© EOSCA EOSCA European Oilfield Speciality Chemicals Association Bioaccumulation Potential of Surfactants: A Review © EOSCA This report was commissioned by the European Oilfield Specialty Chemical Association (EOSCA). EOSCA was founded in 1990 and has grown to an organisation comprising 40 full members and 7 associate members. As it stands today it represents almost all of the chemical manufacturers and chemical services companies involved in the supply and application of chemicals to Oil and Gas Operations in Europe. The primary function is to act as a focus of interest and concern on issues relating to Environmental and Safety Regulation. To this end it is recognised by government and operators as a first point of contact for chemical issues and is a fully recognised Non-Governmental Organisation within the OSPAR framework. It has the intention of acting as an advocacy group with regulatory and governmental bodies. EOSCA provides an opportunity for members to network with Health, Safety and Environmental Affairs professionals in the field of Oilfield Chemicals. Address for Correspondence: Graham Payne (Executive Secretary) Briar Technical Services Ltd 501 North Deeside Road Cults Aberdeen AB15 9ES Tel: +44 (0)1224 868827 Fax: +44 (0)1224 862503 [email protected] i © EOSCA EUROPEAN OILFIELD SPECIALITY CHEMICALS ASSOCIATION SUMMARY REPORT SURFACTANT BIOACCUMULATION REVIEW PROJECT Project funding: EOSCA Project Manager/Editor: Phil McWilliams ILAB Environmental Laboratory Contributors: Astrazeneca Limited, Brixham Environmental Laboratory Aquateam AS Chemex International Environmental and Resource Technology Limited Severn Trent Services The work performed in collating and evaluating the data on surfactant bioaccumulation reviewed in this report was funded entirely by EOSCA. The work was carried out over the period September 1999 to July 2000. The data reviewed was obtained through database and literature searches of material available in the public domain. The conclusions presented in this report are pertinent to the data reviewed, but may need to be modified as more information becomes available. All contributions to this review project by member companies and individuals within EOSCA are gratefully acknowledged. Phil McWilliams, Project Manager Bergen, August 2000 ii © EOSCA Table of Contents Preface ......................................................................................................................................... i List of abbreviations and definitions ………………………………………………… v CHAPTER 1 INTRODUCTION Surfactant Bioaccumulation Review Project - Background ......……… ……………… 1 List of contributors …………………………………………………………………. 2 CHAPTER 2 OILFIELD SURFACTANTS (Aquateam AS) Introduction …………………………………………………………………………. 5 Existing oilfield surfactant chemistry and classification ………………………………. 6 Current use, discharge and future trends ……………………………………………….. 6 Use …………………………………………………………………………... 6 Discharge ……………………………………………………………………. 6 Future trends ………………………………………………………………... 7 Development of new chemistries ……………………………………………………. 7 Aspects important to environmental risk assessment ………………………………… 8 Oil/water partitioning (Pow/OWDF) ………………………………………… 8 Sediment/water partitioning (Psw/Koc) ……………………………………….. 9 Partitioning between biota and water (BCF) …………………………………. 11 References …………………………………………………………………………… 12 CHAPTER 3 TOXICITY OF SURFACTANTS TO AQUATIC ORGANISMS (Astrazeneca Ltd., Brixham Environmental Laboratory) Introduction …………………………………………………………………………. 14 Surfactant Toxicity in the Marine Environment ……………………………………… 14 Taxonomic groups …………………………………………………………… 14 Algae ………………………………………………………………… 14 Crustaceans ………………………………………………………….. 14 Molluscs …………………………………………………………….. 15 Fish ………………………………………………………………….. 15 Table of acute toxicity data for anionic surfactants ………………………………………….. 18 Table of acute toxicity data for cationic surfactants ………………………………………….. 22 Table of acute toxicity data for non-ionic surfactants …….………………………….……….. 23 Table of acute toxicity data for surfactant mixtures ………………………………………….. 26 Table of chronic toxicity data for anionic surfactants ………………………………………….. 28 Table of chronic toxicity data for cationic surfactants ………………………………………….. 31 Table of chronic toxicity data for non-ionic surfactants ……………………………………….. 33 Structural considerations of surfactant toxicity ………………………………. 35 Environmental considerations of surfactant toxicity …………………………. 35 Sediments …………………………………………………………… 35 Salinity ………………………………………………………………. 35 iii © EOSCA Physical phase ………………………………………………………. 35 Conclusions ………………………………………………………………………… 36 References …………………………………………………………………………... 36 CHAPTER 4 ENVIRONMENTAL FATE AND BEHAVIOUR OF SURFACTANTS (Astrazeneca Ltd., Brixham Environmental Laboratory) Introduction ………………………………………………………………………… 38 The environmental fate and behaviour of surfactants in the marine environment …… 39 Mechanisms of removal from the marine environment ……………………… 39 Volatilisation ………………………………………………………… 39 Sorption/desorption ………………………………………………… 39 Abiotic degradation ………………………………………………….. 40 Biotic degradation …………………………………………………… 40 Degradation pathway (LAS) ………………………………… 41 Salinity effects ………………………………………………. 41 Temperature effects ………………………………………… 41 Sediment effects …………………………………………..… 41 Chain length and isomer effects …………………………….. 42 Effect of initial surfactant concentration ………………….… 42 Effect of heavy metals ……………………………….……… 42 Bacteria type ………………………………………………… 42 Anaerobic degradation ……………………………………… 42 Table of data of surfactant degradation in the marine environment …………………………… 43 References ……………………………………………………………….…………. 46 CHAPTER 5 BIOACCUMULATION AND BIOMAGNIFICATION OF SURFACTANTS - Mechanisms and Routes (Environment and Resource Technology Limited) Introduction …………………………………………………………………………… 48 Bioaccumulation factors ……………………………………………………….. 48 Environmental variables ……………………………………………………….. 49 Surfactant types ………………………………………………………………… 49 Evidence of Bioaccumulation ………………………………………………………….. 49 Trends and relationships between bioaccumulation data and chemical structure of surfactants ……………………………………………… 50 Increasing the hydrophobicity of the surfactant molecule …………….. 50 Decreasing the hydrophobicity of the surfactant molecule …………….. 51 Steric effects …………………………………………………………… 51 Summary of trends ……………………………………………………. 52 Mechanisms of bioaccumulation ……………………………………………………… 52 Biotransformation ……………………………………………………………... 54 Biomagnification potential of surfactants ……………………………………… 54 Conclusions …………………………………………………………………………… 55 References ……………………………………………………………………………. 56 iv © EOSCA CHAPTER 6 EXISTING BIOACCUMULATION DATA FOR SURFACTANTS (Chemex International) Introduction …………………………………………………………………………… 57 Available data ………………………………………………………………………… 57 Definition of BCF …………………………………………………………….. 57 Definition of partition coefficient …………………………………………….. 58 Comments on BCF data ……………………………………………………… 58 Comments on log Pow data ……………………………………………………. 59 Reliability of calculated values ………………………………………………… 60 Table of existing BCF data for surfactants ………………………………………………….. 61 Table of existing logP ow data for surfactants ………………………...……………………….. 66 References ……………………………………………………………………………… 68 CHAPTER 7 ALTERNATIVE ANALYTICAL APPROACHES (Severn Trent Services) Introduction …………………………………………………………………………… 70 Available alternative methods …………………….…………………………………… 70 Electrokinetic chromatography ………………………………………………… 70 Micellar elektrokinetic capillary chromatography (MECC) ……………... 70 Microemulsion elektrokinetic capillary chromatography (MEEKC) …… 73 Micellar elektrokinetic chromatography (MEKC) ……………………… 73 Reproducibility in capillary electrophoresis …………………………… 74 Advantages of the elektrokinetic technique …………………………… 75 Semi-permeable membrane device (SMPD) …………………………………... 75 Application of SMPDs in environmental analysis …………………….. 75 How are SPMDs deployed in the environment? ……………………… 76 Future requirements …………………….……………………………………………. 78 References ……………………………………………………………………………. 78 CHAPTER 8 CONCLUSIONS AND SUMMARY Conclusions ……………………………………………………………………………. 80 Summary …………………………….....………………………………………………. 81 Environmental issues ……….....………………………………..………………. 81 How reliable is existing data? .....………………………………..………………. 82 Is logPow/BCF relevant to surfactants? …..……………………..………………. 83 Alternative analytical approaches ………………………………..………………. 86 References ……………………………………………………………………………. 89 v © EOSCA List of Abbreviations and Definitions APE Alkyl phenol ethoxylate BCF Bioconcentration factor CHARM Chemical Hazard and Risk Management CMC Critical micelle concentration CR Concentration ratio DMT Diffusive mass transfer EO Ethylene oxide HOCNF Harmonised Offshore Chemical Notification Format HPLC High-pressure liquid chromatography Koc Sediment partition coefficient LAS Linear alkylbenzene sulphonate MECC Micellar elektrokinetic capillary chromatography MEEKC Microemulsion elektrokinetic capillary chromatography MEKC Micellar elektrokinetic chromatography OSPARCOM Oslo and Paris Commissions PEC Predicted environmental concentration PNEC Predicted no observed effect concentration Pow Octanol-water partition coefficient QSAR Quantitative structure-activity relationship SEBA OSPAR Working Group on Sea-based Activities SPMD Semi-permeable membrane device vi © EOSCA Chapter 1 INTRODUCTION © EOSCA Surfactant Bioaccumulation Review Project Background Surfactants are a chemical group for which it is difficult to obtain reliable partitioning (log Pow) or bioconcentration factor (BCF) data for