title: Diaromatic sulphur-containing 'naphthenic' acids in process waters.
abstract: Polar organic compounds found in industrial process waters, particularly those originating from biodegraded petroleum residues, include 'naphthenic acids' (NA). Some NA have been shown to have acute toxicity to fish and also to produce sub-lethal effects. Whilst some of these toxic effects are produced by identifiable carboxylic acids, acids such as sulphur-containing acids, which have been detected, but not yet identified, may produce others. Therefore, in the present study, the sulphur-containing acids in oil sands process water were studied. A fraction (ca 12% by weight of the total NA containing ca 1.5% weight sulphur) was obtained by elution of methylated NA through an argentation solid phase extraction column with diethyl ether. This was examined by multidimensional comprehensive gas chromatography-mass spectrometry (GCxGC-MS) in both nominal and high resolution mass accuracy modes and by GCxGC-sulphur chemiluminescence detection (GCxGC-SCD). Interpretation of the mass spectra and retention behaviour of methyl esters of several synthesised sulphur acids and the unknowns allowed delimitation of the structures, but not complete identification. Diaromatic sulphur-containing alkanoic acids were suggested. Computer modelling of the toxicities of some of the possible acids suggested they would have similar toxicities to one another and to dehydroabietic acid. However, the sulphur-rich fraction was not toxic or estrogenic to trout hepatocytes, suggesting the concentrations of sulphur acids in this sample were too low to produce any such effects in vitro. Further samples should probably be examined for these compounds.
authors.affiliation: Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK.
authors.forename: Charles E
authors.initials: CE
authors.lastname: West
authors.affiliation: Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK.
authors.forename: Alan G
authors.initials: AG
authors.lastname: Scarlett
authors.affiliation: Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK.
authors.forename: Andrew
authors.initials: A
authors.lastname: Tonkin
authors.affiliation: Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK.
authors.forename: Devon
authors.initials: D
authors.lastname: O'Carroll-Fitzpatrick
authors.affiliation: Shell Global Solutions International B V, Rock and Fluid Science, Kessler Park 1, 2288 GS Rijswijk, The Netherlands.
authors.forename: Jos
authors.initials: J
authors.lastname: Pureveen
authors.affiliation: Shell Global Solutions International B V, Rock and Fluid Science, Kessler Park 1, 2288 GS Rijswijk, The Netherlands.
authors.forename: Erik
authors.initials: E
authors.lastname: Tegelaar
authors.affiliation: Canmet ENERGY, Natural Resources Canada, Devon, Alberta, Canada T9G 1A8; Institute of Chemistry, The University of Silesia, 9 Szkolna Street, 40-006 Katowice, Poland.
authors.forename: Rafal
authors.initials: R
authors.lastname: Gieleciak
authors.affiliation: Canmet ENERGY, Natural Resources Canada, Devon, Alberta, Canada T9G 1A8.
authors.forename: Darcy
authors.initials: D
authors.lastname: Hager
authors.affiliation: Norwegian Institute for Water Research (NIVA), Gaustadalléen 21, N-0349 OSLO, Norway.
authors.forename: Karina
authors.initials: K
authors.lastname: Petersen
authors.affiliation: Norwegian Institute for Water Research (NIVA), Gaustadalléen 21, N-0349 OSLO, Norway.
authors.forename: Knut-Erik
authors.initials: KE
authors.lastname: Tollefsen
authors.affiliation: Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK. Electronic address: srowland@plym.ac.uk.
authors.forename: Steven J
authors.initials: SJ
authors.lastname: Rowland
mesh_terms: D000818:Animals; D002264:Carboxylic Acids / Q000032:analysis* / Q000737:chemistry / Q000633:toxicity; D004797:Enzyme-Linked Immunosorbent Assay; D022781:Hepatocytes / Q000187:drug effects; D008956:Models, Chemical; D015394:Molecular Structure; D017686:Oncorhynchus mykiss; D013457:Sulfur Compounds / Q000032:analysis* / Q000737:chemistry / Q000633:toxicity; D062065:Wastewater / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000633:toxicity
chemical_list: D002264:Carboxylic Acids; D013457:Sulfur Compounds; D062065:Wastewater; D014874:Water Pollutants, Chemical; C046170:naphthenic acid
keywords: Accurate mass; GCxGC-MS; GCxGC-SCD; Naphthenic acids; SO(2) acids