Trace Analysis of Surfactants in Corexit Oil Dispersant Formulations and Seawater.

After the April 2010 explosion on the Deepwater Horizon oil rig, and subsequent release of millions of barrels of oil, two Corexit oil dispersant formulations were used in unprecedented quantities both on the surface and sub-surface of the Gulf of Mexico. Although the dispersant formulations contain four classes of surfactants, current studies to date focus on the anionic surfactant, bis-(2-ethylhexyl) sulfosuccinate (DOSS). Factors affecting the integrity of environmental and laboratory samples for Corexit analysis have not been systematically investigated. For this reason, a quantitative analytical method was developed for the detection of all four classes of surfactants, as well as the hydrolysis products of DOSS, the enantiomeric mixture of α- and ß-ethylhexyl sulfosuccinate (α-/ß-EHSS). The analytical method was then used to evaluate which practices for sample collection, storage, and analysis resulted in high quality data. Large volume, direct injection of seawater followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) minimized analytical artifacts, analysis time, and both chemical and solid waste. Concentrations of DOSS in the seawater samples ranged from 71 - 13,000 ng/L, while the nonionic surfactants including Span 80, Tween 80, Tween 85 were detected infrequently (26% of samples) at concentrations from 840 - 9100 ng/L. The enantiomers α-/ß-EHSS were detected in seawater, at concentrations from 200 - 1,900 ng/L, and in both Corexit dispersant formulations, indicating α-/ß-EHSS were applied to the oil spill and may be not unambiguous indicator of DOSS degradation. Best practices are provided to ensure sample integrity and data quality for environmental monitoring studies and laboratory that require the detection and quantification of Corexit-based surfactants in seawater.

Perfluoroalkyl sulfonates and perfluorocarboxylates in two wastewater treatment facilities in Kentucky and Georgia.

Discharge of effluents from municipal wastewater treatment plants (WWTPs) is a route for the introduction of certain organic contaminants into aquatic environments. Earlier studies have reported the occurrence of perfluorochemicals in effluents from WWTPs. In this study, contamination profiles of perfluorinated compounds (PFCs), including perfluoroalkyl sulfonates (PFASs; PFOS, PFOSA, PFHxS) and perfluoroalkyl carboxylates (PFACs; PFOA, PFNA, PFDA, PFDoDA, PFUnDA), were determined in samples collected at various stages of wastewater treatment during different seasons. The two WWTPs selected for this study represent rural (Plant A, Kentucky) and urban (Plant B, Georgia) areas. PFOS was a major contaminant in samples from Plant A (8.2-990 ng/g dry wt in solid samples and 7.0-149 ng/L in aqueous samples), followed by PFOA (8.3-219 ng/g dry wt in solid samples and 22-334 ng/L in aqueous samples). PFOA was the predominant contaminant in samples from Plant B (7.0-130 ng/g dry wt in solid samples and 1-227 ng/L in aqueous samples), followed by PFOS (<2.5-77 ng/g dry wt in solid samples and 1.8-22 ng/L in aqueous samples). PFHxS, PFNA, PFDA, and PFOSA were detected in most of the samples, whereas PFUnDA and PFDoDA were detected in very few samples. Concentrations of some PFCs, particularly PFOA, were slightly higher in effluent than in influent, suggesting that biodegradation of some precursors contributes to the increase in PFOA concentrations in wastewater treatment processes. No large-magnitude seasonal variations in concentrations were found, although mass flow of PFCs was higher in winter than in summer. In general, samples from the rural plant in Kentucky contained greater concentrations of PFCs than did those from the urban plant in Georgia. Incineration of sludge reduced the PFC levels significantly. The mass flows of PFCs in these two plants were several hundreds of mg/day, comparable to flow values reported earlier.

Quantitation of gas-phase perfluoroalkyl surfactants and fluorotelomer alcohols released from nonstick cookware and microwave popcorn bags.

Fluoropolymer dispersions are used for coating certain cookware products and food-contact packaging to impart oil and water repellency. Since salts of perfluorooctanoic acid (PFOA) are used as a processing aid in the manufacture of many fluoropolymers, it is necessary to determine if these compounds are still present as residuals after the process used to coat nonstick cookware or packaging, and could be released during typical cooking conditions. In this study, we identified and measured perfluoroalkyl carboxylates (PFCAs), particularly PFOA, and fluorotelomer alcohols (FTOHs; 6:2 FTOH and 8:2 FTOH), released from nonstick cookware into the gas phase under normal cooking temperatures (179 to 233 degrees C surface temperature). PFOA was released into the gas phase at 7-337 ng (11-503 pg/cm2) per pan from four brands of nonstick frying pans. 6:2 FTOH and 8:2 FTOH were found in the gas phase of four brands of frying pans, and the sources of FTOHs released from nonstick cookware are under investigation. We observed a significant decrease in gas-phase PFOA following repeated use of one brand of pan, whereas the other brand did not show a significant reduction in PFOA release following multiple uses. PFOA was found at >5 ng during the fourth use of both brands of pans. FTOHs were not found after the second use of either brand of pans. PFOA was found at 5-34 ng in the vapors produced from a prepacked microwave popcorn bag. PFOA was not found in the vapors produced from plain white corn kernels popped in a polypropylene container. 6:2 FTOH and 8:2 FTOH were measured in the vapors produced from one brand of prepacked microwave popcorn at 223 + 37 ng and 258 +/- 36 ng per bag, respectively, but not measured at >20 ng (LOQ) in the other two brands. On the packaging surface of one brand of microwave popcorn several PFCAs, including C5-C12, 6:2 FTOH, and 8:2 FTOH, were found at concentrations in the order of 0.5-6.0 ng/cm2. This study suggests that residual PFOA is not completely removed during the fabrication process of the nonstick coating for cookware. They remain as residuals on the surface and may be off-gassed when heated at normal cooking temperatures.

Perfluorinated contaminants in sediments and aquatic organisms collected from shallow water and tidal flat areas of the Ariake Sea, Japan: environmental fate of perfluorooctane sulfonate in aquatic ecosystems.

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorohexane sulfonate (PFHS), and perfluorooctane sulfonamide (PFOSA) are widely distributed in aquatic ecosystems. Despite studies reporting the occurrence of PFCs in aquatic organisms, the fate of PFCs in tidal flat and marine coastal ecosystems is not known. In this study, we determined concentrations of PFOS, PFOA, PFNA, PFHS, and PFOSA in sediments; benthic organisms, including lugworm, mussel, crab, clam, oyster, and mudskipper fish from tidal flat; and shallow water species, such as filefish, bream, flounder, shark, finless porpoise, gull, and mallard collected from the Ariake Sea, Japan. PFOS and PFOA were detected in most of the samples analyzed, followed by PFNA, PFOSA, and PFHS. In shallow water species, PFOS was the dominant contaminant, and elevated concentrations were found in higher trophic level species, such as marine mammals and omnivorous birds. These results suggest biomagnification of PFOS through the coastal food chain. In contrast, PFOA was the most abundant compound in tidal flat organisms and sediments. PFOA concentrations in sediments, lugworms, and omnivorous mudskippers in tidal flat were approximately 1 order of magnitude greater than the levels of PFOS. This indicates differences in exposure pattern and bioavailability of PFOS and PFOA between shallow water and tidal flat organisms. The accumulation profiles of PFCs were compared with those of organochlorines (polychlorinated biphenyls, PCB), organotin (tributyltin,TBT), and polycyclic aromatic hydrocarbons (PAHs) in tidal flat and shallow water samples collected from the Ariake Sea. Concentrations of PFCs in sediments and in tidal flat organisms were significantly lower than that found for PCBs, TBT, and PAHs. Nevertheless, PFOS concentrations in shallow water species were comparable to and/or significantly greater than those of other classes of contaminants. This implies that the aqueous phase is a major sink for PFCs, which is different from what was observed for nonpolar organic pollutants.

Mass loading and fate of perfluoroalkyl surfactants in wastewater treatment plants.

Wastewater treatment plants have recently been identified as a significant pathway for the introduction of perfluoroalkyl surfactants (PASs) to natural waters. In this study, we measured concentrations and fate of several PASs in six wastewater treatment plants (WWTPs) in New York State. We also monitored and measured matrix effects (ionization suppression and enhancement) by postcolumn infusion and standard additions. Concentrations of perfluorooctanoate (PFOA) in effluents of the six WWTPs ranged from 58 to 1050 ng/L. Perfluorooctanesulfonate (PFOS) was also ubiquitous in effluents of these WWTPs, albeit at much lower concentrations (3-68 ng/L). Two of these WWTPs employed identical treatment processes, with similar hydraulic retentions, but differed only in that Plant B treated domestic and commercial waste, whereas Plant A had an additional industrial influence. We found that this industrial influence resulted in significantly greater mass flows of all of the PASs analyzed. Primary treatment was found to have no effect on the mass flows of PASs. Secondary treatment by activated sludge in Plant A significantly increased (p < 0.05) the mass flows of PFOS, PFOA, perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUnDA). However, in Plant B, only the mass flow of PFOA was significantly increased. The observed increase in mass flow of several PASs may have resulted from biodegradation of precursor compounds such as fluorotelomer alcohols, which is supported by significant correlations in the mass flow of PFOA/PFNA and PFDA/PFUnDA. Furthermore, the masses of PFDA and PFUnDA were significantly correlated only after the secondary treatment. In Plant A, concentrations of odd-number PFCAs were greater than those of even-number PFCAs, and concentration decreased with increasing chain length (from C8 to C12). A different pattern was observed in sludge samples, in which the dominance of PFOA decreased, and PFDA and PFUnDA increased, suggesting preferential partitioning of longer-chain PFCAs to sludge.

Occurrence of perfluoroalkyl surfactants in water, fish, and birds from New York State.

Concentrations of perfluorooctanesulfonate (PFOS) and several other perfluoroalkyl surfactants (PASs) were determined in nine major water bodies (n = 51) of New York State (NYS). These PASs were also measured in the livers of two species of sport fish (n = 66) from 20 inland lakes in NYS. Finally, perfluorinated compounds were measured in the livers of 10 species of waterfowl (n = 87) from the Niagara River region in NYS. PFOS, perfluorooctanoic acid (PFOA), and perfluorohexanesulfonate (PFHS) were ubiquitous in NYS waters. PFOA was typically found at higher concentrations than were PFOS and PFHS. Elevated concentrations of PFOS were found in surface waters of Lake Onondaga, and elevated concentrations of PFOA were found in the Hudson River. PFOS was the most abundant perfluorinated compound in all fish and bird samples. PFOS concentrations in the livers of fishes ranged from 9 to 315 ng/g wet weight. PFOS, PFOA, and PFOSA (perfluorooctanesulfonamide) concentrations in smallmouth and largemouth bass (taken together) caught in remote mountain lakes with no known point sources of PAS contamination were 14 to 207, < 1.5 to 6.1, and < 1.5 to 9.8 ng/g wet weight, respectively. PFOS concentrations in the livers of birds ranged from 11 to 882 ng/g wet weight. PFOS concentrations were 2.5-fold greater (p = 0.001) in piscivorous birds than in non-piscivorous birds. However, PFOA, PFOSA, and PFHS were not found in bird livers. Overall, average concentrations of PFOS in fish were 8850-fold greater than those in surface water. An average biomagnification factor of 8.9 was estimated for PFOS in common merganser relative to that in fish. This study highlights the significance of dietary fish in PFOS accumulation in the food chain. Furthermore, our results provide information on the distribution of PASs in natural waters, fish, and several bird species in NYS.

Analysis of fluorotelomer alcohols, fluorotelomer acids, and short- and long-chain perfluorinated acids in water and biota.

Fluorotelomer alcohols and fluorotelomer acids have been proposed as a source of the perfluorinated carboxylic acids found in remote marine locations. To examine the sources and fate of perfluorinated acids in the environment, a method to determine a wide range of poly- and perfluorinated acids in environmental and biological matrices is needed. In this study, a method has been developed to measure a suite of neutral and acidic fluorochemicals including, fluorotelomer alcohols, fluorotelomer acids, and short- and long-chain perfluorinated acids, in water and biological samples. The method involves solid-phase extraction with weak anion exchange (WAX) cartridges, followed by sequential elution with sodium acetate buffer, methanol, and 0.1% NH4OH in methanol. For biological samples, prior to solid-phase extraction, tissues are digested in 0.5N potassium hydroxide/methanol, diluted in water, and passed through the WAX cartridge. Neutral compounds and telomer alcohols are separated from other poly- and perfluorinated acids. The method is robust (i.e., capable of measuring neutral and acidic compounds), and can be applied for the analysis of a range of poly- and perfluorinated acids, including telomer alcohols, telomer acids, perfluoroalkylcarboxylates, and perfluoroalkylsulfonates in water and biota. With the use of high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), a method detection limit in the range of several tens to hundreds of parts-per-quadrillion (pg/L) in water and at a few tens to hundreds of parts-per-trillion (pg/g) levels in biological matrices can be achieved.

Perfluorinated compounds in aquatic organisms at various trophic levels in a Great Lakes food chain.

Trophic transfer of perfluorooctanesulfonate (PFOS) and other related perfluorinated compounds was examined in a Great Lakes benthic foodweb including water-algae-zebra mussel-round goby-smallmouth bass. In addition, perfluorinated compounds were measured in livers and eggs of Chinook salmon and lake whitefish, in muscle tissue of carp, and in eggs of brown trout collected from Michigan. Similarly, green frog livers, snapping turtle plasma, mink livers, and bald eagle tissues were analyzed to determine concentrations in higher trophic-level organisms in the food chain. PFOS was the most widely detected compound in benthic organisms at various trophic levels. Concentrations of PFOS in benthic invertebrates such as amphipods and zebra mussels were approximately 1000-fold greater than those in surrounding water, which suggested a bioconcentration factor (BCF; concentration in biota/concentration in water) of 1000 in benthic invertebrates. Concentrations of PFOS in round gobies were two- to fourfold greater than those in their prey organisms such as zebra mussels and amphipods. Concentrations of PFOS in predatory fishes (Chinook salmon and lake whitefish) were 10 to 20-fold greater than those in their prey species. Concentrations of PFOS in mink and bald eagles were, on average, 5- to 10-fold greater than those in Chinook salmon, carp, or snapping turtles. Because of the accumulation of PFOS in liver and blood, the biomagnification factor (BMF) of perfluorinated compounds in higher trophic-level organisms such as salmonid fishes, mink, and eagles were based on the concentrations in livers or plasma. Overall, these results suggest a BCF of PFOS of approximately 1000 (whole-body based) in benthic invertebrates, and a BMF of 10 to 20 in mink or bald eagles, relative to their prey items. Eggs of fish contained notable concentrations of PFOS, suggesting oviparous transfer of this compound. PFOA was found in water, but its biomagnification potential was lower than that of PFOS.