 10 m, n = 17) 0.85 453
% oftota! 44.6 55.6 87.0 13.0 60.6 39.4
dissolved form
% oftota! 23.6 76.4 74.1 25.9 76.7 23.3 93.50
content
Deep and bottom content 1.5 2.6 4.1 36.4 15.0 2.7 17.7 5.6 3.3 1.0 4.3 0.6 5.50
(d = 10 m, n = 15) 0.81 1015 327
% oftota! 36.6 63.4 84.7 15.3 76.3 23.7
dissolved form
% oftota! 10.1 89.9 76.0 24.0 87.7 12.3 95.00
content
Forms: 1. inorganic dissolved; II. organic dissolved; III. tota! dissolved; IV. suspended (in nominator: for Fe - % dry weight, and for
Zn and Cu - 10- 4 % dry weight); d =depth; n =number of samples.
-- --
Geochemistry of Dissolved and Suspended Organic Carbon 135
Fig.71. Dissolved Fe (a), Cu (b), Zn (c) in surfacial waters of the southern part of the Riga Bay in July 1978
(mg/l, organic form) (Dyomina and Artemyev, 1984).
waters transition of iron from the dissolved into suspended form takes place as a result
of flocculation (Demina and Artemyev, 1984). As is obvious from Table 49, the biggest
part of iron in the solution is bound with organic compounds of evidently colloid form.
During flocculation, iron is transformed into suspension which is deposited from surface
waters and accumulated in bottom waters. It was also determined that higher content of
both suspended iron and CP and phytoplankton primary production (Figure 65) was found
in the surface waters of the studied part of the Riga Bay water area, on the boundary of
mixture of river waters with sea waters.
Thus, the concentration and the behaviour of suspended iron in the southern part of the
Riga Bay is controlled primarily by the processes of primary production of organic matter
by phytoplankton.
Distribution of the "organically dissolved" form of iron and copper in surface waters
shows the same character as that of Cd (Figure 71): low concentrations are found near
the Daugava mouth and high ones in the area of mixing of waters, at some distance
from the river mouth, with high values of primary production (Figure 65). At the same
time, the "organically dissolved" form of zinc is distributed in the opposite way: high
concentrations are near the river mouth and there is a drop of concentration with an
increase of the distance from it. Evidently, the river run-off is the only source for the
"organically dissolved" form of zinc in the studied waters, where as for iron and copper
the main factor of organic complex formation is bound up with production of organic
matter by phytoplankton in the area of mixing between river and sea waters.
3.5.5. CONCLUSIONS
1. The structure of water thickness in the southern part of the Riga Bay is characterized by
a clear stratification and the presence of two types of water: surface, mainly riverine with
high Cd content (8-12 mgll) and subsurface, mainly sea water, with low concentrations
of Cd (4-6mgll).
2. The dissolved form of organic matter (85-98%, average 94% of the sum of dissolved
and particulate organic matter) prevails in the studied waters of the bay.
136 Chapter3
3. In the zone of transition from refreshed waters to sea waters (salinity 6--7%0) we found
a noticeable increase of CP content, which is principally bound up with the activation of
the process of primary production of organic matter by phytoplankton. Another factor
affecting the increase of CP in these waters is the flocculation of dissolved organic matter,
which is testified to by the decrease of Cd concentration.
4. The identical character of behaviour of particulate organic matter and a number
of micro-elements (chromium, copper, zinc) in the studied waters depending on salinity
testify to the transportation of these micro-elements in close connection with particulate
organic matter.
5. Variation of concentration of particulate organic matter and micro-elements at the
initial stage of waters intermixture is caused, mainly, by physico-chemical processes (ad-
sorption-desorption, flocculation) and the primary production of organic matter is of minor
importance here.
3.6.1. BASIC FEATURES OF THE HYDROLOGY OF THE SOUTHERN PART OF THE BAY
The lavish continental run-off into the White Sea averages 215 km 3 and causes the
permanent current, velocity which is equal to 0.3-0.7 knots. The value of this current is
great for the dynamics of sea waters and for other elements of this hydrological regime.
Continental run-off during all seasons affects the thermal and salinity regimes of the sea,
especially in the region of neighbouring mouths of large rivers. The main part of this
drainage is supplied into the White Sea in May-June (45%) and during the five winter
months (December-April) when drainage is equal to 15%. The North Dvina river gives
48% of the total river drainage into the White Sea (Nadezhdin, 1966).
Normal thermal and salinity stratification accompanied by the decrease of temperature
and increase of salinity with depth, is almost always kept in the Dvina Bay at relatively
small depths and flat relief of bottom. Such schemes of salinity distribution are clearly
revealed in the summer, autumn and especially in the winter (Figure 72).
The North Dvina river mouth includes the coast section of the river from Ust-Pinega
to the coast shelf and the southern part of the Dvina Bay (Zotin and Mikhailov, 1965).
The peculiarities of the hydrological regime of the North Dvina river mouth is mainly
determined by the value and distribution of river run-off and by the tidal character of the
sea. The upper boundary of the river mouth region goes near the Pinega river mouth
(Figure 73) where tidal level variations are stopped. The sea boundary follows the slope
of depths. The North Dvina river mouth area is subdivided into three parts: (1) river
mouth section, from the Pinega river mouth to Arkhangelsk; (2) delta with the three main
branches and numerous channels; and (3) river mouth shelf (Figures 72 and 73). The
complicated hydrological regime of the river mouth region is formed as a result of the
permanent interaction between river and sea waters.
Geochemistry of Dissolved and Suspended Organic Carbon 137
e6
-
.r:i 8
c:a.
! 10
___ 9
7
12
1'1 Winter
16
The main features of the hydrological regime of the North Dvina river mouth region
are as follows: periodical tidal-ebb tidal variations of the level which have a half-day
character and the value of up to 1.5 m, spring flood, rise (1.5-2.0 m above the full
water level) and lowering of level (0.5-1.0 m below the low water level). At the coast
section of the river, variations of water level are clearly annual ones, two maxima and two
minima being underlined. The first maximum is the spring flood at the end of April-May;
the second maximum is autumnal in September-October, when run-off increases from
autumn rains and piling up lifts the level. The minimum levels are in winter and in
summer (February-March and August-beginning of September).
Distribution of salinity at the North Dvina river mouth shelf is characterized by the
presence of a zone of considerable horizontal gradients (hydrological front) of salinity,
being the boundary of two main water masses - river water and the water of the Dvina
138 Chapter3
Fig. 73. The scheme of the North Dvina river mouth area (Zotin and Mikhailov, 1965). 1. Near-mouth region;
2. delta, 3. river-sea water mixing area.
Bay. The hydrological front is traced not only on the surface, but near the bottom too.
The zone of maximum horizontal gradients of salinity lies at the slope of depth during the
period of spring flood and is shifted towards the river, going along the line from Lebedin
Island to the mouth of the Nikolsky branch during the other seasons (Artemyev et at.,
1984).
The seasonal character of the distribution of salinity, temperature, suspension and Cd and
CP in the area of mixture of waters of the North Dvina river and the Bay is shown in
Figure 74. The temperature of the waters, as it should be expected, regularly increases
from the winter to the summer season, from -1°C to + 18°. Salinity of surface and bottom
waters during all seasons of the year, except for spring, increases in the direction towards
the sea, from 0.0 to 4.3%0 in surface waters and from 0.5 to 10%0 in bottom ones. The
most saline waters were found in the winter: 0.5-4.3%0, average 2.0%0 on the surface and
about 10%0 near the bottom.
In spring, during the flood period, fresh waters propagate in particularly the whole
thickness of waters. The value of salinity during the studied seasons correspond on the
whole to the average mUltiyear values in the North Dvina river mouth area (Lupatchev
and Makarova, 1984).
Differences of surface and bottom water salinity and the presence of clear stratification
of the studied water thickness during all seasons, except the spring, testify to the different
nature of water layers: surface ones are mainly river waters; bottom ones mainly sea
waters. It also determines the differences of dissolved and particulate organic matter
Geochemistry of Dissolved and Suspended Organic Carbon 139
0.6 "
""' " ... .
:.
... 0,5
o.~
!!E," 0.3
/ir
z
~ ;:1
0.2
;~oo.G::::==. =.=.=..=t'="='T'="="$=·="="="·~·~
::: 0
;j 1: I ....;..
A
:l.:O~
i
... 0.15
ri(l 05
0,10
•••••••• ""'"
.,0..
l.I ~~
~
~",'"
,.11. ...
~
~ ,c>:-::~~ 1 2 3 4 5 6
Z 0 - ' ,----!.. Slillion N
2 3 4 5 Station ft 6 _eSummcr_A Autumn ·.-oSprlng --e. Winter
Fig. 74a. Seasonal peculiarities of the behaviour of hydrochemical components, particulate matter, cd, CP
and carbohydrates at the profile "North Dvina river mouth-sea" (Artemyev and Rornankevich, 1988). Surfacial
layer.
content in surface and bottom waters, their proportions in various points of section river-
sea, hydrochemical and physico-chemical peculiarities of medium, etc.
Concentration of the suspension in studied waters varies from 1.8 to 10.9 mg/l av-
eraging, for both surfacial and bottom waters, 5.0 mg/l. In this case, no temporal or
140 Chapter3
t!~ -1 _ ; --: _
/ .:-----J
Q,6 ................
...." 114
r
~
o.z
:>::
~
0
0
"
: o.o~tt:~::m:==~R'=·-=--::li:::--:::--:::-g/E::--=--=-=--=--::!j{
10
8
~ 6
e
i
~
II
2
CP, my/l
e', mgll
c~. mg/l
19
·-0.·····1"\····.0 ........... '-0-'" •••••••••
I \
J 15 I ,
I \
--- --
2 I \
10 A/
I
)(
2 J 5 5
Station r..
-eSUlnlllm --#'\1111111111 .... _ .. -0 Spring --a.Winh',
suspension, equal to 96.1 %, was found in surface waters of the station of the section
furthest from the sea, in winter.
The winter suspension is enriched with organic matter to the highest extent, compared
with the suspension taken during the other seasons: 21.8-91.6%, average 46.8%.
In the organic matter of the area of mixture of the North Dvina river waters and waters
of the Dvina Bay, the dissolved form prevails: 75.2-98.8%, average 91.4%. This is also
indicated by the ratio of Cd and CP at the section (Figure 74). The share of particulate
organic matter is increased during the flood period, in spring, when it is equal to 5.7-24.8%,
averaging 12.4% of the total organic matter.
The content of Cd and CP in the studied waters varies respectively from 7.1 to 24.7 mg/l
and from 0.2 to 3.8 mg/l, averaging 14.3 and 1.1 mg/l for surface waters and 11.6 and
1.0 mg/l for bottom waters. It is obvious from Figure 74 that the concentration of both
Cd and CP varies insignificantly, but it does vary with the increase of distance from the
river mouth towards the sea, in the area of river and sea water intermixture. First of all,
142 CluJpter 3
4
A Summer
:::::
01 3 • Autumn
El
U 2 Spring
DO • C
o Winter
~R~· .A ••
0 ~'. • •
30
25 0
:::::
01
Ei 20
...U
15 ~~
• ••
0
0
10
• • • • •0 •• 0&
5
o 2 4 6 8 10 Cl. %..
Fig. 75. Cd and CP behaviour in the North Dvina river and sea waters mixing area in different seasons plotted
against salinity (Artemyev and Lazareva, 1984; Artemyev and Romankevich. 1988).
The Cd/Cp ratio varies in the surfaciallayers from 3 to 90, and averages 23. In spring
and winter, this values from 3 to 20. In autumn the ratio Cd/Cp increases sharply due to
the decrease of the suspension concentration. In bottom waters, the ratio Cd/Cp varies
from 5 to 52 and averages 18. As for surface waters, the highest values ofCd/CP in bottom
waters are typical for autumn.
Essential variations of Cd/cP values on the section river-sea in both surface and in
bottom (to a lesser extent) waters testify to the variations in the proportion of forms
(dissolved and suspended) and composition of organic matter on the whole length of the
section. An increase of Cd/cP with an increase of off-shore distance is typical for both
surface and bottom waters.
Since the proportion Cd/Cp for sea (oceanic) waters exceeds that for coastal waters,
estuaries and near river-mouth areas of rivers, it may be considered as the index of the
proportion of organic matter of continental and sea genesis for the river and sea waters
intermixture area.
The analysis of particulate and dissolved carbohydrates (PC and DC) showed that these
organic compounds compose a small part of organic matter (Figure 74). On average,
the content of particulate carbohydrates in surface and bottom waters totals 0.06 and
0.10 mgCn respectively (or 12.4 and 1l.6% of CP) and that of dissolved carbohydrates
144 Chapter 3
equals 0.92 and 0.66 mgC/l (or 7.0 and 6.1% of Cd). When moving from the North
Dvina river mouth towards the Dvina Bay, concentrations of particulate and dissolved
carbohydrates increase, reaching more or less stable values by the early stages of mixing
between fresh and salt waters. Thus, the non-carbohydrate components of organic matter
take part in physico-chemical processes (flocculation, etc.) on the studied section river-
sea, since neither particulate nor dissolved carbohydrates are subjected to any noticeable
fluctuations during the process of transition from river waters to sea water.
3.6.3. CONCLUSIONS
The dissolved form noticeably predominates in the organic matter of the studied waters
during all seasons; it averaged 91.4% of the sum of dissolved and particulate organic
matter.
The largest quantity of organic matter in suspension, with an average of 46.8%, was
found in winter, the lowest one in summer suspension, with average of 19.3%. The
quantity and the quality of dissolved and particulate organic matter, peculiarities of its
spatial distribution in the section river-sea are bound up with the supply of organic matter
into water from the three sources: primary production of phytoplankton, with products of
economic activity (for example residues of floating wood) and pollutions. The behaviour
of dissolved and particulate organic matter at the studied section is a very complicated one
and is characterized by alternation of maxima and minima over the entire river-sea section.
In fresh waters (up to 1%0), as well as in waters with salinity exceeding 8%0, variations
of organic matter concentrations are bound up with its supply from natural sources and
pollutions. The physico-chemical processes (adsorption-desorption, flocculation) clearly
revealed during all the seasons in 4-8%0 salinity waters, play an important role for the
transformation of organic matter forms in waters of the intermixture area.
The ratio of Cd/cP varies from 3 to 90 and averages 20, and may be considered as the
index of the proportion of organic matter of continental and marine origin for the waters
of the river and sea water mixing area.
The content of dissolved and suspended carbohydrates in the region of mixing between
the waters of the North Dvina and the Dvina Bay averages 7.5% of Cd and 12% of cP,
i.e. the main part of the studied dissolved and particulate organic matter is represented by
organic matter which are more resistant to decomposition.
The typical peculiarity of the regions of mixing between mountain rivers and sea waters
is their small length and sharp transformation of all the parameters from "river" ones into
"sea" ones. As is obvious from Figure 76, the zone of the maximum gradients of salinity
is equal to just 0.5 km.
The distribution of suspension and CP on the section "Mzymta river mouth-Black
Sea" is characterized by the decrease of their concentrations in the direction river-sea
Geochemistry of Dissolved and Suspended Organic Carbon 145
~~~
'----------.--.--"---~~
Fig. 76. Sampling stations at the profile "Mzymta river mouth-Black Sea" in May 1979.
3.8. General Regularities for the Behaviour of Dissolved and Suspended Organic
Substances in River and Sea Water Intermixture Regions (Comparative Analysis)
The results of the laboratory modelling of processes of intermixing of river and sea waters,
and the data of natural observations in the regions of river and sea water intermixture,
showed that the process of transformation of dissolved into particulate organic matter, and
vice versa, takes place at all the stages of water intermixture (but most actively in waters
146 Chapter 3
~ >100
_ 100-30
_ 30-2Q
E---j<20
•
100
200
JOO _>0,5
Fig. 77. Vertical distribution of particulate matter (a) and CP (b) at the profile "Mzymta river mouth-sea" in
May 1979.
Geochemistry of Dissolved and Suspended Organic Carbon 147
c~ mgtl
* /'9
¢> : I
I
, 10
J
""..-
I
o
"-
2 I
"-
150
100
50
~------------+-----------~~o
River Mixing area
Ocean
CP.% C/N
I
15
CP I o Surface
I t:. Bottom
I
I
I C/N
10 10
I .. /
I
.".
,," ,
' 5
0 0
River Ocean
Mixing Area
Fig. 78. Cd and CP behaviour in the area of the Loire river and ocean. waters mixing (Saliot etal., 1984).
'[8 EJ
co
" 0000 0
z .
8
2 6
6
"
2
10
J
8
"
2
8
6 0
0 " 8
"
2
5 15 25 5 15 255,%0
Fig. 79. cJ behaviour in estuaries (Fox, 1983). Estuaries: Murderkill (I, 9); Leipsic (2,13); Mullica (1980) (3,
11); Broadkill (10, 1978) (4); St. Jones (5, 10); Delaware (6, 14); Mullica (1979) (7, 15); Broadkill (OS, 1978)
(8); Broadkill (12); Mispillian (16); 9-16 see Figure 80.
various sources (soils, plankton, phytobenthos, pollutions, etc.) and with hydrodynamic
factors (direction and velocity of currents, peculiarities of water stratification).
The estimation of river organic matter "losses" in the case of mixture of river and
sea waters was given in the example of the Amazon estuary by means of the developed
model: for dissolved organic matter it is equal to 25%, for particulate organic matter it
is 80%. These results correlate well with the data of Edmond et al. (1981), according
to whom the quantity of CP in the Amazon estuary is. decreased by 60-70% compared
with river particulate organic matter, which in the opinion of the authors is caused by
partial mineralization of particulate organic matter in the tidal zone, or in the estuary at
Geochemistry of Dissolved and Suspended Organic Carbon 149
Coo.'
50.-------,
IJ
JO
20
10
10 III
40
20
15
100
60
20
16
60
110
o
o
20 0
o
o 0
01020JO
low salinities, i.e. at the initial stages of water mixture. By the data of Eisma et at. (1985),
only 25 % or less of particulate organic matter delivered by rivers is supplied to the sea, and
the largest part of river particulate organic matter is fractured and mineralized in estuaries.
From the data of Degens and Ittekkot (1985), up to 70% of CP may be destructed in the
coastal sea medium.
Comparative consideration of the factors determining organic matter behaviour in the
studied regions of river and sea waters intermixture showed that physico-chemical pro-
cesses (flocculation, adsorption-desorption) are the first to be responsible for changes in
the proportion of dissolved and particulate organic matter at the initial stages of water in-
150 Chapter 3
termixture, with salinities of up to 10%0. The effect of the processes of primary production
of organic matter by phytoplankton on the delivery of dissolved and particulate organic
matter to estuaries is revealed only at a distance from the river mouth in waters accessible
to the penetration of light. The distance between these waters and the river mouth is
determined by several factors: river run-off value, concentration of suspension and the
character of water circulation in the sea or ocean neighbouring the river mouth. So, in
the Amazon estuary (where concentration of suspension in river mouth is 100-150 mg/l)
high values of primary production of phytoplankton are observed at a distance of 150 km
from the river mouth, in waters with salinity of 10-12%0, where suspension concentration
is equal to 5-10 mg/l.
In the Temryuk, Taganrog and Riga Bays (where concentration of suspension in the
mouths of the studied rivers is 40-60 mg/l) high values of primary production of phy-
toplankton are observed 5-7 km from the river mouths, in waters with salinity of 4-6%0
where suspension concentration is 10-30 mg/1.
Peculiarities, revealed by us, of Cd and CP behaviour in estuaries and regions of
intermixture of river and sea waters confirm the studies of foreign scientists. So the
mutually contrary character of the behaviour of Cd and CP in the region of the transition
from river to oceanic waters was found in the estuary of the Loire river, see Figure 78
(Saliot et al., 1984). The non-conservative behaviour of organic matter was observed in
the majority of studied estuaries of the Atlantic coast of the U.S.A. (Figures 79 and 80;
Fox, 1983), England (Hunter and Liss, 1982), in the estuaries of the Elba and Ems rivers
(Michaelis et al., 1986) and the Yang Tze and Yellow rivers (Cauwet and Mackenzie,
1993).
The areas of mixing ofthe North Dvina river and the Dvina Bay waters are characterized
by suspension which is the richest in organic matter of all the studied regions: 46.8%
in winter and 19.3% in summer. Content of organic matter in suspension in estuaries of
moderate latitudes averages, as a rule, 9.4%.
The similar character of behaviour of CP and a number of micro-elements (copper,
nickel, zinc) in the studied regions of river and sea water intermixture with increase of
salinity (Temryuk and Riga Bays) testifies to their interaction and transportation in the
form of complexes organic matter-metal or sorption complexes.
Variation of dissolved and particulate organic matter composition in the regions of
river and sea water intermixture is affected by phytoplankton, which in particular plays
the main role in the delivery of dissolved carbohydrates into water.
Chapter 4
Dissolved and particulate organic matter transported to the ocean with river run-off af-
fect the distribution and composition of organic matter in sea sediments. Organic matter
serves as the regulator of many biogeochemical processes in both the water column and
in bottom sediments. These processes are bound up with the formation of many minerals,
including a number of rare and non-ferrous metals. Therefore, the knowledge of the nature
and regularities of the distribution of organic compounds in waters and sediments of the
river-sea system is extremely important for the knowledge of sedimentation processes in
the ocean.
The studied organic compounds in the suspension and bottom sediments of the Amazon
estuary include amino acids, humic acids and bitumoids (Artemyev and Lazareva, 1986;
Artemyev and Danyushevskaya, 1988).
The content of amino acids in suspension of the Amazon estuary varies from 0.020 to
0.030% and averages 0.027%, converting into dry weight of suspension, and to 0.09% of
organic matter. Compared with the river suspension, the content of amino acids in the
Amazon estuary is lower.
As a natural result, the content of amino acids in the suspension decreases with an
increase of distance from the river mouth towards the ocean (Table 25).
The proportion of amino acids groups varies in the direction river-ocean: the share of
neutral amino acids is increased from 49.9% in river waters to 54.5% in the estuary waters,
and the content of basic amino acids is decreased from 16.3 to 12.1 %. The following acids
prevail among the individual acids in the Amazon estuary (in decreasing order): glycine,
glutamic acid and proline, and glutamic acid-glycine-asparagin acid in river waters.
151
IS2 Chapter 4
Table 50. Organic carbon (CP) and particulate carbohydrates (C~) on the section "Amazon
river-Atlantic Ocean" (Artemyev and Lazareva, 1986).
1042 0.01 2.0 27.4 9.6 36.7 27.4 230 1\.5 2.3
1043 0.02 1.4 20.3 22.5 15.0 42.1 133 9.5 2.8
1044-4 0.83 1.9 44.6 9.9 9.9 36.2 251 13.2 1.0
1044-8 1.26 2.0 12.6 17.3 30.7 39.3 127 6.3 5.5
1052 9.79 1.2 25.0 7.1 23.2 44.6 56 4.7 2.7
1050 10.66 0.7 56.5 25.3 10.1 8.2 269 38.4 0.3
1049 17.52 1.4 33.8 4.2 36.6 25.3 71 5.0 1.8
1047 22.18 1.1 37.0 14.8 18.5 29.6 54 4.9 1.3
1045 38.24 0.3 36.8 5.3 15.8 42.1 19 6.3 1.6
Average 1.3 32.7 12.9 21.5 32.5 134 11.0 2.1
The study of carbohydrates in the Amazon estuary showed (Table SO) that their concen-
tration varies from 19 to 269 J.lgll and averages 134 J.lgll. The share of particulate carbo-
hydrates in particulate organic matter varies from 4.7 to 38.4%, average 11 %. Aqueous,
alkaline, weak acid and strong acid fractions in particulate carbohydrates composition
are equal to 32.7, 12.9, 21.S, 32.S% respectively. Thus, about SO% of all particulate
carbohydrates is represented by reactable compounds.
Comparative analysis of carbohydrate behaviour in suspension on the section "Amazon
river-Atlantic Ocean" (Table SO) shows that river waters, waters of intermixture region
and ocean waters differ noticeably by their composition of carbohydrates. The index of
such differences may be the ratio of carbohydrates of acid fractions, most resistant to
decomposition structure polysaccharides, to carbohydrates of aqueous fraction, to mainly
reserve polysaccharides and oligo saccharides (Artemyev, 1976). As it is obvious from
Table SO, this ratio for river waters averages 2.S, for intermixture areas 3.1 and for waters
with salinity exceeding 17%0 it averages 1.6.
Thus, the least labile and reactive carbohydrates are particulate carbohydrates of river
waters (mainly of soil origin). In ocean waters where the main source of organic matter
is phytoplankton, particulate carbohydrates are more labile. In the estuary waters, as it
is obvious, one may meet particulate carbohydrates which differ in their composition and
degree of reactivity.
The most variable concentrations of particulate carbohydrates are in aqueous and acid
(sum of weak and strong acid) fractions. So, within the borders of water intermixture
we may separate two clear maxima of particulate carbohydrates content in the aqueous
fraction, in waters with salinities of about 1%0 (station 1044-4) and about 11%0 (station
1OS0) where they are equal to 44.6 and SS.5% respectively. It is obvious from the given
Transformation of Particulate Organic Matter 153
data (Table 45, Figure 48) that the essential "losses" of dissolved organic matter take place
just in these waters of the intermixture region as a result of the flocculation process and
dissolved organic matter transition into the suspended form.
High contents of carbohydrates in the aqueous fraction of suspension at these stations
testify that at least a part of organic matter transformed into the suspended form from the
dissolved one in the composition of floccules is represented by reactive carbohydrates.
The first maximum is followed by a sharp decrease of aqueous fraction content (Table 50),
this being caused by the particulate organic matter desorption process taking place here,
as a result of which the most labile compounds are the first to be transformed into
dissolved form; those are carbohydrates of aqueous fraction (for example, water-soluble
oligo- and polysaccharides). In water with high salinity (more than 17%0) of the studied
section, the composition of particulate carbohydrates is stabilized, which is testified by
the insignificantly varying (with increase of salinity) ratio of reactive (aqueous fraction)
and decomposition resistant (acid fraction) carbohydrates. It may be only noted that with
the decrease of distance to typically ocean waters the share of carbohydrates of strong
acid fraction, which are most resistant to decomposition, increases.
According to the data of analysis of carbohydrates by gas-liquid chromatography, the
following compositions of monosaccharides of aqueous and alkaline fraction of river
suspension predominate (Table 50): rhamnose; arabinose; xylose; and ribose, which are
respectively equal to 26.6; 24.3; 26.6; 19.8% and 28.9; 18.0; 16.2,26.0% of the sum of
monosaccharides.
Glucose and galactose were found in these fractions in trace quantities, but their content
in the weak acid fraction is increased to 7.3% (glucose) and 3.3% (galactose). Application
of gas-liquid chromatography for the analysis of particulate carbohydrates made it possible
to determine the monosaccharide composition of those parts of particulate carbohydrates
which, evidently, participate in the processes of flocculation during transportation of
organic matter in the estuary waters.
Humic acids were not found in the Amazon estuary suspension and in river suspension
(Table 31). Consequently, the process of transformation of organic matter towards the
formation of geopolymers of humic acid type (humification) is not typical for river and
estuary suspension, in contrast to pelagic processes of the ocean, where according to
the data of Romankevich (1977) particulate organic matter composition includes humic
acids with an average of 6.2%. In our opinion, this is bound up with various sources
of particulate organic matter in the river-sea system (mostly terrigenous) and in the
ocean pelagic (mainly planktonic) which mayor may not he able to be transformed into
geopolymers of humic acid type.
The typical peculiarity of particulate organic matter composition variation towards "the
Amazon-estuary-ocean" is the decrease in the content ofbitumoids (first of all ofbitumoid
Ad), transformed, evidently, into "residual" organic matter or "complex" organic matter
(Fichez et aL, 1993) or humines (Romankevich, 1977) resistant to chemical and biological
fracture. Thus, the transformation of organic matter in the direction river-estuary-ocean
is characterized by two interconnected processes: "debituminization-huminization".
154 Chapter4
30
25
~
• - 20
.
... !
... 0
o ...
I ~ 15
~!
"' ~... 10 --- .. 60 ~ ,:;-'
5 511 .'" i
1:0
40/l
~
.. 0
60 243°~1
RiYer Ocean
Fig. 81. Change of particulate organic matter composition in the Amazon river-ocean system.
The boundary of river run-off effect on the composition of organic matter in the system
river-estuary-ocean may be set by a sharp change of organic matter composition in the
direction river-sea (Figures 81 and 82).1
The shelf in front of the Amazon river reaches a width of 300 km, narrowing noticeably
northwards. Noticeable features of the shelf and continental slope are numerous canyons.
The main canyon of the Amazon begins at the depth of 50 m and is traced to depths of
1.5 km (Demuth and Kumar, 1975). A part of the shelf and the slope are occupied by the
Amazon debris cone (fan), which extends 650-700 km, reaching a depth of 4750 m.
The main part of the Amazon river "solid" run-off is accumulated on the shelf. Fine-
grained muds occur in the immediate vicinity of the river mouth, up to the 60 m isobath,
followed by the strip of sands. Deposition of muds near the river mouth is bound up with
high rates of sedimentation of river deposits, exceeding 2 cm/year (Kuehl et ai., 1982).
The studied bottom sediments of the Amazon estuary are represented by mainly terrige-
nous pelite muds (Table 21) with insignificant amounts of amorphous silica and calcium
carbonate (average 0.5 and 0.2% respectively). Content of Corg in these sediments is equal
to 0.29-1.67%, averaging 0.47%, with nitrogen from traces up to 0.05%. The ratio CIN
averages 11.8.
With an increase of the distance from the river mouth towards the ocean, the content
of organic matter in terrigenous muds decreases from 5.3 to 0.9%.
1The other possible criteria to distinguish organic matter inputs and origin are biomarkers (LauveiIIard and
Saliot, 1993).
Transformation of Particulate Organic Matter 155
..
2,0
M
:"i
.... 1,6
i.....l',2
~~
• .! 0,8
River Ocean
Fig. 82. Change of terrigenous muds organic matter composition in the Amazon river-ocean system.
Similar values of concentrations of Corg and nitrogen were found in the deltaic sediments
of Arctic Alaska (Naidu, 1985). As it is obvious from Table 21, the value C/N decreases
towards the river mouth, which is caused by the decrease of the quantity of terrigenous
organic material and an increase of the share of "sea" organic matter in bottom sediments.
Terrigenous organic matter is enriched with residues of higher plants with high content
of lignin and cellulose, and therefore with a higher C/N ratio. In contrast to this, the sea
biogenic residues are relatively enriched with nitrogen-containing compounds, such as
proteins, pigments, etc. (Naidu, 1985).
Content of humic acids in terrigenous muds of the Amazon estuary is essentially lower
compared with river muds (Tables 25 and 26) and averages 0.04%, converting into dry
residue weight, and 8.3% of organic matter (in river muds it is equal to 2.39 and 47.7%,
respectively).
Content of bitumoid Acl and Aal.b in the estuary muds remains approximately the same
as in the river, and is equal in sum to 3.8% of organic matter (in river muds 3.7%).
Content of the least reactive and resistant to decomposition "residual" organic matter
(humines) is considerably increased in the estuary muds, averaging 87.8% (in river muds
48.6%).
Thus, the predominating process in terrigenous muds in the direction river-estuary-
ocean is dehumification-huminization, i.e. the fracture of humic acids and the relative
increase of the share of humines, which are stable to decomposition in this context.
The boundary separating bottom sediments with river type organic matter from bottom
sediments with ocean type organic matter (Figure 82) may be set by the variation of ratio of
basic components (bitumoids, humic acids, "residual" organic matter) in the composition
of organic matter of bottom sediments in the direction river-ocean.
156 Chapter 4
~ @)c:::J Carbohydrates
(fJ
IIIIlIIIIID HA
®
. ~ ~Ilumold. mmD ROM
A - asfaltens, 0 - oils, R - resins
Fig. 83. Transformation of particulate matter and bottom sediments organic matter composition in the river-sea
system.
The study of Ac\ composition in terrigenous muds of the Amazon estuary showed its
similarity with bitumoid Ac\ in river muds in both northern humid and in equatorial humid
zones, which testifies to their genetic similarity (Figures 83 and 84).
In the line "suspension-bottom sediments" we observe a sharp decrease of organic
matter content (by approximately 40 times) which is bound up with its utilization by
plankton, benthos and micro-organisms in the water column and on the boundary water-
bottom.
The content of bitumoid Acl+al.b in the composition of organic matter of bottom sedi-
ments is essentially lower when compared with particulate matter, from 47.6% (suspen-
sion) to 3.8%, mainly at the expense of bitumoid AaI-b; humic acids appear (terrigenous
muds) and the content of "residual" organic matter is increased considerably. Thus, the
typical process of organic matter composition transformation in the line "suspension-
terrigenous muds" in the estuary, as in the river, are humification-debituminization.
Transformation of Particulate Organic Matter 157
73
~-
6J
..
...
.5 5J
~
¥J
3J
18 28 38 *8 58 68
Oils, I
Fig. 84. The composition of chloroform bitumoid "X' in organic matter of terrigenous muds and sands in
the river-sea system (Romankevich et al.• 1982; Danyushevskaya, 1984; Romankevich and Danyushevskaya,
1981; and the author).
The shores of the Dvina Bay, located in the eastern part of the White Sea are formed by
residual rocks. The Dvina Bay was formed on the old skerries. The White Sea formation
began here; the eastern boundary of this sea has existed for millions of years (Palenichko,
1968).
The southern part of the Dvina Bay is mainly characterized by large-sized detrital
fractions (sandy, with gravel-pebble admixture). The North Dvina river run-off transports
into the bay mainly fine pelite suspensions, as well as some quantities of sandy-aleurite
material (Kalinenko et at., 1976).
The delta and river-mouth regions of the White Sea are characterized by the diversity
of colours of the granular components of sediments, with prevailing aleurite differences
between the sediments. This complex is characterized by a sharply expressed patchy
distribution of various granular types of sediments directly neighbouring each other.
Bottom sediments of the White Sea are characterized by Corg distribution zonality,
bound up with hydrodynamics, depth and bottom relief, as well as by the relation of Corg
distribution with river run-off deposits, primarily of the large rivers such as the North
Dvina and the Onega rivers (Nevessky et ai., 1977). At the same time, the data on
distribution of Corg in bottom sediments of the Dvina Bay, respectively in its river mouth
part (southern), are practically absent.
As it is obvious from Table 18, the content of Corg in bottom sediments of the "sea"
part of the section "North Dvina river mouth-Dvina Bay" in the river and sea water
intermixture area is equal to 0.32-0.96%, averaging 0.59% (or 1.07% converting into
organic matter), the content of nitrogen being equal to 0.006-0.029%, average 0.020%,
and the ratio CJN varying from 16.5 to 53.3 and averages 34.3.
The typical process of transformation of organic matter composition of sands in the
river-sea system is "debituminization", accompanied with an increase of the "residual"
158 Chapter4
organic matter share in organic matter composition. Absence of humic acids in organic
matter of sand in the "North Dvina river-sea" system also indicates that humification
of organic matter does not take place due to sharply oxidizing conditions, helping the
destruction oflabile organic matter, being a potential base for the formation of geopolymers
of humic acid type.
Another peculiarity of organic matter of sands in the "North Dvina-sea" system is
the similarity of composition of bitumoid AcI in river and estuary sands, which differs
essentially from composition of bitumoid AcI of terrigenous muds (Figure 83). Thus,
independently from various climatic conditions for the formation of bottom sediments
organic matter, terrigenous sands in the river-sea system have the same bitumoid AcI
composition.
The distinctive peculiarity of terrigenous mud organic matter composition variation,
as in the equatorial zone, in the direction "North Dvina-sea" is "dehumification", and
as a consequence of this there is an increase of the share of humines in organic matter
composition. Consequently, the trend of transformation process for terrigenous mud
organic matter composition in the river-sea system is "dehumification-huminization".
The composition of bitumoid AcI in complexes with grains from North Dvina river
bottom sediments (sandy muds with admixture of aleurite material) differs from the
composition ofbitumoid Ac1 of river muds and estuary muds, and occupies an intermediate
place between sands and muds.
Comparison between the distribution character for CP and Corg of bottom sediments
on the section "North Dvina river mouth-Dvina Bay" (Figure 85) gives a possibility to
witness a number of peculiarities in their behaviour. CP is characterized by a decrease in
concentrations in the direction from the river mouth to the sea by both observational data
during various seasons and by averaged data. Variations of CP concentrations observed
in river waters are related to the inhomogeneity of rivers particulate organic matter com-
position at various sections of the river mouth. Low concentrations of Corg (about 0.1 %)
are typical for river bottom sediments, medium-grained sands, and high concentrations of
C org (0.5-1.0%) for sediments in the river and sea water intermixture area, which are also
mainly sands. The highest concentrations of Corg were marked in aleurites with admixtures
of clay muds, which is bound up with their superior sorption ability, when compared with
sands. Thus, we do not observe the uniformity in distribution of CP and C org in bottom
sediments on the studied river-sea section. This is mainly bound up with the peculiarities
of the considered region being the geochemical barrier. On the one side of the barrier,
in river waters the content of Corg in bottom sediments is extremely low, despite high
concentrations of cP. This is caused by the fact that fine particles of suspension, which
are enriched with organic matter to the greatest extent, have no favourable conditions for
sedimentation due to the high velocity of the current. On the other side of the barrier,
in waters of river and sea water admixture, the concentration of CP is lower than in the
river waters, but Corg content in bottom sediments (fine- and medium-grained sands) is
higher than that in similarly composed river sediments (Table 18). This is associated to a
considerable extent with more favourable hydrodynamic conditions for sedimentation of
suspended particles, mainly due to a decrease of water current velocity.
Transformation of Particulate Organic Matter 159
1,',
,1
I ,
,
1,3 I I
,,
I I
I
I
1,2
•I I
I
I I
1,1 I I
I I
I I
,
I I
1,0 I I 2
•,I
, ,,
..- 0,5
Of
••\
,,,
5
" 0,*
\
\
\
\ ,, 4
¥ ...
0,3 J ....
..•-
III!
0.2 2 u
0,1 1
~3River
"
5 61 7 Istuary.-
I
8 9 Stations II
I
Fig. 85. The behaviour of CP (1, 3, 4) and bottom sediments Corg (2) of the profile "North Dvina river
mouth-sea" in different seasons. 1. Spring; 3. winter; 4. middle data (Artemyev et al., 1984; Danyushevskaya
et al., 1990).
In February-June 1981 during the 32nd cruise of the research vessel "Akademik Kurcha-
tov" we studied the peculiarities of organic matter composition transformation in water,
suspension and bottom sediments on the periphery of river and ocean water mixing area
in waters neighbouring the Limpopo (plankton, water, suspension. bottom sediments) and
the Zambezi (suspension, bottom sediments) river mouths (Figures 86 and 87).
The studies were carried out in poorly refreshed waters with salinity of 30-35%0 which
were propagated to the south-west from the Limpopo river mouth, under the effect of
the Mozambique stream (Figure 88). The station nearest to the river mouth was located
3-5 km from the coast. It is obvious from Figure 88 that the Limpopo run-off effects
the character of the distribution of all the studied parameters: suspension, plankton and
160 Chapter 4
~~:~---------t--------t
eml
33·30'
Fig. 86. Sampling stations at the profile "Limpopo river mouth--ocean" (May 1981),
organic matter. Their higher concentrations are near the zone of the refreshed waters and
decrease towards the open ocean, reaching more or less stable values in waters with salinity
of 35%0 and more, i.e. those which are not subjected to the influence of river run-off. The
propagation of zones of high index concentrations towards the south-west is determined by
the Mozambique Stream, and the decrease of concentrations with an increase of distance
from the Limpopo river mouth is a result of both dilution of river waters with oceanic
waters and the effect of flocculation processes (or adsorption-desorption) taking place on
the boundary of refreshed and salt waters. The process of variation (decreasing) of all the
studied components' concentrations towards the section "Limpopo river mouth-ocean" is
accomplished with transition to ocean waters, and therefore the boundary of concentration
stabilization is the 35%0 isohaline.
Concentration of suspension on the section "Limpop.o river mouth-ocean" varies from
0.3 to 2 mgn and is equal to 1.5-1.7 mgn in the region of the Limpopo river mouth, and to
0.3--0.6 mgn at the remote ocean stations (Figure 88). The suspension content in coastal
Transformation of Particulate Organic Matter 161
19"
00'
19"
30'
20"
OO'~----~~----------------------------~
,00
Fig. 87. Sampling stations at the profile "Zambezi river mouth-ocean" (May 1981).
... '.:
'd . : :.; .'
.
:., .····If.f(.",
:1:'\
6t.?-
~
.
<100
•
Fig. S8. Distribution of salinity (a). particulate matter. mgll (b) plankton biomass. mg/m3 (c). cPo mgll (d). in
the Mozambique channel waters adjacent to the Limpopo river mouth (Artemyev. 1982).
waters does not essentially vary vertically. from the surface to the bottom (2 m from bottom)
layer of water. In spite of the effect (although a minor one) of river run-off, plankton in
the studied region are mainly oceanic, but for that at one station (3357) where the brackish
162 Chapter 4
....
..... ....
..... 2,0
eo .........
.,.•-
eo
B
.,,,-
II
eo
--aeo
PH
,,
a
.~,A.':iII
..- ,,
,
~.
\.
0,4 2,6 -',6
.
",
z
",
<1
• ,,
0,3 2,2
l,B
90
70
1,2
0,8
c·
'\\~ \
0,2
...... ~-
-~~
/
PB
If" "'-_
0,1 1,4 50 0,4
A
A
0 1,0 30 0
30 31 32 33 3* 351. J6J,%D
Mixing area Ocean
I I I I I II
~
~ ..,~ Stations N
~
~
~~~tl;
I::i~~~
Fig. 89. Dependence of particulate matter, plankton biomass, Cd and CP concentrations on salinity at the
periphery of Limpopo river and ocean waters mixing area (Artemyev, 1982).
tolerant Acartia genus was found (Ponomareva, 1982). The biomass of plankton on the
studied section is equal to 34-86 mglm 3, average 55 mg/m3, which is essentially lower
than in the productive waters of the Indian Ocean. The character of the plankton biomass
distribution on the section is similar to that for suspension (Figure 89) and explained by
the proximity of its high concentrations to waters enriched with biogenous substances,
delivered to coastal waters with river run-off.
Poorly refreshed waters on the studied section are characterized by high (compared
with oceanic waters) concentrations of Cd. The source of Cd is river run-off and plankton.
Content of Cd in the studied waters exceed cP content by an order, and is equal to
1.2-2.4 mg/l, averaging 1.5 mg/l.
Content of CP on the section "Limpopo river-ocean" varies from 0.014 to 0.443 mg/l
and averages 0.12 mg/l. As it is obvious, the concentration of suspended organic material
exceeds the biomass of plankton by several times, especially in coastal waters (Figure 88).
The sources of particulate organic matter in the studied section are not only planktonic
organisms, residues of their tissues, etc., but also the river run-off. Comparison of the
character of distribution of the plankton biomass and CP shows that terrigenous organic
matter in the total quantity of particulate organic matter prevails noticeably in refreshed
waters; in the direction of the "Limpopo river mouth-ocean" its content decreases, and
the share of CP in suspension varies from 30% in the Limpopo river mouth to 10-15 % in
the Mozambique Channel waters far from the river mouth. Content of CP in the zone of
Transformation of Particulate Organic Matter 163
t ..
~,~
. ~l
'.: ......'!o~.!) •
~<.,5
~.
~)
'-
..I
/ .
•
n \
\ • •
<50 <00
'... \~
Fig. 90. Distribution of cP, % (a), carbohydrates, fLgCIl (b), lipids, fLgC/l (c), lignin, fLgClI (d) in oceanic
waters adjacent to Limpopo river waters (Artemyev, 1982).
Stations N
33593360 3351 3352 3363 336" 3356
--------------
---
Fig. 91. Vertical distribution of particulate carbohydrates (fLgIl) at the profile "Limpopo river mouth-ocean"
(March-April 1981).
refreshed waters decreases vertically from the surface to the bottom by a factor of 1.5-2.
Here we also observe the decrease of particulate organic matter in suspension composition,
approximately by 30%. This is bound up not only with destruction of organic compounds
during sedimentation, which is typical for open regions of the ocean, but also with the
differences in genesis of particulate organic matter in surface and bottom water layers
in the river-mouth regions. The source of particulate organic matter of surface water
layers here are primarily river waters and plankton, and in the bottom waters the source is
suspended particles, brought from other regions of the ocean.
As it was already noted, the main feature of distribution of individual components
of particulate organic matter (carbohydrates, lipids, lignin) on the section "Limpopo
river-ocean" is expressed by the decrease of their absolute concentrations when moving
towards the ocean (Figures 90 and 91). The content of carbohydrates varies from 4
to 21 j.£gn and averages 10 j.£g/l. The content of particulate carbohydrates in bottom
164 Chapter 4
Fig. 92. Carbohydrates (l),lipids (2) and lignin (3) in the particulate organic matter (%) at the profile "Limpopo
river mouth--<>Cean" (Artemyev, 1982).
layers, especially in refreshed waters is, as a rule, lower than that for surface waters.
The content of carbohydrates of particulate organic matter composition varies from 3.6
to 42.8% and averages 12.8% The content of carbohydrates of particulate organic matter
composition in bottom water layers increases, as a rule, because of selective preservation of
decompositionally resistant structural polysaccharides of the cellular walls of planktonic
organisms in the composition of particulate organic matter (Artemyev, 1976). On the
whole, it is obvious that carbohydrates equal an insignificant part of the total sum of
organic matter.
In the studied samples of suspension, lipids are equal to 18-101 p,gn, average 45 p,gn.
When moving away from the Limpopo river mouth to the ocean, their content in surface
waters decreases from 100 to 20 mgn (Figure 90). The content of lipids of particulate
organic matter composition varies from 18.7 to 55.5% and averages 40.7%; consequently,
lipids are one of the basic components of the studied suspension organic matter.
The content of lignin in surface suspension, and more precisely the content of one
of the basic lignin components, paraoxybensaldehyde, various from 15 to 174 p,gn and
averaged 54 p,gn. In the direction of the ocean, the content of lignin in suspension
decreases from 150 to 20-30 p,gn (Figure 90). The share of lignin in particulate organic
Transformation of Particulate Organic Matter 165
....
~----~~r-.---~~------------~
9 3379
...
26 I
I c
!c 18
.
I
I o
c
22 I u
I
".
c I
I
0
u.
f8
I
I
~
,,
I
!•
0
11f I
~
fa
, Depth, •
,,
.
~J.178
!l0
6 .. .. 3J77
... ,,_. 3{,81
Fig. 93. Change ofbitumoid content in organic matter of the surfacialJayer of bottom sediments at the profile
"Zambezi river-ocean" (Danyushevskaya and Romankevich, 1987).
matter composition is equal to 4.4-55.8%, averaging 39.0%. When moving away from the
Limpopo river mouth towards the ocean, the content of lignin of particulate organic matter
composition increases (Figure 92). In the ocean regions located far from the continent,
the main source of lignin in suspension and bottom sediments may be atmospheric dust,
containing spores and pollen of ground plants (Boby leva, 1982).
The results of studying organic matter composition of bottom sediments on the sections
"Zambezi river mouth-ocean" and "Limpopo river mouth-ocean" by Danyushevskaya et
al. (1990) showed that the content of Corg in terrigenous pelite and aleurite-pelite muds
was equal to 0.16-2.2%, biogenous amorphous silica was equal to 0.08-D.62%, nitrogen
was equal to 0.04-D.16%, and the ratio C/N varied from 10 to 26.
Bottom sediments on the studied sections are characterized by bitumoid concentrations,
close to the background one for the World Ocean (content of bitumoid AcI averages 0.9%
of organic matter). High bitumoid content is typical for the fine-grained sands of the
Zambezi (Figure 93). In the upper layer of bottom sediments (sands) the bitumoid content
decreases in the pelagic direction. The boundary for the sharp drop of bitumoid content
is the upper part of the continental slope (Figure 93). This is, evidently, bound up with
the fact that more conservative polymerized organic matter is accumulated in bottom
sediments of deep water zones (Romankevich, 1977).
Humic acids are present in almost all samples of bottom sediments except for sands.
Variations of content and composition of humic acids in pelite muds in the direction river-
ocean are observed on the section of the "Limpopo river mouth-ocean" (Danyushevskaya
and Romankevich, 1987). The average content of humic acid in the bottom sediments of
the shelf is equal to 0.56%, converting into dry sediment, and 17.8% of organic matter.
The deep water sediments contain about 10 times less humic acids (0.5% converting into
166 Chapter4
dry weight and 1.7% of organic matter) which is caused by polymerization of deep water
organic matter and humic acids transformation into non-soluble organic matter, which is
stable to decomposition (Danyushevskaya and Romankevich, 1987).
Concentration of lignin in the surface layer (0-5 m) of bottom sediments on the section
"Limpopo river-ocean" varies from 0.4 to 1.8 mgC/l, or 7-9% of organic matter (Bobyleva,
1982). High concentrations of lignin are typical for bottom sediments in the Limpopo
river mouth region. Content of lignin in bottom sediments drops sharply toward the
ocean (converting into dry weight), but at the same time its proportion in organic matter
composition increases.
4.4. Conclusions
The river-sea system may be clearly subdivided into three groups by organic matter
composition: river waters, estuary waters and ocean waters. In the direction river-ocean
we observe in suspension the following: a decrease of content of most labile components
(amino acids and particulate carbohydrates), a change of ratio of amino acids groups
(increase of content of neutral amino acids and decrease of content of main amino acids)
and of their individual composition, composition of particulate carbohydrates (increase of
share of carbohydrate-like compounds most resistant to decomposition, and a decrease of
content of bitumoids (first of all at the cost of bitumoid Acl), transformed, evidently, into
"residual" organic matter (humines) resistant to decomposition. Thus, the typical process
of particulate organic matter transformation in the direction "sea-estuary-ocean" is the
decrease of reactive compounds and the increase of a proportion of biologically resistant
organic matter (humines).
The border of river run-off effect on the particulate organic matter composition in the
river-sea system can be determined by a sharp change of organic matter composition,
change of structure and concentrations of particulate organic matter components.
Absence of humic acids is typical for the estuary and river particulate organic matter;
consequently, the process of particulate organic matter transformation towards the forma-
tion of geopolymers of humic acids type (humification) is not characteristic for particulate
organic matter of the river-sea system.
The predominating process of organic matter transformation in terrigenous muds in
the direction river-sea in both the equatorial humid zone and the northern humid zone is
dehumification-huminization.
Two types of bottom sediments, terrigenous sands and muds, are separated in the river-
sea system, which testifies the existence of two types of bitumoid Acl, the composition
formation of which is not determined by the organic matter source, but by the sedimentation
medium and by the bond with the mineral part of the sediment.
The typical process of organic matter composition transformation in the line "sus-
pension-bottom sediments" in the estuary, as in the river, is humification-debituminization.
The typical process of transformation of organic matter composition of sands in the
river-sea system is debituminization and the increase of the proportion of humines of
organic matter composition. Organic matter of estuary sands, as that of river sands, are
Transformation of Particulate Organic Matter 167
characterized by the absence of humic acids, which testifies that humification of organic
matter does not take place in coarse-grained bottom sediments, due to the quick fracture of
relatively labile compounds which are able to be transformed into geopolymers of humic
acids type.
The boundary separating bottom sediments with river forms of organic matter from
sediments with oceanic forms of organic matter may be determined by the change of
organic mater composition of bottom sediments.
The boundary of transition from river to sea (or ocean) forms of organic matter is
clearly seen by the change of content of amino acids, humic acids, bitumoid Acl and
Aal.ben in organic matter of bottom sediments. The location of this boundary in relation
to the distance from the river mouth is determined by the value of river run-off and the
hydrodynamics of waters adjoining the river mouth, and therefore is different for each
estuary or area of river and sea water intermixture.
Summary Conclusion
Consideration of the problems of the geochemistry of organic matter washed out by river
run-off into the ocean and into the system "river-area of river and sea water mixing-sea"
made it possible to obtain new data on the content and distribution of organic matter
in rivers and areas of sea and river water mixing, as well as to determine the general
regularities and peculiarities of organic matter in the river-sea system and its effect on the
environment.
The main mass of organic matter is transported by rivers into seas and oceans in
a dissolved form (60-90%). The analysis of data on the quantity of dissolved and
particulate organic matter, transported by river run-off into seas and oceans, leads to the
conclusion that distribution of river dissolved and particulate organic matter streams is
dependent on climatic zonality. The greatest fluxes of dissolved and particulate organic
matter are typical for rivers of the equatorial humid zone, where they are equal to 75.8
and 90.2%, respectively, of the total quantity of dissolved and particulate organic matter
annually transported into seas and oceans by rivers of the world, or 0.204 x 109 tJyear and
0.184 x 109 tJyear, respectively. The climatic zonality is also revealed by the distribution
of relative concentrations of Cd and CP in world rivers.
High concentrations of Cd are typical for rivers of the northern humid zone, which
is bound up with the delivery of organic matter, of mainly humic genesis, from soils
of taiga-forest, forest-tundra and tundra zones. Relative increases of particulate organic
matter proportions in river waters takes place in mountain rivers and it is bound up with
a plentiful supply of suspended particles in river water. The highest concentrations of
particulate organic matter are found in rivers of the equatorial humid zone with complex
mountain-type relief of water accumulating basins (rivers of south-east Asia, etc.).
Seasonal variety of concentration and composition of river organic matter is bound up
with climatic peculiarities of the region, which control the development of ground plants.
The highest concentrations of organic matter in river mouths of the northern and
moderate humid zones are observed during the spring flood periods. In rivers of the
168 Chapter4
northern humid zone, high concentrations of CP also occur in winter, due to the low rates
of particulate organic matter destruction under conditions of low water temperature.
The distinctive peculiarity of dissolved and particulate organic matter distribution along
river beds, which are not subjected to anthropogenous pollutions, is the absence of clearly
expressed external concentrations of dissolved and organic matter. Just such a regularity
was revealed in the main bed of the Amazon, where we measured concentrations of Cd
and CP at the extent of 2000 km from the place of confluence of So limo ins and Negro
rivers to the Amazon river mouth. The main part of river water dissolved organic matter
(60-80%) is made up of decompositionally resistant geopolymers of humic acids type,
the source of which is soil (Table 51). The content of labile components (amino acids,
carbohydrates) in the majority of rivers of the world is equal to 30% (in total) of dissolved
organic matter and 15% of particulate organic matter.
The process of humification in the river-sea system in the line "suspension-bottom
sediments" only takes place in terrigenous muds. Humification of organic matter is not
observed in suspension, or in terrigenous sands due to the rapid destruction of the labile
compounds that are potentially able to form geopolymers of humic acids type under
sharply oxidizing conditions (Figure 83).
The study of organic matter transformation processes in river waters and bottom sedi-
ments revealed a number of regularities. The distinctive feature of organic matter transfor-
mation on the line "suspension-bottom sediments" is debituminization, i.e. utilization of
bitumoid components, especially prevailing in suspension, in the process of diagenesis on
the surface of bottom sediments (Figure 83). In this case, bitumoids are transformed into
insoluble complexes (humines) or sorptional complexes with humic acids (Romankevich,
1977). Absence of humic acids in the suspension testifies to the fact that humic acids are
mainly formed in bottom sediments in situ.
Nevertheless, it is impossible to exclude a principal possibility of the delivery of soil
humic acids to the surface of bottom sediments by the route: soils - river water - plankton
- products of activity and destruction of plankton - bottom sediments. Under certain
conditions, humic acids dissolved in water may be the source of food for water organisms
(Spitzy et at., 1991), and consequently get into the food chain and be buried in bottom
sediments during the process of biosedimentation.
Comparison of the data on composition of organic matter of river terrigenous muds of
the northern and equatorial humid zones, shows that the intensity ofhumification processes
of organic matter in bottom sediments is determined by the climatic zone. The process of
organic matter humification in river terrigenous muds of the northern humid zone occurs
less activity than under conditions of tropical climates. In river terrigenous muds of the
equatorial humid zone, conditions for organic matter humification are more favourable
than that in respective granulometric type of sediments at northern latitudes due to the
high temperature of the water (average 29°C over the whole year) and more active work of
micro-organisms and bottom fauna on the transformation of organic matter in the surface
layer of bottom sediments, leading to organic matter humification.
Independently from the climatic and circum-continental zonality of sedimentation in
the river-sea system, we separated two types of organic matter, bound up with sands and
terrigenous muds respectively. Organic matter of sands differs from organic matter of
Table 51. Transformation of organic matter in the river-sea system (Semenov, 1967, 1971; Romankevich, 1977; Srrrirnov et al., 1978; Varshal
et al., 1979; Artemyev, 1981; Artemyev and Danyushevskaya, 1988; Seifert and Ittekot, 1985; Ittekot et aL, 1982a; Degens and Ittekot, 1985;
Ertel et al., 1986).
% of Organic Matter
Corg Amino- Carbo- Hurrric Bitumoids "Residual"
Object of research content acids hydrates substances ACl Aal.b. organic matter
~
.,~
0\
'-0
170 Chapter 4
Table 52. Composition ofbitumoid Ac. (%) in bottom sediments of the river-sea
system.
MUDS
Amazon river 18.3-30.2 61.8-69.3 8.1-12.7 2:6:1
25.6 65.5 10.1
North Dvina 20.4-23.1 60.7-67.9 10.1-11.0 2:6:1
21.8 64.3 10.5
Amazon estuary 27.841.6 47.7-59.6 4.8-12.2 3:6:1
32.5 54.1 9.8
SANDS
Amazon river 39.9-52.0 40.9-43.4 5.3-16.0 4:4:1
4S.l 42.1 10.7
North Dvina 41.6-62.9 33.7-S2.7 2.5-6.0 12:10:1
SI.O 43.7 4.4
Dvinsky Bay Sl.6 3S.4 12.8 4:3:1
muds by the absence of humic acids, higher content of bitumoids and "residual" organic
matter, as well as the composition of bitumoid Ac\ (bitumoid Ac\ of sands contains more
oils, see Figures 83 and 84, and Table 52). The difference of composition of organic
matter of terrigenous sands and muds and, in particular, of the composition of bitumoid
Ach are connected with conditions of organic matter formation in the surface layer of
bottom sediments, their relationship with the mineral part of sediments, as the "medium of
inhabitance" and of micro-accumulations of organic matter, supplied to bottom sediments
or with a suspension or formed in situ with participation of bottom-dwelling fauna and
micro-organisms.
It is known that processes of sorption of organic matter by clay minerals in terrigenous
muds help to preserve organic matter against micro-biological attack in the early stages
of diagenesis. In sands, particles of organic matter are not bound with the mineral part
of sediments as in clay muds, and are, therefore, subjected to mechanical destruction and
biodegradation.
Being supplied to the sea or ocean medium with river run-off, dissolved and particulate
organic matter are subjected to complex transformation under the effect of physico-
chemical and biogeochemical processes in the area of river and sea water intermixture.
The data of natural observations in the river estuaries of various climatic zones of the Earth,
as well as the results of experiments on mixing filtered river and ocean waters showed
that the process of dissolved and particulate organic matter transformation occurs under
the action of mainly physico-chemical processes (flocculation, adsorption-desorption) at
all stages of water intermixture. This process goes on most intensively in waters with
a salinity of 5-10%0. Performed calculations, statistical processing of the obtained data
Transformation of Particulate Organic Matter 171
showed that Cd and CP behaviour in the area of river and sea water intermixture does not,
as a rule, correspond to the line of simple dilution and has a "non-conservative" character
as a result of dissolved organic matter transition into suspended form and vice versa, into
the dissolved form, at various stages of river and sea water intermixture.
Estimation of river organic matter losses during the mixing between river and ocean
waters is given by means of our model on the example of the Amazon estuary: for
dissolved organic matter 75%; for particulate organic matter 80%. If it is assumed that
such values of losses are, on the whole, typical for river and sea water intermixture areas
we can infer that every year 153 x 106 tons of river Cd and 37 x 106 tons of river CP are
delivered to the ocean pelagic zone and 51 x 106 tons of Cd and 147 x 106 tons of CP
respectively remain in the river water and sea water mixing area.
The behaviour of organic matter and a number of micro-elements (copper, zinc, nickel,
chromium) in river and sea water mixing areas have a similar intercombined character,
dependent on the salinity of the waters, which testifies to their migration in the river-sea
system in the form of complex compounds "organic matter-metal".
If physico-chemical properties determine the behaviour of dissolved and particulate
organic matter in the case of the mixing of fresh and salt water, and are associated with
variation of water salinity, the biogeochemical processes predetermine the transforma-
tion of organic matter going in two directions "river-estuary" and "suspension-bottom
sediments".
The basic trend of particulate organic matter composition transformation in the direction
river-ocean is "huminization" or decrease of concentration of the most reactive, labile
compounds (amino acids, carbohydrates), content of bitumoids (primarily at the cost of
bitumoids Ac]) and increase of chemically and biologically resistant organic matter.
The dominating process of organic matter transformation in terrigenous muds in the
direction river-sea, in both the northern humid zone, and in the equatorial humid zone, is
"dehumification-huminization", and in sands it is "debituminization-huminization".
The higher humic acids content in terrigenous muds of the Amazon estuary, in com-
parison with the North Dvina estuary, testifies that most active humification processes are
characterized by terrigenous muds of equatorial humid zone.
The characteristic process for the line "suspension-bottom sediments" (terrigenous
muds) in estuaries and also in rivers, is "debituminization-humification".
The boundary of river run-off effect of organic matter composition in the river-sea
system, separating the medium with river and ocean types of organic matter, may be
determined by variation of the ratio of particulate organic matter components and organic
matter of bottom sediments in the direction "river-estuary-ocean". This makes it possible
to forecast the remoteness of propagation of the main mass of organic matter, including
pollutions, in seas and oceans that has the main practical value, and is very important for
solving a number of economical problems (Figures 82 and 84).
As it is known, the main regularity of Corg distribution in oceanic sediments is the
circum-continental localization of concentrations of Corg (Romankevich, 1977). It is
expressed by the proximity of high content of Corg to periphery zones of oceans, to
sediments of bays, lagoons, etc. Especially large masses of Corg are accumulated in
zones of sedimentary material run-off by rivers of South and South-East Asia and West
172 Chapter 4
Africa (more than 200 g/m2/looO years (Romankevich and Bobyleva, 1990)) for which
largest streams of river dissolved and particulate organic matter are typical. The maximum
reserves of oil in delta bottom sediments were found here, at tropical latitudes (Geodekyan
et al., 1988).
Thus, we may state that the regional peculiarities of river organic matter accumulation
in river mouth areas of seas and oceans, typical for the geological past, also remain at
present.
It is known that very favourable conditions for accumulation and relatively fast depo-
sition of muds enriched with organic matter and the formation of various forms of sand
bodies exist in river-mouth regions of seas and oceans.
Bottom sediments most favourable for oil formation are accumulated under conditions
specific to bays and deltas. These bottom sediments were called "delta-estuary" (Veber et
al., 1960). All the required prerequisites for the subsequent generation, accumulation and
preservation of oil and gas are created here. Thick layers of terrigenous rocks with good
reservoir properties and enriched with organic matter are accumulated in the river-sea
zone.
Numerous investigations prove the regular relationship of the largest oil fields with
avandelta deposits of paleorivers. The river valleys of many modern and paleorivers
coincide in their main features (Volga, Don, Dnieper, Ob, Orinoko, Missuri, Mississippi,
Ganges, Brakhmaputra, etc.).
An exclusive role of delta areas of palaeorivers in oil-and-gas accumulation is confirmed
by the following data: the productivity of delta deposits was revealed in more than 40 oil-
and-gas bearing basins of the world, and about 1500 hydrocarbons accumulations were
discovered among these deposits. Collectors (reservoirs) of deltaic origin in basins of
passive peripheries of continents contain more than 1010 tons of oil and almost 7 x 1012 m3
of gas. For example, in basins located in the zone of transition from the Phillippine
Arc to the continent of Asia, deltaic sediments become the main oil-and-gas-containing
formations: they contain 9 x 108 tons of oil and 1.1 x 1012 m3 of gas (Geodekyan et al.,
1988).
Investigation of modern biogeochemical processes in the river-sea system expands our
understanding of processes for organic matter transformation in paleorivers mouths. Only
as a result of studying physico-geographical, geochemical and biological processes going
on in modern river mouths is it possible to explain the reasons for high productivity of
deposits in these areas, then subjected to deepening to an optimal depth, corresponding to
the main stage of oil-and-gas formation (Markovsky, 1981).
Thus, the study of specific features of organic matter behaviour in the river and sea water
intermixture area and biogeochemical processes in the river-sea system is closely bound
up with problems of oil-and-gas formation. The modern estuaries and river mouth sections
of rivers are the natural polygons, the study of which will help our better understanding
of conditions for formation of oil fields in the distant parts.
Works on the geochemistry and biogeochemistry of organic matter in the river-sea sys-
tem are also of doubtless practical interest in connection with the extremely unfavourable
ecological situations which exist in mouths of many of the largest rivers on the territory
of some countries.
Transformation of Particulate Organic Matter 173
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INDEX
accumulation 4, 7,69,77 sediments xi, 2, 3, 23, 26, 35, 36, 59, 60-62,
adsorption 31, 77, 82, 83, 94, 104, 107, 108, 113, 64-66,69-73,95, 151, 154-159, 165-168,
130, 133, 136, 142, 144, 147, 149, 158, 170 170-173
aggregates 83, 112, 142
aldehyde 64, 66-69, 73 canyon 154
aminoacids 3, 35, 49-54, 56, 70, 151, 166, 169 carbohydrates 3, 7, 51, 55, 61, 70, 152, 153, 163,
aminosugars 35 166, 168, 169
antbropogenous dissolved 51, 123, 141, 143, 150
pollution 21,130, 142, 168 particulate 51, 141, 143, 150, 152, 163, 164
sources 32 carbonic acid 81
aromatic compounds 61 cellulose 155
area chemical interaction 78
of mixture (mixing, intennixture) of waters 88, composition 6
129,134-136, 141, 157, 167, 168, 171 degradation 72
asphaltenes 61 processes 75, 77
atmospheric(al) transfonnation 76
dust 165 chromatography 3, 153
precipitations 4, 6, 79, 83, 85 chlorophyll 103-105
avalanche type of sedimentation 88 clay minerals 72, 119
climatic zonality I, 8, 167, 168
bacteria 31, 32, 47, 109 zone I, 8, 21, 22
bacterial 2 peculiarities 21
barrier geochemical ix, x, 77, 158 coagulation 81, 83, 109
behaviour colloid(s) 46, 47, 81-83, 112, 128
conservative 81, 100 colloidal substances 48, 82, 83
non-conservative 81, 100, 107, 128, 171 consumers 86
of dissolved compounds 81 continental slope 15, 154, 165
inorganic compounds 82
metals 112, 113 debituminization 71, 153, 156, 157, 166, 168, 171
microelements 131, 171 decomposition 6, 70, 153, 155, 166
nitrates 81 delta 15, 88, 110, 172
organic matter (carbon) I, 83, 97, 100, 108, dehumification 155, 158, 166, 171
109,113,115, 120, 121, 123, 127-129, 138, deposits 172
142,145,148,158,159, 171 deposition 127
phosphates 81, 96 desorption 82, 83, 102, 103, 107, 108, 115, 130, 142,
benthos 7, 13, 156 144, 149, 153, 160, 170
biodegradation 55, 56, 61, 66, 72, 73, 170 destruction 6, 61, 66, 72, 158, 163
biogeochemical processes ix, x, 55,151,170-172 differentiation
biogenic elements 31, 43, 44,84,85,106 mechanical 95
bioproduction 31, 85 mineralogical 95
bioproductivity 39, 91 dilution 81, 100, 128, 171
biosedimentation 168 dispersion 46, 95
bitumoid 37, 56, 59-61, 63, 72, 149, 153-158, 165, double electric layer 82
166,168-171 drainage 6, 39
blooming of algae 104
bottom waters 34, 35, 43 ecological groups 85
187
188 Index
peculiarities 21 period 39
ecosystem 8, 87 phase 2
estuaries types 74 regime 136, 137
estuary x, xi, 6, 15, 35-37, 47, 64, 68-70, 74-77,
82-87,95-97,104,105,151,153-155,171- ionic run-off 17
173 composition 78
interaction
fauna 8,170 between river and sea waters 136
flocculation 82, 83, 98,102-104,107,108,115,122, of organic matter and microelements 112, 113
123, 128, 130, 133, 135, 136, 142, 144, 147, interrelation 130
149,153,160,170
floccules 82,98,99, 103, Ill, 112, 130 labile compounds 55, 70
flood 2, 10, 11, 23, 24, 29, 39-41, 137, 138, 141, lignin 3, 61, 64, 66-69, 71, 73, 155, 163, 164, 166
167 derivatives 68-70
plains 11 liquid run-off 16, 87
plain soils 10, 13 lipids 61, 163, 164
flora 8 living substance 7
flux 34 low water season 89
formation 8, 82, 128
fresh water drainage 77 macroalgae 86
fresh and salt waters intermixture 78 macrophytes 31-33, 49, 64, 86, 87
fulvic acids 9, 10, 12,47, 49, 56--58, 70 marginal seas 20, 87
microbial activity 6
geochemistry x, 3 microelements 1, 3, 5, 43, 82, 111-114, 129, 130,
geographical zonality 8 132, 134, 136
geopolymers 153, 158, 166--168 microorganisms 6--9, 55, 71, 72, 84, 86, 154, 168
grass 49 migration xi, 17
granulometric composition 95 mineralization 4, 70
growth of phytoplankton 81 mixing between fresh and salt waters 142
mixing (intermixture) of (river and sea) waters x, 78,
heavy metals 96 80, 99, 104, 110--114, 117, 119, 121-123,
heterotrophic organisms 46 127-130, 133, 141-143, 167, 171
high water 94 monosaccharides 153
higher plants 59, 61, 79 mountain rivers 21, 25, 55, 144
horizontal distribution 25
gradients 91 negative charge 82
humic acids 3, 9-11,13,37,49,50,57-61,70,71, nitrates 44, 81, 96, 109, 115
153, 155, 156, 158, 165-168, 170 nitrogen 7, 10,24,34,38,43, 154, 155, 157
compounds 47, 50 nutrient substances (salts), nitrients 11,31,81, 109,
substances 13,31,56--59, 100, 112, 167, 169 117
humid zone 15, 17, 18,40,47,49,72,156,166--168,
170,171 oil (and gas) formation 89, 172
humification 4, 58, 60, 72, 153, 156, 166--168 accumulation 172
huminization 153, 166, 171 oil reserves 16
humus 7-13, 13,38,47 oligosaccharides 152, 153
hydrocarbons 7, 13, 63, 172 opthical characteristics 94, 95, 104
hydrochemical boundary 78 organic matter ix, 1,6,9, 13, 36, 39, 47, 49, 70, 72
parameters 79, 88 accumulation 170
peculiarities 130, 139 a1lochtonous 50
regime 4, 79 analysis 3
hydrodynamics 157 antbropogenous 83
hydrodynamic regime 77, 88 colloidal 47, 82, 128
facotrs 81 composition 49, 55, 59, 152, 154-157, 164, 165
hydrological factors 128 consumption 50
front 135, 137 decomposition 39
Index 189