| Content Provider |
World Health Organization (WHO)-Global Index Medicus |
| Author |
Wilde, Michael J. Rowland, Steven J. Frank, Richard A. Hewitt, L. Mark West, Charles E. Scarlett, Alan G. Jones, David |
| Description |
Country affiliation: United kingdom Author Affiliation: Wilde MJ ( Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK.); West CE ( Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK.); Scarlett AG ( Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK.); Jones D ( Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK.); Frank RA ( Water Science and Technology Directorate, Environment Canada, 867 Lakeshore Road, Burlington, ON, Canada L7R 4A6.); Hewitt LM ( Water Science and Technology Directorate, Environment Canada, 867 Lakeshore Road, Burlington, ON, Canada L7R 4A6.); Rowland SJ ( Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK. Electronic address: srowland@plym.ac.uk.) |
| Abstract |
Although bicyclic acids have been reported to be the major naphthenic acids in oil sands process-affected water (OSPW) and a well-accepted screening assay indicated that some bicyclics were the most acutely toxic acids tested, none have yet been identified. Here we show by comprehensive multidimensional gas chromatography-mass spectrometry (GC×GC-MS), that >100 C8-15 bicyclic acids are typically present in OSPW. Synthesis or purchase allowed us to establish the GC×GC retention times of methyl esters of numerous of these and the mass spectra and published spectra of some additional types, allowed us to identify bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[4.3.0]nonane, bicyclo[3.3.1]nonane and bicyclo[4.4.0]decane acids in OSPW and a bicyclo[2.2.2]octane acid in a commercial acid mixture. The retention positions of authentic bicyclo[3.3.0]octane and bicyclo[4.2.0]octane carboxylic acid methyl esters and published retention indices, showed these were also possibilities, as were bicyclo[3.1.1]heptane acids. Bicyclo[5.3.0]decane and cyclopentylcyclopentane carboxylic acids were ruled out in the samples analysed, on the basis that the corresponding alkanes eluted well after bicyclo[4.4.0]decane (latest eluting acids). Bicyclo[4.2.1]nonane, bicyclo[3.2.2]nonane, bicyclo[3.3.2]decane, bicyclo[4.2.2]decane and spiro[4.5]decane carboxylic acids could not be ruled out or in, as no authentic compounds or literature data were available. Mass spectra of the methyl esters of the higher bicyclic C12-15 acids suggested that many were simply analogues of the acids identified above, with longer alkanoate chains and/or alkyl substituents. Our hypothesis is that these acids represent the biotransformation products of the initially somewhat more bio-resistant bicyclanes of petroleum. Although remediation studies suggest that many bicyclic acids can be relatively quickly removed from suitably treated OSPW, examination by GC×GC-MS may show which isomers are affected most. Knowledge of the structures will allow the toxicity of any residual isomers to be calculated and measured. |
| ISSN |
00219673 |
| Volume Number |
1378 |
| e-ISSN |
18733778 |
| Journal |
Journal of Chromatography A |
| Language |
English |
| Publisher |
Elsevier |
| Publisher Date |
2015-01-23 |
| Publisher Place |
Netherlands |
| Access Restriction |
One Nation One Subscription (ONOS) |
| Subject Keyword |
Carboxylic Acids Analysis Gas Chromatography-mass Spectrometry Oil And Gas Fields Chemistry Water Pollutants, Chemical Alkanes Isolation & Purification Esters Petroleum Journal Article Research Support, Non-u.s. Gov't Discipline Analytical Chemistry |
| Content Type |
Text |
| Resource Type |
Article |
| Subject |
Organic Chemistry Medicine Analytical Chemistry Biochemistry |
