Fatty Alcohols – a review of their natural synthesis and environmental distribution Stephen M Mudge School of Ocean Sciences, University of Wales – Bangor For SDA and ERASM November, 2005 © 2005 The Soap and Detergent Association. All Rights Reserved. Table of Contents Executive Summary.....................................................................................................3 Chapter 1. Definitions..................................................................................................5 Names and structures .....................................................................................................5 Physico-Chemical Properties.........................................................................................7 Solubility vs. chain length..............................................................................................7 Partitioning (Kow) and sediment associations ................................................................9 Chapter 2. Biological Synthesis ................................................................................12 Animals........................................................................................................................12 Unsaturated chains.......................................................................................................14 Plants and Bacteria.......................................................................................................15 Unsaturated Compounds..............................................................................................15 Branched chains...........................................................................................................16 Fatty Acid Degradation................................................................................................16 Fatty Acyl-CoA Reductase (FAR)...............................................................................17 Synthesis from carbohydrates (Copepods) ..................................................................21 Chapter 3. Occurrence ..............................................................................................23 Bacteria ........................................................................................................................23 Chlorophyll side chain (phytol) ...................................................................................25 Marine Plants ...............................................................................................................26 Terrestrial Plant Waxes................................................................................................27 Mosses and other peat forming plants .........................................................................29 Marine animals.............................................................................................................30 Insects ..........................................................................................................................32 Birds.............................................................................................................................33 Detergents ....................................................................................................................34 Chapter 4. ...................................................................................................................45 Metabolism of Fatty Alcohols .....................................................................................45 Natural degradation......................................................................................................48 Short chain moieties.....................................................................................................49 Long chain moieties.....................................................................................................53 Degradation Rate Constants.........................................................................................55 Phytol degradation .......................................................................................................57 Effect of chemical associations on transformation rates..............................................57 “Natural” fatty alcohols in STPs..................................................................................57 Anthropogenic fatty alcohols in STPs .........................................................................59 Chapter 5. Analytical methods .................................................................................61 Overview of Methods ..................................................................................................61 Methods for analysis of free fatty alcohols (and ethoxylates) .....................................61 Environmental Samples ...............................................................................................62 Comment on inter-laboratory comparisons .................................................................68 © 2005 The Soap and Detergent Association. All Rights Reserved. 1 Chapter 6. Environmental Concentrations .............................................................69 Global Locations..........................................................................................................73 A. Victoria Harbour, BC – Surface Sediments............................................................73 B1. Concepcíon Bay, Chile.........................................................................................75 B2. San Vicente Bay, Chile .........................................................................................75 C. Rio de Janeiro – surface sediments in a contaminated bay.....................................79 D1. Arade Estuary........................................................................................................80 D2. Ria Formosa lagoon – surface sediments..............................................................82 D3. Ria Formosa lagoon – suspended and settled sediments ......................................85 D4. Ria Formosa lagoon – shallow core from intertidal sediments.............................87 E. Eastern North Atlantic.............................................................................................88 F. San Miguel Gap, California – long core..................................................................91 G. Rio Grande Rise (516F of leg 72 ODP), Brazil ......................................................92 H. Falkland Plateau (511 of leg 71 ODP), S. Atlantic.................................................93 I. Guatemalan Basin (Legs 66 & 67 ODP), Central America......................................94 J1. Continental slope, SW of Taiwan...........................................................................95 J2. East China Sea, N of Taiwan..................................................................................95 K. Pasture land, Southern Australia.............................................................................98 L. Prairie Zone soils, Alberta, Canada.........................................................................99 UK Studies.................................................................................................................100 1. Conwy Estuary – Core (50 cm) .............................................................................100 2. Mawddach Estuary – surface sediments................................................................103 3. Menai Strait............................................................................................................106 4. Loch Riddon, Scotland – mid-length core .............................................................106 5. Lochnagar, Scotland. .............................................................................................108 6. Clyde Sea, Scotland ...............................................................................................109 7. Loe Pool, Cornwall ................................................................................................111 8. Bolton Fell Moss, Cumbria....................................................................................112 9. Blackpool Beach – see Chapter 7. .........................................................................113 10a. Loch Lochy, Scotland – a freshwater deep loch core ........................................114 10b. Loch Eil, Scotland – a mid-depth (~70m) seawater loch core...........................114 Summary....................................................................................................................116 Chapter 7. Multivariate Statistics ..........................................................................118 Chemometric methods of use with fatty alcohols......................................................118 PCA............................................................................................................................118 PLS.............................................................................................................................127 Recommendations....................................................................................................131 References.................................................................................................................132 Appendix Synthetic Pathways of Detergent Alcohols …………………………...141 © 2005 The Soap and Detergent Association. All Rights Reserved. 2 Executive