Interlaboratory Comparison of a Biomimetic Extraction Method Applied to Oil Sands Process-Affected Waters.

Biomimetic extraction using solid-phase microextraction is a passive sampling analytical method that can predict the aquatic toxicity of complex petroleum substances. The method provides a nonanimal alternative to traditional bioassays with the potential to reduce both vertebrate and invertebrate aquatic toxicity testing. The technique uses commercially available polydimethylsiloxane-coated fibers that, following nondepletive extraction of water samples, are injected into a gas chromatograph with flame ionization detection. As the predictive nature of the method is operationally defined, it is critical that its application be harmonized with regard to extraction, analysis, and standardization parameters. Results are presented from a round robin program comparing the results from 10 laboratories analyzing four different sample sets of dissolved organics in water. Samples included two incurred oil sands process-affected waters and a cracked gas oil water accommodated fraction. A fourth sample of cracked gas oil blended in an oil sands process-affected water was analyzed to demonstrate the method's ability to differentiate between neutral and ionizable dissolved hydrocarbons. Six of the 10 laboratories applied an automated version of the method using a robotic autosampler where the critical extraction steps are precisely controlled and which permits batch screening of water samples for aquatic toxicity potential. The remaining four laboratories performed the solid-phase microextraction manually. The automated method demonstrated good reproducibility with between-laboratory variability across the six laboratories and four samples yielding a mean relative standard deviation of 14%. The corresponding between-laboratory variability across the four laboratories applying the manual extraction was 53%, demonstrating the importance of precisely controlling the extraction procedure. Environ Toxicol Chem 2022;41:1613-1622. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Analysis of Sublethal Toxicity in Developing Zebrafish Embryos Exposed to a Range of Petroleum Substances.

The Organisation for Economic Co-operation and Development (OECD) test guideline 236 (fish embryo acute toxicity test; 2013) relies on 4 endpoints to describe exposure-related effects (coagulation, lack of somite formation, tail-bud detachment from the yolk sac, and the presence of a heartbeat). Danio rerio (zebrafish) embryos were used to investigate these endpoints along with a number of additional sublethal effects (cardiac dysfunction, pericardial edema, yolk sac edema, tail curvature, hatch success, pericardial edema area, craniofacial malformation, swim bladder development, fin development, and heart rate) following 5-d exposures to 7 petroleum substances. The substances investigated included 2 crude oils, 3 gas oils, a diluted bitumen, and a petrochemical containing a mixture of branched alcohols. Biomimetic extraction-solid-phase microextraction (BE-SPME) was used to quantify freely dissolved concentrations of test substances as the exposure metric. The results indicated that the most prevalent effects observed were pericardial and yolk sac edema, tail curvature, and lack of embryo viability. A BE-SPME threshold was determined to characterize sublethal morphological alterations that preceded embryo mortality. Our results aid in the understanding of aquatic hazards of petroleum substances to developing zebrafish beyond traditional OECD test guideline 236 endpoints and show the applicability of BE-SPME as a simple analytical tool that can be used to predict sublethal embryo toxicity. Environ Toxicol Chem 2019;38:1302-1312. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Water solubility of selected C9-C18 alkanes using a slow-stir technique: Comparison to structure - property models.

Aqueous solubility is a fundamental physical-chemical substance property that strongly influences the distribution, fate and effects of chemicals upon release into the environment. Experimental water solubility was determined for 18 selected C9-C18 normal, branched and cyclic alkanes. A slow-stir technique was applied to obviate emulsion formation, which historically has resulted in significant overestimation of the aqueous solubility of such hydrophobic liquid compounds. Sensitive GC-MS based methods coupled with contemporary sample extraction techniques were employed to enable reproducible analysis of low parts-per billion aqueous concentrations. Water solubility measurements for most of the compounds investigated, are reported for the first time expanding available data for branched and cyclic alkanes. Measured water solubilities spanned four orders of magnitude ranging from 0.3 µg/L to 250 µg/L. Good agreement was observed for selected alkanes tested in this work and reported in earlier literature demonstrating the robustness of the slow-stir water solubility technique. Comparisons of measured alkane water solubilities were also made with those predicted by commonly used quantitative structure-property relationship models (e.g. SPARC, EPIWIN, ACD/Labs). Correlations are also presented between alkane measured water solubilities and molecular size parameters (e.g. molar volume, solvent accessible molar volume) affirming a mechanistic description of empirical aqueous solubility results and prediction previously reported for a more limited set of alkanes.

Slow-stir water solubility measurements of selected alcohols and diesters.

Experimental data are presented for 11 C8-C15 aliphatic alcohols and 12 phthalate and adipate diesters using a slow-stir water solubility test method. The slow stirring method provides more reliable water solubility measurements for these liquid substances than previous studies since the formation of emulsions is avoided. Because the solubility of these chemicals spanned a range of more than six orders of magnitude, several different analytical procedures were employed. The water solubility data reported in this work agree well with other recently reported slow-stir measurements and with structure-property model predictions (SPARC and WSKOWWIN).