Brian F. Scott

Perfluoroalkyl Acids in the Atlantic and Canadian Arctic Oceans

We report here on the spatial distribution of C(4), C(6), and C(8) perfluoroalkyl sulfonates, C(6)-C(14) perfluoroalkyl carboxylates, and perfluorooctanesulfonamide in the Atlantic and Arctic Oceans, including previously unstudied coastal waters of North and South America, and the Canadian Arctic Archipelago. Perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were typically the dominant perfluoroalkyl acids (PFAAs) in Atlantic water. In the midnorthwest Atlantic/Gulf Stream, sum PFAA concentrations (∑PFAAs) were low (77-190 pg/L) but increased rapidly upon crossing into U.S. coastal water (up to 5800 pg/L near Rhode Island). ∑PFAAs in the northeast Atlantic were highest north of the Canary Islands (280-980 pg/L) and decreased with latitude. In the South Atlantic, concentrations increased near Rio de la Plata (Argentina/Uruguay; 350-540 pg/L ∑PFAAs), possibly attributable to insecticides containing N-ethyl perfluorooctanesulfonamide, or proximity to Montevideo and Buenos Aires. In all other southern hemisphere locations, ∑PFAAs were <210 pg/L. PFOA/PFOS ratios were typically ≥1 in the northern hemisphere, ∼1 near the equator, and ≤1 in the southern hemisphere. In the Canadian Arctic, ∑PFAAs ranged from 40 to 250 pg/L, with perfluoroheptanoate, PFOA, and PFOS among the PFAAs detected at the highest concentrations. PFOA/PFOS ratios (typically ≫1) decreased from Baffin Bay to the Amundsen Gulf, possibly attributable to increased atmospheric inputs. These data help validate global emissions models and contribute to understanding of long-range transport pathways and sources of PFAAs to remote regions.

Detection of a Cyclic Perfluorinated Acid, Perfluoroethylcyclohexane Sulfonate, in the Great Lakes of North America

Perfluoroethylcyclohexanesulfonate (PFECHS) is a cyclic perfluorinated acid (PFA) mainly used as an erosion inhibitor in aircraft hydraulic fluids. It is expected to be as recalcitrant to environmental degradation as aliphatic PFAs including perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). For the first time, PFECHS is reported in top predator fish (<MDL to 3.7 ng g(-1) wet weight in whole body homogenate) from the Great Lakes and in surface waters (0.16-5.7 ng L(-1)). PFOS was the major aliphatic PFA in fish from the Great Lakes. Concentrations of most of the PFAs were not statistically different from previously reported 2004 trout data in Lake Ontario. Shorter chain perfluorocarboxylates were prevalent in surface waters of the Great Lakes, dominated by PFOA (0.65-5.5 ng/L). An impurity in the commercial PFECHS formulation, perfluoromethylcyclohexane sulfonate (PFMeCHS), was also detected in the dissolved phase but not above detection limits in fish tissue. Bioaccumulation factors (BAFs) were estimated by taking the ratio of fish to water concentrations. The mean log BAF values corresponded to 2.8 for PFECHS, 2.1 for PFOA, and 4.5 for PFOS. It is not certain whether the fish-water BAF for PFECHS is an overestimate due to the influence of precursor biotransformation. Further studies are recommended to understand the extent of PFECHS contamination.

Manufacturing Origin of Perfluorooctanoate (PFOA) in Atlantic and Canadian Arctic Seawater

The extent to which different manufacturing sources and long-range transport pathways contribute to perfluorooctanoate (PFOA) in the worlds oceans, particularly in remote locations, is widely debated. Here, the relative contribution of historic (i.e., electrochemically fluorinated) and contemporary (i.e., telomer) manufacturing sources was assessed for PFOA in various seawater samples by an established isomer profiling technique. The ratios of individual branched PFOA isomers were indistinguishable from those in authentic historic standards in 93% of the samples examined, indicating that marine processes had little influence on isomer profiles, and that isomer profiling is a valid source apportionment tool for seawater. Eastern Atlantic PFOA was largely (83-98%) of historic origin, but this decreased to only 33% close to the Eastern U.S. seaboard. Similarly, PFOA in the Norwegian Sea was near exclusively historic, but the relative contribution decreased to ∼50% near the Baltic Sea. Such observations of contemporary PFOA in coastal source regions coincided with elevated concentrations, suggesting that the continued production and use of PFOA is currently adding to the marine burden of this contaminant. In the Arctic, a spatial trend was observed whereby PFOA in seawater originating from the Atlantic was predominantly historic (up to 99%), whereas water in the Archipelago (i.e., from the Pacific) was predominantly of contemporary origin (as little as 17% historic). These data help to explain reported temporal and spatial trends from Arctic wildlife biomonitoring, and suggest that the dominant PFOA source(s) to the Pacific and Canadian Arctic Archipelago are either (a) from direct emissions of contemporary PFOA via manufacturing or use in Asia, or (b) from atmospheric transport and oxidation of contemporary PFOA-precursors.

Peer Reviewed: Analytical Challenges Hamper Perfluoroalkyl Research

The growing concern over these organohalogens, some of which have been found in human blood and appear to be widespread in the environment, led researchers to gather in Hamburg, Germany, in 2003 to evaluate the current state of methods to analyze for the organic contaminants. Jonathan Martin of the University of Toronto and 20 colleagues from industry, government, and academia summarize the main recommendations from the workshop.

Investigation of the sublethal effects of some petroleum refinery effluents

In Canada, environmental regulations for protection of the biota from the adverse effects of effluents from petroleum refineries have tended to focus on acute toxicity. There is concern those effluents may have other subtle, but still deleterious, long-term effects on aquatic ecosystems. We have used a battery of toxicity tests to assess the acute toxicity, genotoxicity, and chronic toxicity of effluent samples from two Ontario refineries. The test organisms included representatives of the bacterial, algal, plant, cladoceran, and fish communities. The results of our preliminary study indicate that the effluent samples had little acute toxicity to the test organisms. There were indications of some sublethal toxicity to Ceriodaphnia dubia, Panagrellus redivivus, and Pimephales promelas. One of the effluents inhibited the growth of Selanastrum capricornutum (IC50 of 59.9%) and Lemna gibba (IC25 of 73.3%) and also caused a 15 percent reduction in the germination of Lactuca sativa seeds. The SOS-Chromotest, a commercially available test that measures the activity of a bacterial DNA repair system, detected genotoxic effects in a single effluent that had been concentrated ten fold. There was no apparent relationship between several chemical parameters and the observed sublethal effects. Further research is needed to establish whether or not the observed toxic effects are typical of effluents from Ontario refineries.

The fate of oil and oil—dispersant mixtures in freshwater ponds

The fate, distribution and composition of oil and oil-dispersant mixtures were studied in a series of five, lined, inground ponds containing sandy gravel sediment and mesotrophic water. Normal Wells crude oil and Corexit 9527 were added at nominal concentrations of 100 and 20 ppm, respectively, to two of the ponds, and the crude oil alone was added at 100 ppm to a third pond. The water surface, water column, the sediment, pond liner and attached biota were systemically sampled for a year. While only about 2% of the oil remained in the water column of the pond with no dispersant addition, in the pond with the dispersant, about 10% of the oil persisted in the water for several weeks. Most of the oil initially dispersed in the water returned to the water surface, then eventually sank to the sediment. Thinner surface films showed a higher dispersant content than the thicker slicks , and the thinner films had higher infrared carbonyl absorption. Final distribution calculations revealed that about 45% of the oil had degraded in the oil-dispersant-treated ponds during the one year study, while only 23% could not be accounted for in the oil pond. Changes in the oil composition during the experiment were similar in all ponds, with no evidence to suggest that the dispersant affected oil composition in any special manner.

Impact of oil and oil-dispersant mixtures on flora and water chemistry parameters in freshwater ponds.

Oil and oil-dispersant mixtures at nominal concentrations of 100 and 20 ppm, respectively, were added to a series of ponds constructed for the study. In the pond treated with oil, there were no discernible short or long term effects on the phytoplankton. Both oil-dispersant treated ponds exhibited fluctuations in the dominant class of algae while the concentration of oil was greater than in the water column. Once the oil concentrations were below this value, there was no apparent effect. Periphytic material on the sides and bottoms of the oiled and control ponds were similar in mass and composed of a large number of species. Periphyton biomass was at least three times greater in both oil-dispersant-treated ponds with one genus dominating the growth. These conditions persisted in one of the oil-dispersant-treated ponds one year after treatment but those in the other pond had decreased to levels in the control pond at this time. Dissolved oxygen (DO) values decreased to about 4.6 ppm in both oil-dispersant-treated ponds shortly after treatment, but remained at approximately the saturation level in the other ponds for 6 weeks after treatment. Then these lower values gradually increased until they were slightly greater than in the controls. During the late winter months, both oil-dispersant ponds had anoxic zones above the sediment, the extent depending on the contours of the bottom. The DO values in the other ponds were at the saturation level. In the early spring, the nitrate ion-concentrations in control and oil-treated ponds were twice those measured for the oil-dispersant ponds. No discernible differences dependent on treatment were observed for nutrients or other ions monitored on a regular basis.

Impact of oil and oil-dispersant mixtures on the fauna of freshwater ponds

In a series of 5 artificial ponds, one was treated with a nomial concentration of 100 ppm of crude oil, two others were treated with a nominal 100 ppm of oil and 20 ppm of dispersant. Mesozooplankton populations were reduced in the oil-treated pond relative to the control pond, and eliminated in the oil-dispersant ponds. This condition persisted until the following year when the mesozooplankton was similar in all ponds. The protozooplankton experienced species shifts with Halteria and Strobilidium being eliminated initially in all treated ponds, but Halteria was collected in samples the following spring. Other protozoans such as thecamoebae increased in the treated ponds, while others, like zooflagellates , did not appear to be affected by the chemicals. Zoobenthos was affected by treatment, with the number of different types being reduced. The zoobenthos had recovered in one of the treated ponds the following spring, and that in the other treated ponds were recovering. Surface insects were eliminated after treatment, but recolonized during the next spring. Nekton were initially reduced by treatment. The population changes are discussed with respect to the fate of oil.

ECOLOGICAL EFFECTS OF OIL-DISPERSANT MIXTURES IN FRESH WATER

ABSTRACT A series of spills using oil and dispersant was begun July 5, 1978 in a set of artificial freshwater ponds. Prior to the spills, the ponds had been allowed to stabilize and the water as we...

Analytical Challenges Hamper Perfluoroalkyl Research : researches need better tools to get to the bootom of the contamination mystery

The growing concern over these organohalogens, some of which have been found in human blood and appear to be widespread in the environment, led researchers to gather in Hamburg, Germany, in 2003 to evaluate the current state of methods to analyze for the organic contaminants. Jonathan Martin of the University of Toronto and 20 colleagues from industry, government, and academia summarize the main recommendations from the workshop.