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2nd edition
Fatty Alcohols
Anthropogenic and Natural Occurrence in the Environment
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-FP001

     
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 View Online

Fatty Alcohols
Anthropogenic and Natural Occurrence in
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-FP001

the Environment
2nd edition

By

Stephen M. Mudge
Norwegian Institute for Air Research, Kjeller, Norway
Email: [email protected]

Scott E. Belanger
Central Product Safety, Procter & Gamble, USA
Email: [email protected]

and

Paul C. DeLeo
Formerly American Cleaning Institute, Washington DC, USA
Integral Consulting Inc., Annapolis, MD, USA
Email: [email protected]
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-FP001 View Online

Print ISBN: 978-1-78801-362-8

PDF ISBN: 978-1-78801-384-0
EPUB ISBN: 978-1-78801-421-2

A catalogue record for this book is available from the British Library

© American Cleaning Institute (ACI) 2019

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Preface

Fatty alcohols are widespread in the environment; they are produced by a

very wide range of organisms including bacteria, plants and animals. Typical
chain lengths for these compounds are from 10 to 30+ carbons and are usu-
ally of an even length. Approximately 2.7 million tonnes of these compounds
were also manufactured industrially from either natural fatty acid sources
or from petroleum derived carbon in 2016. The second edition of this book
updates their environmental occurrence, fate and behaviour with new data
and presents new information on their occurrence in wastewaters and their
hazard assessment. The principal focus of past research has been on the
natural production, which occurs in all living organisms from bacteria to
man, and the profiles and concentrations of these compounds in water, soils
and sediments. Their relatively non-polar nature means they are principally
associated with solid phases (e.g., sediments) rather than dissolved in water.
The major biological synthetic pathway is from the reduction of fatty acids,
through aldehyde intermediates, to fatty alcohols and in many organisms to
esters with fatty acids to form waxes. These waxes are used by organisms for a
variety of purposes from the prevention of desiccation in the terrestrial envi-
ronment to energy reserves in the marine environment. They are ubiquitous
and occur in most environments around the world including the deep ocean
and in sediment cores.
Due to the nature of the synthetic pathway using acetyl-CoA, most fatty
alcohols are of an even chain length. Terrestrial plants utilise fatty alcohols
as waxy coating and these compounds are dominated by long chain moieties
with chain lengths from C22 to C32. In contrast marine organisms synthe-
sise smaller compounds with peak chain lengths of C14 to C16. Bacteria also
produce fatty alcohols but these can also be odd chain lengths and contain
branches. This aspect of their occurrence enables them to be used as bio-
markers for organic matter sources.

Fatty Alcohols: Anthropogenic and Natural Occurrence in the Environment

2nd edition
By Stephen M. Mudge, Scott E. Belanger and Paul C. DeLeo
© American Cleaning Institute (ACI) 2019
Published by the Royal Society of Chemistry, www.rsc.org

v
 View Online

vi Preface
As well as their natural production and occurrence, fatty alcohols are also
utilised in detergent formulations principally as sulfates, ether sulfates or
polyethoxylates. The analytical method preferred by contemporary envi-
ronmental scientists used to measure the concentration of the ethoxylates
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-FP005

involves direct derivatisation with a pyridinium complex and quantification

via LC-MS (liquid chromatography-mass spectrometry). This technique will
detect free fatty alcohols as well as the ethoxylates but will not detect any of
the bound alcohols such as the waxes. To detect this group, a saponification
step is required. This second method in combination with the LC method
will detect all of the ethoxylates and may be considered a good measure of
the total fatty alcohols present in the system.
The concentration of individual fatty alcohols in the environment ranges
from low values in old deep cores and the open ocean floor (undetectable to
12 ng g−1 DW for C16) to high values near natural sources and especially in
suspended particulate matter (2.7 mg g−1 DW for C16); this is almost a fac-
tor of 106 difference in their concentrations. The short chain compounds
are more readily degradable than the longer chain compounds and in many
cases are removed first as a food source for bacteria. The longer chain com-
pounds may also degrade to short chain compounds with time but, in gen-
eral, the >C20 class of alcohols are better preserved in sediments and soils
rather than the <C20 class.
The different compound profiles for each source has made them suitable
as biomarkers and the use of multivariate statistical methods can clearly
distinguish compounds from each potential source as well as sites. Princi-
pal component analysis (PCA) is particularly useful in this regard. Signature
analysis using partial least squares (PLS) analysis has been used successfully
when the marine/terrestrial sources are used to discriminate between sam-
ples, however, due to the commonality of fatty alcohols present in detergent
formulations and the natural environmental alcohols, source partitioning
on the basis of compounds alone is not as successful. When ascribing pro-
portions to such sources, a different approach, such as stable isotopes, may
be more appropriate. There is a clear difference between the different natural
and industrial sources when using 13C and 2H to develop chemical signatures
of the compounds. Such work has indicated that the aqueous discharges from
WWTPs do not contain the same compounds that entered with the influent.
The ecotoxicity testing of fatty alcohols has shown that they are relatively
benign in the environment due to low environmental exposures. Free fatty
alcohols have been shown to possess very rapid and complete biodegrada-
tion. Fatty alcohols lack effects on genotoxicity, reproductive and develop-
mental toxicity, carcinogenicity. Routes of oral, ingestion, inhalation, and
skin penetration have all shown good margins of safety for human health.
The first edition of this book in 2008 sprang from a multi-year review of the
occurrence, behaviour and use of fatty alcohols to inform the registration of
such chemicals through the REACH process in the EU. It became apparent
that there had been no synthesis of the available environmental data and
the review and subsequent book presented the state-of-the-art at that time.
 View Online

Preface vii
However, the initial review did highlight some aspects of fatty alcohol envi-
ronmental chemistry that were lacking and these were posed as “what we
don't know” sections in the first edition of this book. Recognising this lack
of information, the American Cleaning Institute (ACI) funded several proj-
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-FP005

ects targeting the areas where data and knowledge was lacking. Since 2008,
significant changes have been made in the production and formulation of
commercial products and this has been supplemented with data from mar-
keting data for thousands of products containing fatty alcohol derivatives;
the fate of these down-the-drain products in wastewater systems has been
substantially enhanced and the use of compound specific stable isotope
methods has enabled differentiation between all the pertinent sources. Addi-
tionally, there has been a European Mandate (M/491) to grow the size of the
bio-based economy in Europe. This includes surfactants, such as the fatty
alcohol derivatives, and has led to new work to assist in provenancing. These
new additions substantially update the reader with new data and presents a
comprehensive view of our knowledge after another nine years of research.
Stephen M. Mudge, Scott E. Belanger and Paul C. DeLeo
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-FP009

Acknowledgements

The authors are deeply appreciative of discussions and research collaborations

with many individuals over the past several years that have culminated in the
contents of this book, We especially appreciate the interactions with Hans
Sanderson (Aarhus University), Kathy Stanton and Rich Sedlak (American
Cleaning Institute), Charles Eadsforth (Shell Global Solutions), Thorsten
Wind (Henkel), Allen Nielsen (for the chapter on industrial production in
the first edition) and Andreas Willing (Cognis). Funding and collaborations
across a variety of professional and industry associations are acknowledged
including the ACI, ERASM (European Risk Assessments and Surfactants
Management), APAG (European Chemicals and Allied Products Group), and
the ICCA Aliphatic Alcohol Consortium.

Fatty Alcohols: Anthropogenic and Natural Occurrence in the Environment

2nd edition
By Stephen M. Mudge, Scott E. Belanger and Paul C. DeLeo
© American Cleaning Institute (ACI) 2019
Published by the Royal Society of Chemistry, www.rsc.org

ix
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-FP011

About the Authors

Stephen Mudge developed the world's first degree in environmental forensics

during 20 years in academia. While at Bangor University, he routinely used
fatty alcohols as indicators of the source of organic matter in marine and
estuarine sediment samples. It was this use of these compounds that led him
to review their production and occurrence in the environment in response to
the need to understand their fate. He later worked as a consultant but is now
at the Norwegian Institute for Air Research (NILU) conducting environmen-
tal investigations into source identification and allocation for contaminants.
He is a Fellow of the Royal Society of Chemistry and Chairs the International
Network of Environmental Forensics.
Scott Belanger is a Research Fellow in The Procter & Gamble Company
corporate environmental safety organization. His research spans a wide
range of topics including understanding the effects of consumer product
chemicals in the environment at the levels of the organism to the ecosystem.
He has assisted in several efforts to assess the environmental risk of alco-
hols and alcohol-derived surfactants in recent years frequently working with
trade associations, academic partnerships, and the regulatory community
on these affairs.
Paul DeLeo is a Principal at Integral Consulting Inc. From 2007 to 2017,
he was Associate Vice President for Environmental Safety at the American
Cleaning Institute (Washington, D.C.), an industry trade association of
more than 150 member companies manufacturing consumer and commer-
cial cleaning products and their ingredients for the $30 billion US cleaning
products market. He directs research supporting the environmental safety
of cleaning product ingredients and develops tools to further advance the
science of consumer product ingredient safety. He has a particular inter-
est in the development of human and environmental exposure assessment

Fatty Alcohols: Anthropogenic and Natural Occurrence in the Environment

2nd edition
By Stephen M. Mudge, Scott E. Belanger and Paul C. DeLeo
© American Cleaning Institute (ACI) 2019
Published by the Royal Society of Chemistry, www.rsc.org

xi
 View Online

xii About the Authors

tools for chemicals in products. Over the past twenty years, his career has
been directed at the safety of chemicals in a number of applications such
as food additives, drugs, pesticides and other consumer product uses,
including eight years working as a regulator at the US Food and Drug
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-FP011

Administration.
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-FP013

Contents

Chapter 1 Definitions  1

1.1 Names and Structures  1

1.2 Physicochemical Properties  3
1.2.1 Solubility Versus Chain Length  3
1.2.2 Partitioning (Kow) and Sediment
Associations  5
1.3 Summary  8
References  8

Chapter 2 Biological Synthesis  11

2.1 Type I Fatty Acid Synthesis  11

2.1.1 Unsaturated Chains  13
2.2 Type II Fatty Acid Synthesis  14
2.2.1 Unsaturated Compounds  14
2.2.2 Branched Chains  16
2.3 Fatty Acid Degradation  17
2.4 Fatty Acyl-CoA Reductase (FAR)  18
2.5 Synthesis from Carbohydrates (Copepods)  20
2.6 Summary  21
References  21

Chapter 3 Occurrence in Biota  24

3.1 Bacteria  25
3.2 Chlorophyll Side Chain (Phytol)  26
3.3 Marine Plants  27

Fatty Alcohols: Anthropogenic and Natural Occurrence in the Environment

2nd edition
By Stephen M. Mudge, Scott E. Belanger and Paul C. DeLeo
© American Cleaning Institute (ACI) 2019
Published by the Royal Society of Chemistry, www.rsc.org

xiii
 View Online

xiv Contents
3.4 Terrestrial Plant Waxes  28
3.5 Mosses and Other Peat Forming
Plants  30
3.6 Marine Animals  31
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3.7 Insects  33
3.8 Birds  34
3.9 Summary  35
References  35

Chapter 4 Consumer and Cosmetic Product Uses and

Production  40

4.1 Detergent Alcohols Manufacture  40

4.1.1 Oleochemical Based Alcohols  41
4.1.2 Oleochemical Fatty Alcohols  41
4.2 Petrochemical Based Alcohols  45
4.2.1 Normal Paraffin  45
4.2.2 Internal Olefins  45
4.2.3 Conventional OXO Alcohols Based on
Internal Olefins  45
4.3 Alcohols Based on Ethylene  46
4.3.1 Ziegler Ethylene Growth Process  46
4.3.2 Ziegler Alcohols  47
4.4 Modified OXO Alcohols  47
4.4.1 SHOP (Shell Higher Olefin Process)
α-Olefins  47
4.4.2 SHOP Internal Olefins and Modified
OXO Alcohols  48
4.4.3 OXO Alcohols Derived from
Fischer–Tropsch α-olefins  49
4.5 Summary of Production Methods  49
4.6 Detergent Formulations  50
4.7 Global Production  56
4.7.1 Asia  56
4.7.2 China  58
4.7.3 Japan  58
4.7.4 Southeast Asia  60
4.7.5 Western Europe  60
4.7.6 North America  62
4.8 Usage of Fatty Alcohol-based Consumer
Products  64
4.8.1 Contributions to the WWTP
Influent  69
4.9 Summary  72
References  72
 View Online

Contents xv
Chapter 5 Environmental Transformations  75

5.1 Metabolism of Fatty Alcohols  76

5.2 Natural Degradation  78
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5.2.1 Short Chain Moieties  79

5.2.2 Long Chain Moieties  81
5.3 Degradation Rate Constants  83
5.3.1 Phytol Degradation  84
5.4 Branched Chains  85
5.5 Wastewater Treatment Plants (WWTPs)  85
5.6 Effect of Chemical Associations on
Transformation Rates  87
5.6.1 “Natural” Fatty Alcohols in WWTPs  87
5.6.2 Anthropogenic Fatty Alcohols in
Synthetic WWTPs  88
5.6.3 Faecal Fatty Alcohols  90
5.7 What We Still Don’t Know  90
5.8 Summary  91
References  91

Chapter 6 Analytical Methods  94

6.1 Overview of Methods  94

6.2 Methods for Analysis of Free Fatty
Alcohols (and Ethoxylates)  94
6.3 Environmental Samples  96
6.4 Inter-laboratory Comparisons  98
6.5 Stable Isotope Analysis  99
6.6 Summary  102
References  102

Chapter 7 Environmental Concentrations  104

7.1 The Marine Environment  107

A. Victoria Harbour, BC – Estuarine Surface
Sediments  107
B1. Concepcíon Bay, Chile and B2. San Vicente
Bay, Chile  109
C. Rio De Janeiro – Surface Sediments in a
Contaminated Bay  111
D1. Ria Formosa Lagoon – Surface Sediments  112
D2. Ria Formosa Lagoon – Suspended and
Settled Sediments  114
D3. Ria Formosa Lagoon – Shallow Core
from Intertidal Sediments  116
 View Online

xvi Contents
E. Eastern North Atlantic  118
F. San Miguel Gap, California – Long
Marine Core  118
G. Rio Grande Rise (516F of Leg 72 ODP),
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Brazil  120
H. Falkland Plateau (511 of Leg 71 ODP),
S. Atlantic  121
I. Guatemalan Basin (Legs 66 & 67 ODP),
Central America  121
J1. Continental Slope, SW of Taiwan  122
J2. East China Sea, N of Taiwan  122
7.2 The Terrestrial Environment  124
K. Pasture Land, Southern Australia  124
L. Prairie Zone Soils, Alberta, Canada  125
M. Luray River Catchment, Virginia  125
N. Ohio, Oklahoma and Oregon, USA  131
7.3 UK Studies  136
1. Conwy Estuary – Estuarine
Core (50 cm)  137
2. Mawddach Estuary – Surface
Sediments  139
3. The Menai Strait – Surface Sediments  141
4. Loch Riddon, Scotland – Mid-length
Marine Core  143
5. Clyde Sea, Scotland – Surface Sediments  143
6. Loe Pool, Cornwall – Coastal Lake  145
7. Bolton Fell Moss, Cumbria–Mire  146
8. Lochnagar, Scotland – Mountain Lake  146
9a. Loch Eil, Scotland – a Marine
Core and 9b. Loch Lochy, Scotland – a
Freshwater Core  147
7.4 Summary of Concentrations  149
7.5 Summary  149
References  150

Chapter 8 Using Fatty Alcohols as Biomarkers  154

8.1 Profiles  154

8.2 Stable Isotopes  155
8.2.1 13C Composition  155
8.2.2 2H Composition  155
8.3 Bacterial Biomass  156
8.4 Marine Fauna and Unicellular Algae  157
8.5 Terrestrial Plants  158
8.6 Photosynthetic Activity  159
8.7 Summary  160
References  160
 View Online

Contents xvii
Chapter 9 Multivariate Statistics  162

9.1 Chemometric Methods of Use with

Fatty Alcohols  162
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9.1.1 Principal Components Analysis (PCA)  163

9.1.2 Partial Least Squares (PLS)  169
9.1.3 Polytopic Vector Analysis (PVA)  173
9.2 Summary  176
References  176

Chapter 10 Environmental and Human Safety

Aspects of Fatty Alcohols  178

10.1 Physical Chemistry Relevant to Safety

Assessments  178
10.1.1 OECD SIAR Summary  178
10.1.2 Physicochemical Overview from
the OECD SIAR  180
10.1.3 Conclusions for Characterising the
OECD Long Chain Alcohols Category  180
10.2 Human Health and Risk  180
10.2.1 Uses and Products  180
10.2.2 Hazards for Human Health  183
10.2.3 Exposure Characterisation for
Human Health  184
10.2.4 Risk Characterisation for
Human Health  185
10.3 Environmental Risk  186
10.3.1 Pathways of Environmental
Exposure  186
10.3.2 Environmental Effects  188
10.4 Measurements of Exposure for the
Purpose of Environmental Risk
Assessment  192
10.5 Risk Characterisation in the
Environment  192
10.6 Summary  194
References  194

Subject Index  197

Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-00001

Chapter 1

Definitions

This chapter introduces the family of compounds, how they are referred to, the
likely structures that will be found and their chemistry from an environmental
point of view.

1.1 Names and Structures

Fatty alcohol is a generic term for a range of aliphatic hydrocarbons contain-
ing a hydroxyl group, usually in the terminal or n-position. The accepted defi-
nition of fatty alcohols states that they are naturally derived from plant or
animal oils and fats and used in pharmaceutical, detergent or plastic indus-
tries (e.g. Dorland's Illustrated Medical Dictionary). However, it is possible to
find the hydroxyl (–OH) group in other positions within the aliphatic chain,
although these secondary or tertiary alcohols are not discussed to any great
extent in this book.
The generic structure of fatty alcohols or n-alkanols can be seen in Figure 1.1
and specific examples in Figure 1.2. The value of the n component is variable
and is discussed below.
The range of chain lengths for these n-alkanols can be from 8 to val-
ues in excess of 38 carbons. With such a wide range of chain lengths, the
chemical properties and consequently their environmental behaviour vary
considerably. As well as these straight chain moieties, a range of branched
chain compounds are also naturally produced by micro-organisms in the
environment and wastewater systems. The major positions for the methyl

Fatty Alcohols: Anthropogenic and Natural Occurrence in the Environment

2nd edition
By Stephen M. Mudge, Scott E. Belanger and Paul C. DeLeo
© American Cleaning Institute (ACI) 2019
Published by the Royal Society of Chemistry, www.rsc.org

1
 View Online

2 Chapter 1
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-00001

Figure 1.1 Generic structure of a fatty alcohol – the total number of carbons needs
to be greater than 9–10 to be a “fatty” alcohol; shorter chain compounds
such as ethanol have an appreciable water solubility and are generally
just called alcohols.

Figure 1.2 
Examples of typical fatty alcohol structures. The majority found in nature
are of the straight chain type with smaller amounts of the branched
chain compounds also being present. Secondary alcohols and diols are
relatively uncommon.

branches are on the carbons at the opposite end of the molecule to the
terminal –OH. If the methyl branch is one in from the end of the molecule
(ω–1) it is termed an iso fatty alcohol; if it is two in from the end (ω–2) it is
called an anteiso fatty alcohol. Examples of these branches can be seen in
Figure 1.2.
Most fatty alcohols are saturated in that they have no double bonds
present in their structure. However, there are a limited number of mono-
unsaturated compounds that can be found in nature. The two most common
compounds are phytol (3,7,11,15 – tetramethyl-2-hexadecen-1-ol), an iso-
prene1 derived from the side chain of chlorophyll (Figure 1.3) and a straight
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Definitions 3
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Figure 1.3 The chlorophyll a molecule with the phytyl side chain labelled. Cleav-
age of this chain at the COO– group produces free phytol in the environ-
ment. Eicos-11-en-1-ol or 20 : 1 fatty alcohol, is one of the most frequently
observed straight chain mono-unsaturated alcohol in the environment.

chain C20 alcohol with a double bond in the ω9 position counted from the
terminal carbon (eicos-11-en-1-ol, Figure 1.3).2
There have been occasional reports of polyunsaturated fatty alcohols, but
these are relatively rare3 and tend to be confined to di-unsaturates such as
octadecadienol, 18 : 2. There is a group of isoprenoid lipids that may be found
in bacteria that are essentially repeating isoprene subunits strung together
and terminated by a hydroxyl group.4 These compounds are also uncommon
in environmental analyses and are not reported to any great extent.
Fatty alcohols together with many other groups of compounds have both
systematic and trivial or common names. This trivial name is based on the
length of the alkyl chain and the root is common between aliphatic hydro-
carbons and fatty acids. These names together with the systematic name and
carbon number are shown in Table 1.1.

1.2 Physicochemical Properties

1.2.1 Solubility Versus Chain Length
One of the key factors in determining the environmental behaviour of any
compound is its water solubility; this will determine the partitioning between
solid and solution phases and its ability to be bioaccumulated. Compounds
with low water solubility will be preferentially adsorbed to particulate matter,
Published on 28 September 2018 on https://pubs.rsc.org |

Table 1.1 Names and key properties of fatty alcohols from C4 to C30. The horizontal dashed line indicates the arbitrary division between
alcohols and fatty alcohols.

4
Trivial name Water Predicted Water
(excluding Carbon Molecular Melting Boiling Solubility Solubilityc
Systematic name “alcohol” part) number Weight (D) d20 (g cm−3) point (°C) pointa (°C) (@25 °C) (mg l−1)
Butanol Butyl 4 74.12 0.810 −90 117 91 ml l−1
Pentanol Amyl 5 88.15 0.815 −79 137.5 27 g l−1
Hexanol Caproyl 6 102.17 0.815@25 °C −51.6 157 5.9 g l−1 7671.3
Heptanol Oenantyl 7 116.20 0.819@25 °C −34.6 175.8 1.6 g l−1 1743.6
Octanol Caprylic 8 130.23 0.827 −16 194 0.5 g l−1 400.7
Nonanol Pelorgonyl 9 144.25 0.828 −5 215 0.1 g l−1 94.2
Decanol Capryl 10 158.28 0.830 6.4 232.9 0.04 g l−1 22.9
Undecanol 11 172.31 0.832 15 244 0.008 g l−1 d 5.8
Dodecanol Lauryl 12 186.33 0.831@24 °C 24 259 BMLb 1.6
Tridecanol 13 200.36 0.915 30 278 BML 4.51 × 10−1
Tetradecanol Myristyl 14 214.39 0.824 38 289 BML 1.41 × 10−1
Pentadecanol 15 228.41 0.893 42 BML 4.90 × 10−2
Hexadecanol Cetyl 16 242.44 0.811 49 344 BML 1.90 × 10−2
Heptadecanol Margaryl 17 256.47 0.885 53 BML 8.42 × 10−3
Octadecanol Stearyl 18 270.49 0.811 59 360 BML 4.33 × 10−3
Nonadecanol 19 284.31 0.882 62 BML
Eicosanol Arachidyl 20 298.55 0.88 65 BML 1.93 × 10−3
Henicosanol 21 312.57 68.5 BML
Docosanol Behenyl 22 326.60 0.8 70 BML 1.98 × 10−3
Tricosanol 23 340.63 72 BML
Tetracosanol Lignoceryl 24 354.65 72 BML
Pentacosanol 25 368.68 75 BML
Hexacosanol Cerotyl 26 382.71 73 BML
Heptacosanol Carboceryl 27 396.73 80 BML
Octacosanol Montanyl 28 410.76 81 BML
Nonacosanol 29 424.79 83.5 BML

Chapter 1
Triacontanol Melissyl 30 438.81 87 BML
a
 he boiling point values are quoted at atmospheric pressure.
T
b
BML, below measurement limit.
c
As the water solubility becomes harder to measure, the predicted water solubility is used instead. The values presented here are taken from the ECOSAR model.5
d
At 20 °C.
 View Online

Definitions 5
either settled or suspended in water. These compounds will also partition
into the lipid phase of organisms and would have higher bioconcentration
factors if not off-set by metabolism. The available physicochemical proper-
ties for the fatty alcohol series from C4 to C30 are summarised in Table 1.1.
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-00001

These data are drawn from many sources but principally from the Beilstein
Chemical Database (Elsevier MDL) and ChemSpider (RSC). The density and
melting points in the summary data (Table 1.1) have a degree of uncertainty
about them as some compounds, especially the longer chain and odd carbon
number moieties, are less well studied. The density data are not available
for all compounds. Most of the longer chain compound's data come from
predictions from models such as EPISuite from the US Environmental Pro-
tection Agency.
The short chain compounds (up to C9) have an appreciable water solubility
(Table 1.1) and would not be classified as a “fatty” alcohol as the free com-
pounds are more likely to be in solution than on the solid phase (abiotic or
biotic). Compounds with a chain length greater than 10 carbons are increas-
ingly insoluble in water and will predictably partition to a greater degree
onto the solid phase in the environment as chain lengths increase. Despite
this, there will still be a small amount of the free alcohol in solution at even
longer chain lengths.

1.2.2 Partitioning (Kow) and Sediment Associations

It is usual to measure the water solubility and related factors such as the bio-
concentration factor (BCF) through the octanol–water partition coefficient
(Kow) or its log10 (log Kow). Until recently, there has been relatively little infor-
mation published for measured Kow values for fatty alcohols although there
are some data from estimated from HPLC retention times.6 A summarisation
of data from industry was presented as part of an OECD High Production Vol-
ume Chemicals programme on fatty alcohols.7 Difficulties arise in the mea-
surement of these coefficients due to the hydrophobic–hydrophilic nature of
the different parts of the molecule (Figure 1.4). The hydroxyl group gives that

Figure 1.4 
The –OH group is weakly ionisable to form –O – and H+ and as such will
“dissolve” in water. However, on increasing the alkyl chain length, the
effect of this is diminished and the compound has lower water solubility.
This property does allow the molecule to be used as a detergent, one of
the principal anthropogenic functions of fatty alcohols.
 View Online

6 Chapter 1
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-00001

Figure 1.5 The effect of carbon chain length in fatty alcohols on the log Kow. Data
from Table 1.2.

end of the molecule a degree of water solubility, while the alkyl carbon chain
is hydrophobic. Therefore, these compounds sit at the interface of the octa-
nol and water in the experimental situation and may be called surfactants
(surface active agents) on their own.
The log Kow values for compounds (Table 1.2 and shown graphically in
Figure 1.5) with a chain length greater than C9 are above 4 and are indica-
tive of materials that will be preferentially absorbed to particulate matter.
In most environmental situations, this means the compounds will be asso-
ciated mainly with particles such as settled and suspended sediments. The
negative buoyancy of these particulate materials means they will settle out
to the benthos at some stage and will be transferred to the geosphere. This
partitioning between the solution phase for short chain compounds and
solid phase for long chain compounds may lead to the separation of mix-
tures such that short chain moieties will remain in solution, while longer
chain moieties may settle out. There will also be different degradation steps
possible as materials in the solid phase may enter anaerobic environments
in sediments; this may lead to preservation of some materials and differen-
tial products of degradation.
The bioaccumulation of chemicals tends to increase with decreasing water
solubility and increasing log Kow up to a point; at some critical measure
of molecular size, compounds tend not to accumulate in cells as the com-
pounds are simply too big to pass across the cell membrane. Several cut-offs
have been proposed based on such criteria as the effective molecular diame-
ter,10 the relative solubility in water and octanol,11 the maximum molecular
diameter12,13 or the more widely used molecular weight cut-off of 700 Dal-
tons.14 While the fatty alcohols considered here do not reach this weight,
ethoxylated derivatives used as surfactants might.
The association of fatty alcohols with suspended matter will be of impor-
tance in wastewater treatment plants as incoming compounds may be
 View Online

Definitions 7
a b c
Table 1.2 Octanol–water partition coefficients from ref. 8 , 6 and 9 .
Fatty alcohol Carbon number Log Kow
Butanol 4 0.785a
0.84c
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-00001

Pentanol 5 1.53a
Hexanol 6 2.03a
1.84c
Heptanol 7 2.57a
2.34c
Nonanol 9 3.31b
3.77a
Decanol 10 4.77d
Undecanol 11 4.28d
Dodecanol 12 5.36b
Tridecanol 13 5.26d
Tetradecanol 14 6.03b
Pentadecanol 15 6.24d
Hexadecanol 16 6.65b
Heptadecanol 17 7.23d
Octadecanol 18 7.19b
Nonadecanol 19 8.21d
Eicosanol 20 7.75b
a
 ata from: Tewari et al.8
D
b
Data from: Burkhard et al.6
c
Data from: Hansch et al.9
d
Data from: EPISuite KOWWIN v1.67 estimate (USEPA).

Table 1.3 The mean (±1 standard deviation) partition coefficients (Kd) for fatty alco-
hols with activated sewage sludge suspended in river water.a
Time
(h) C12 C14 C15 C16 C18
1 4100 ± 267 14 700 ± 645 4070 ± 387 34 100 ± 1700 107 000 ± 6330
5 3410 ± 119 12 700 ± 675 3820 ± 183 33 300 ± 1600 90 300 ± 3070
16 3320 ± 276 10 500 ± 167 3590 ± 104 28 600 ± 1720 89 900 ± 1980

30 3100 ± 143 10 200 ± 670 3480 ± 77 27 600 ± 1930 82 400 ± 2970

72 3000 ± 78 8490 ± 916 3080 ± 271 23 800 ± 3160 78 700 ± 5350

a 15
Data from van Compernolle.

removed from the system by partitioning into the solid phase that subse-
quently settles out. Experiments using radio-labelled alcohols with activated
sewage sludge15 measured the time dependent partition coefficients (Kd) for
a range of alcohols typically used in detergent formulations (Table 1.3). The
mean Kd values can be seen in Figure 1.6; the data are presented on a log axis
and a linear relationship can be seen in this figure. These values are rela-
tively high, implying that in such a system, free fatty alcohols will be actively
 View Online

8 Chapter 1
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Figure 1.6 The mean Kd for the even carbon numbered fatty alcohols (data from
Table 1.3). Note that the y-axis has a log scale.

scavenged by the particulate phase and may be removed with the sludge or
associated with suspended solids in wastewater. Thus, alcohols may leave
wastewater treatment plants either bound or unbound (free). It is possible to
demonstrate the fate of fatty alcohols using the wastewater treatment model,
SIMPLETREAT16 (a module in the European environmental distribution
model, EUSES); as carbon chain length increased, the fraction of fatty alcohol
that is degraded by microbes in wastewater declines as the amount sorbed
increases. Itrich and Federle17 postulated that eventually at chain lengths of
16 and greater, the equilibrium desorption controls the biodegradation rate.

1.3 Summary
●● Fatty alcohols found in the environment are principally linear with a
terminal hydroxyl group.
●● Chain lengths from C10 to C38 and beyond may be found in the environ-
ment and may be called “fatty” due to their low water solubility.
●● As the alkyl chain becomes longer, the water solubility decreases lead-
ing to a wide range of octanol–water partition coefficients (Kow).
●● Compounds with a chain length greater than C10 are more likely to be
associated with the solid phase and become coupled with sediments and
soils in the environment. These lower water solubility compounds will
tend to bioaccumulate more than their short chain moieties, although
all may be metabolised by bacteria.

References
1. Y. Chikaraishi, et al., Hydrogen, carbon and nitrogen isotopic fraction-
ations during chlorophyll biosynthesis in C3 higher plants, Phytochemis-
try, 2005, 66(8), 911–920.
 View Online

Definitions 9
2. G. Kattner, et al., Fatty acid and alcohol composition of the small polar
copepods, Oithona and Oncaea: indication on feeding modes, Polar
Biol., 2003, 26(10), 666–671.
3. S. J. Ju and H. R. Harvey, Lipids as markers of nutritional condition and
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-00001

diet in the Antarctic krill Euphausia superba and Euphausia crystallo-

rophias during austral winter, Deep Sea Res., Part II, 2004, 51(17–19),
2199–2214.
4. J. J. Perry, J. T. Staley and S. Lory, Microbial Life, Sinauer Associates, Sun-
derland, Massachusetts, 2002.
5. P. R. Fisk, et al., Environmental properties of long chain alcohols. Part 1:
Physicochemical, environmental fate and acute aquatic toxicity proper-
ties, Ecotoxicol. Environ. Saf., 2009, 72(4), 980–995.
6. L. P. Burkhard, D. W. Kuehl and G. D. Veith, Evaluation of Reverse Phase
Liquid-Chromatography Mass-Spectrometry for Estimation of N-Octa-
nol Water Partition-Coefficients for Organic-Chemicals, Chemosphere,
1985, 14(10), 1551–1560.
7. H. Sanderson, et al., An overview of hazard and risk assessment of
the OECD high production volume chemical category-Long chain
alcohols C-6-C-22 (LCOH), Ecotoxicol. Environ. Saf., 2009, 72(4),
973–979.
8. Y. B. Tewari, et al., Aqueous Solubility and Octanol Water Partition-Co-
efficient of Organic-Compounds at 25.0-Degrees-C, J. Chem. Eng. Data,
1982, 27(4), 451–454.
9. C. Hansch, J. E. Quinlan and G. L. Lawrence, Linear free-energy relation-
ship between partition coefficients and the aqueous solubility of organic
liquids, J. Org. Chem., 1968, 33(1), 347–350.
10. A. Opperhuizen, et al., Relationship between bioconcentration in fish
and steric factors of hydrophobic chemicals, Chemosphere, 1985, 14,
1871–1896.
11. R. Anliker, P. Moser and D. Poppinger, Bioaccumulation of dyestuffs and
organic pigments in fish-Relationships to hydrophobicity and steric fac-
tors, Chemosphere, 1988, 17, 1631–1644.
12. S. D. Dimitrov, et al., Predicting bioconcentration factors of highly hydro-
phobic chemicals. Effects of molecular size, Pure Appl. Chem., 2002, 74,
1823–1830.
13. S. D. Dimitrov, et al., Bioconcentration potential predictions based
on molecular attributes-An early warning approach for chemicals
found in humans, birds, fish and wildlife, QSAR Comb. Sci., 2003, 22,
58–68.
14. Community, E., Second edition of the technical guidance document in
support of commission directive 93/67/eec on risk assessment for new
notified substances. Commission regulation (EC) 1488/94 on risk assess-
ment for existing substances and directive 98/8/EC of the European Par-
liament and of the Council concerning the placing of biocidal products
on the market, Luxembourg (BE), 2003.
 View Online

10 Chapter 1
15. T. Kurevija and N. Kukulj, Global environmental issues concerning.
large scale biodiesel production, Energy and the Environment 2006, ed. B.
Frankovic, Hrvatsko Udruzenje Suncevu Energiju Rijeka-Croation Solar
Energy Assoc., Hrvatska, 2006, vol II, pp. 197–206.
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-00001

16. M. Kah and C. D. Brown, Sensitivity analysis for the Simple Treat model
to simulate fate of chemicals in sewage treatment plants, Water Sci. Tech-
nol., 2011, 63(9), 2052–2060.
17. T. Federle and N. R. Itrich, Fate of free and linear alcohol-ethoxylate-de-
rived fatty alcohols in activated sludge, Ecotoxicol. Environ. Saf., 2006, 64,
30–41.
Published on 28 September 2018 on https://pubs.rsc.org | doi:10.1039/9781788013840-00011

Chapter 2

Biological Synthesis

The biochemical mechanisms that lead to their formation highlighting the

differences between bacteria, that can produce odd chain and branched com-
pounds, with everything else that produces even chain compounds.

The synthesis of fatty alcohols by living organisms is intimately linked to

the production of fatty acids in most cases. In order to understand the types
of fatty alcohols present in the environment, it is necessary to appreciate
the biochemical synthetic pathways that lead to their formation in the first
place.
The formation of fatty acids can progress through two major pathways;
animals, fungi and some Mycobacteria use the Type I synthetic pathway.
In this system, the synthesis takes place within a large single protein unit
and has a single product in the form of a C16 unsaturated fatty acid (palmitic
acid). This system has genetic coding in one location. In contrast, plants and
most bacteria use a series of small discrete proteins to catalyse individual
steps within the synthesis; this is termed Type II fatty acid synthesis.1 These
proteins are genetically encoded in several different locations. Yeasts are
intermediate between these two extremes, where the synthesis activities take
place in two separate polypeptides.2

2.1 Type I Fatty Acid Synthesis

Type I fatty acid synthesis (FAS) occurs primarily in animals. As well as hav-
ing this initial style of fatty acid synthesis, there are a series of subsequent
reactions that lead to the elongation of the primary fatty acid (hexadecanoic
acid, C16) to higher carbon numbers and desaturation mechanisms leading

Fatty Alcohols: Anthropogenic and Natural Occurrence in the Environment

2nd edition
By Stephen M. Mudge, Scott E. Belanger and Paul C. DeLeo
© American Cleaning Institute (ACI) 2019
Published by the Royal Society of Chemistry, www.rsc.org

11
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T7~ nip I Jesus is our Shepherd, mp 3 Jesus is our Shepherd :
Wiping every tear ; For the sheep He bled ; Folded in His bosom,
Every lamb is sprinkled What have we to fear? With the blood He
shed; cres Only let us follow Then on each He setteth Whither He
doth lead, His own secret sign: — To the thirsty desert cres " They
that have My Spirit, Or the dewy mead. These," saith He, " are
Mine." mp 2 Jesus is our Shepherd : mf 4 Jesus is our Shepherd:
Well we know His voice ; Guarded by His arm, How its gentlest
whisper Though the wolves may raven, Makes our heart rejoice !
None can do us harm : Even when He chideth, p When we tread
death's valley, Tender is its tone; Dark with fearful gloom. cres None
but He shall guide us ; cres We will fear no evil, We are His alone. /
Victors o'er the tomb. —Hugh Stowell, 1799-1865
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593 CLEETHORPES 7.6.7.6.7.6.7.6 with Refrain T. Richard

Matthews, 1826-1910 iiifPp^pSpippiip «U-JL taa^^^^^^^ AAA A.
J. fe^i^ ^^f^^p rrrr r B^^^^^gj^ f^-rrTFr u f-rrrP'fJ P ■Sr p r
rrnTfr re/" r r Glo - ry be to Je - sus, Let all His chil-dren AAA £ aa~-
,jj
 jffor tfrg tloung m/ J Again the morn of gladness, The morn
of light, is here; And earth itself looks fairer, And heaven itself more
near, The bells, like angel voices, Speak peace to every breast, And
all the land lies quiet To keep the day of rest. / Glory be to Jesus, Let
all His children say; He rose again, He rose again, On this glad day 1
mf 2 Again, O loving Saviour, The children of Thy grace Prepare
themselves to seek Thee Within Thy chosen place. cres Our song
shall rise to greet Thee, If Thou our hearts wilt raise ; If Thou our
lips wilt open, Our mouths shall show Thy praise. mf 3 The shining
choir of angels, That rest not day or night, The crowned and palm-
decked martyrs, The saints arrayed in white, The happy lambs of
Jesus In pastures fair above — These all adore and praise Him,
Whom we too praise and love. mf 4 The Church on earth rejoices To
join with these to-day; In every tongue and nation She calls her sons
to pray; Across the Northern snow-fields, Beneath the Indian palms,
She makes the same pure offering, And sings the same sweet
psalms. cres 5 Tell out, sweet bells, His praises! Sing, children, sing
His name! Still louder and still further His mighty deeds proclaim, Till
all whom He redeemed Shall own Him Lord and King, Till every knee
shall worship, And every tongue shall sing, f Glory be to Jesus, Let
all creation say ; He rose again. He rose again, On this glad day ! —
John Ellerton, 1826-1893
 iFor Ifrg %fltmg TOURS 7.6.7.6.7.6.7.6 594 Barthold Tours,
1838-1897 ^mm^Mf^$ s k -U -A ±U r ^pp^f^pg U^d^M 3 1221 r
njrTf* ifflSHiii A-men. r By permission of Nov«llo and Company,
Limited wif I When, His salvation bringing, To Zion Jesus came, The
children all stood singing Hosanna to His name; Nor did their zeal
offend Him, But, as He rode along, cres He let them still attend Him,
And smiled to hear their song. mf 2 And since the Lord retaineth His
love to children still, Though now as King He reigneth On Zion's
heavenly hill, We'll flock around His standard, We'll bow before His
throne, And cry aloud, " Hosanna To David's royal Son." mf 3 For
should we fail proclaiming Our great Redeemer's praise, The stones,
our silence shaming, Would their hosannas raise. But shall we only
render The tribute of our words? / No; while our hearts are tender,
They too shall be the Lord's. —J. King, 1787-1858
 595 ANGEL'S SONG (II) 7.6.7.6.7.6.7.6 3far thg f tmrtg G. F.
Root, 1820-1895 sg p ^r ^ p^=f^ i^^^^p^ ^S JJJ ^ ^£Ef^£ J. J J
J A A ^ff§ifpip| S^^^^g^p^^d zz: ::?— ^^^I^S ff frf ^
^gfef^^^ r r f t r A-men. Alternative Tune: Angels Story, \o. f=f^£
m mf i I love to hear the story Which angel voices tell. How once the
King of Glory Came down on earth to dwell. p I am both weak and
sinful ; cres But this I surely know. The Lord came down to save me,
Because He loved me so. mp 2 I'm glad my blessed Saviour Was
once a child like me, To show how pure and holy His little ones
might be; And if I try to follow His footsteps here below, He never
will forsake me. Because He loves me so. 3 To sing His love and
mercy My sweetest songs I'll raise; And though I cannot see Him, I
know He hears my praise : For He has kindly promised That even I
may go To sing among His angels. Because He loves me so. —Mrs.
Emily Miller,. 1833 
 3ar tfrg ffomig 596 EDEN GROVE 7.6.7.6.7.6.7.6 Samuel
Smith, 1821--pU^LJ±=d ^=d^ A w^ ~F=F ..Q. 1 m^w^WfW^ A
ity r i^=J=d-d: ^ f=P=tf=p ^^^d^^g ==a=3^l 1 P§ :d=i^ ^ a
hcU-l-J-J-J WtTIIP^1 i f? rrf2 A-men. p^r=^^; S I£21 m/ J We bring
no glittering treasures, No gems from earth's deep mine; We come,
with simple measures, To chant Thy love divine. Children, thy
favours sharing, Their voice of thanks would raise ; cres Father,
accept our offering, Our song of grateful praise. mf 2 That priceless
gift of heaven, Love's written" word of truth, To us is early given, To
guide our steps in youth ; We hear the wondrous story, The tale of
Calvary; We read of homes in glory, From sin and sorrow free, 3
Redeemer, grant Thy blessing ! O teach us how to pray, That each,
Thy fear possessing. May tread life's onward way! Then, where the
pure are dwelling We hope to meet again, And, sweeter numbers
swelling, For ever praise Thy name. —Miss H. C. Phillips, 1806 
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597 JESUS LOVES ME 7.7.7.7, with Refrain *m wm^ HifePPl

3far ti|g f oung dbti 3 W. B Bradbury, 1816-1868 d=3 ^i p—p- P^P"
"P~~ p ^JitgiS^s^r :rJ -rr-f-r ^ =1: rr ^T:z^Tr-r"rFf:^ g§|: - -
U^i^^ ■■■-£e£ r=f^=^±rzT # 1 Refrain. fe^^^^E : 5
__0_|l_|Et^fr?j Yes, Je - sus loves me — Yes. Je - sus loves me*=
Yes, Je - sus loves me. The Bi - ble tells me so. A - men. mf i Jesus
loves me, this I know. For the Bible tells me so; Little ones to Him
belong; They are weak, but He is strong. crei Yes, Jesus loves me —
Yes, Jesus loves me— Yes, Jesus loves me. The Bible tells me so. m/i
2 Jesus loves me, He who died Heaven's gate to open wide ; He will
wash away my sin. Let His little child come in. mp 3 Jesus loves me,
loves me still. When I'm very weak and ill. From His shining throne
on high Comes to watch me where I lie. mf 4 Jesus loves me. He will
stay Close beside me all the way; If I love Him, when I die cres He
will take me home on high. —Anna Bartlett Warner, 1820-188S
 3far Ifye ffnuttg 598 MERRIDALE 7.6.7.6.7.6.7.6 R. S.
Newman. 1850wmmm rr Fa5-1 E £ ipg*fJ PT"P" I ^ ^^ w A - men.
Composer's copyright Used by permission mf J God, who hath made
the daisies, And every lovely thing, He will accept our praises. And
hearken while we sing. p He says, though we are simple, Though
ignorant we be, Suffer the little children, And let them come to Me.
mf 2 Though we are young and simple, In praise we may be bold ;
The children in the temple He heard in days of old ; And if our
hearts are humble. He says to you and me, Suffer the little children.
And let them come to Me.
 jffor tifi ffoung ?nf 3 He sees the bird that wingeth Its way
o'er earth and sky; He hears the lark that singeth Up in the heaven
so high; He sees the heart's low breathings, And says, well pleased
to see, Suffer the little children, " And let them come to Me. / 4
Therefore we will come near Him, And joyfully we'll sing ; No cause
to shrink or fear Him, We'll make our voices ring ; For in our temple
speaking, He says to you and me, Suffer the little children, And let
them come to Me. — E. P. Hood, 1820-1885 CELESTIAL VOICES 8
3.8.3 599 fa^^^^g^ E. F. Lloyd ZZ2I r r r r r r f n^ ^tf^fM^ J-J-d.
Mee\ fe^^si^^^l rrrrrrfw \m Y ^ A - men. Bj=fe^^^^Siggj ^ -z?'
■np i In our hearts celestial voices Softly say — Day is passing, night
is coming; Kneel and pray! 2 Father, we obey the summons; Hear
our cry: Pity us, and help our weakness, Thou Most High! / 3 For the
joys that most we cherish Praised be Thou! dim Good and gentle art
Thou ever; Hear us now. mp 4 Coming morrows we may never Live
to see; All we ask Thee is to keep us Safe with Thee. 5 May our
dreams be of Thy kingdom Full of grace, cres Where at last we hope
to meet Thee Face to face. P 6 We are only little children Kneeling
here, And we want our loving Father Always near. 7 Take us in Thy
arms, and keep us As Thine own ; Gather us like little sunbeams
Round Thy throne. 8 There, when all our prayers are Faults forgiven,
[ended, cres May we live with Thee for ever Up in heaven. —Miss
Marie CorelU
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INFANT PRAISE 7.7.7.7, with Refrain 600 Juvenile

Harmonist," 1843 ijjJLU ■*r=f=¥=? gJE^^^EgE^I m^p^tmm^ f w
p^-r *& i ' Refrain. pppp^^p^^^ f r. i r rr i , p Hark, hark, hark!
while in-fant voi-ces sing, Hark, hark, hark! while J_J J I I J J r> J J J
J Hill i FS^-Pff^ ^^ppc^^^^ in - fant voi - ces sing f Loud 1AAA n
X ho - san-nas, JJ-J1 Jpjf^rrfefe^^pEEfe^ p^&mm san-nas, Loud
ho-san - nas to our King. A - men. A. >.# ^Pf- if^f^ fe^ -^- ^2_
SIB
 3far tbt ffnattg mf t Children of Jerusalem Sang the praise
of Jesus' name: Children, too, of modern days, Join to sing the
Saviour's praise. 2 We are taught to love the Lord, We are taught to
read His word, We are taught the way to heaven : Praise for all to
God be given. 3 Parents, teachers, old and young, All unite to swell
the song ; cres Higher and yet higher rise, Till "hosannas reach the
skies. —J. Henley, 1800-1842 EVER FAITHFUL 7.7.7.7 601 Sir Arthur
Sullivan, 1842-1900 PPPW^FPPPP -JBJm M AaaA i AAA pzpr-^UfEg^
* rf=r ttftftft-ma^ & iM AAA ^A-A-J J> J Q£^=^^^^ By permission
of Novello and Company, Limited mp i Father, lead me day by day
Ever in Thine own sweet way ; Teach me to be pure and true, Show
me what I ought to do. mf 2 When in danger, make me brave ; Make
me know that Thou canst save; mp Keep me safe by Thy dear side ;
Let me in Thy love abide. p 3 When I'm tempted to do wrong, Make
me steadfast, wise, and 6trong ; And when all alone I stand, Shield
me with Thy mighty hand. mf 4 When my heart is full of glee, Help
me to remember Thee — »n Copyright. By permission Happy most
of all to know That my Father loves me so. p 5 When my work
seems hard and dry, May I press on cheerily; Help me patiently to
bear Pain and hardship, toil and care. mf 6 May I see the good and
bright When they pass before my sight; May. I hear the heavenly
voice When the pure and wise rejoice. 7 May I do the good I know,
Be Thy loving child below, / Then at last go home to Thee, Evermore
Thy child to be. —J. Page Hopps. t834of the Sunday School Union
 3far tfrg f outtg 602 PENARTH 7.3.7.3.7.7 * Children
(Unison or Duet) or Solo. Not too fast. Samuel F. Deyes m^^^u^M
mp 1. God is kind; He made the flowers : God is Love, God is Love;
;i53^ sa J-J T=T^ Si ^j. n j. K^=E§1 US £ ^M^p^i Sends the sun -
shine, sends the^ showers From a - bove, from a - bove.
.^jE;3^,mSi4dU £=fejS Refrain in Harmony ^^^M^W God loves all
thingc. He loves me^ . . Lit- tie one.5 His face shall see. A -men. / '
^b f^aSS Copyright of the Wesleyan Methodist Sunday School
Department mp i God is kind ; He made the flowers : God is Love;
Sends the sunshine, sends the showers From above. / God loves all
things, He loves me: Little ones His face shall see. 2 God is good ;
He watches me Night and day, Keeps me safe, and guards my steps
All the way. God loves all things, He loves me : Little ones His face
shall see. 3 God is great ; His eye can see Everywhere : Dark can
never hide from Him; He is there. God loves all things, He loves me :
Little ones His face shall see. dim 4 God is Love ; He gave His Son
Once to die, cres So that we might live in heaven By and by. God
loves all things, He loves me : Little ones His face shall see. —
Elizabeth Benians, 1852 
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603 JEWELS 8.6.8.5, with Refrain 3far tift ffiamtg G. F.

Root. 1820-1895 PffW^FW^ ££B^=f=S 1 3-Lj: fT -jzz ^ff^^P^
^t=j _^LJ_J_j. r r pip r^ p f=ff=g^£ rT~r~r~ * i^te^s^^ g r~r
P^f rr r r r f ■ike the stars of the morr Like the stars of the morn -
ing. His bright crown a - dorn - ing. Ff=f Ll\j j_j.|,i j_^ rrf ip :ST si
rrrrrrrnr They shall shine in their beau - ty, Bright gems for His
crown. A - men. i^iss mf I When He cometh, when He cometh, To
make up His jewels, AH His jewels, precious jewels, His loved and
His own, c res Like the stars of the morning, His bright crown
adorning. They shall shine in their beauty. Bright gems for His
crown. rr=F=?L mf 2 He will gather, He will gather, The gems for His
kingdom ; All the pure ones, all the bright ones, His loved and His
own. 3 Little children, little children, Who love their Redeemer, Are
the jewels, precious jewels, His loved and His own. — W. O.
Cushing, 1823-1903
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3far tift f oitttg 604 EVENING PRAYER (II) 8.7.8.7 (First

Tune) Children in Unison. Sir J. Stainer, 1840-1901 fr^g^^MzJrzJzOj
J J ,J|f|.J „ 1 1 Je - sus, ten - der Shep-herd, hear me, BJess Thy lit -
He Iamb to -night; ^^^PP^pP^^ mm a* (»):. 4 o iez: ggtr^^^l s
j^p r r fUJ^m,! J J A J j „L » Through the dark-ness be Thou near
me. Keep me safe till morn-ing light. A- men. ^^j=itt±^tU-l4l^-\
*=r f f f ^ I FF^ ^=fFi tT^t S By permission of Novello and
Company ,a Limited mp 2 Through this day Thy hand has led me, 3
Let my sins be all forgiven, And I thank Thee for Thy care ; Bless the
friends I love so well ; Thou hast warmed me, clothed, and fed me,
Take me, when I die, to heaven, Listen to my evening prayer. Happy
there with Thee to dwell DIJON 8.7.8.7 (Second Tune) Lieder-Buch
fur Kleinkinder-Schulen, 1842
 605 REDEMPTION 8.7.8.7.4.7 3for tfrg ffinimg Charles F.
Gounod, 1818-1893 mm^pff^mm ^h^SAm^ w&mk^m ■e—e22:
fcfc im pl^pi^rtfs J J JJJJ ^y J^.J «u A-men. I^rrrrirr/n'^^^^ fp By
permission of Novello and Company, Limited mp t Saviour, like a
shepherd lead us, Much we need Thy tenderest care; In Thy
pleasant pastures feed us, For our use Thy fields prepare: Blessed
Jesus, [are. Thou hast bought Us, Thine we mf mp 2 We are Thine,
do Thou befriend us, Be the guardian of our way; Keep Thy flock,
from sin defend us, Seek us when we go astray: mf Blessed Jesus,
Hear, O hear us, when we pray! mp 3 Thou hast promised to receive
us, Poor and sinful though we be; Thou hast mercy to relieve us,
Grace to cleanse, and power to free: mf Blessed Jesus, We will early
turn to Thee. mp 4 Early let us seek Thy favour, Early let us do Thy
will; Blessed Lord and only Saviour, With Thy love our bosoms fill: mf
Blessed Jesus, Thou hast loved us, love us still. — Authorship
uncertain
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