Perfluoroalkyl carboxylates and sulfonates and precursors in relation to dietary source tracers in the eggs of four species of gulls (Larids) from breeding sites spanning Atlantic to Pacific Canada

In the present study, we identified and examined the spatial trends, sources and dietary relationships of bioaccumulative perfluorinated sulfonate (PFSA; C(6), C(8), and C(10) chain lengths) and carboxylate (PFCA; C(6) to C(15) chain lengths) contaminants, as well as precursor compounds including several perfluorinated sulfonamides, and fluorotelomer acids and alcohols, in individual eggs (collected in 2008) from four gull species [glaucous-winged (Larus glaucescens), California (Larus californicus), ring-billed (Larus delawarensis) and herring (Larus argentatus) gulls] from 15 marine and freshwater colony sites in provinces across Canada. The pattern of PFSAs was dominated by perfluorooctane sulfonate (PFOS; >89% of ΣPFSA concentration) regardless of egg collection location. The highest ΣPFSA concentrations were found in the eggs collected in the urbanized areas in the Great Lakes and the St. Lawrence River area [Big Chicken Island 308 ng/g ww, Toronto Harbour 486 ng/g ww, and Ile Deslauriers (HG) 299 ng/g ww]. Also, eggs from all freshwater colony sites had higher ΣPFSA concentrations, which were significant (p<0.05) in many cases, compared to the marine sites with the exception of the Sable Island colony in Atlantic Canada off the coast of Nova Scotia. C(6) to C(15) chain length PFCAs were detected in the eggs, although the pattern was variable among the 15 sites, where PFUnA and PFTrA dominated the pattern for most colonies. Like the ΣPFSA, the highest concentrations of ΣPFCA were found in the eggs from Big Chicken Island, Toronto Harbour, Ile Deslauriers (HG), and Sable Island, although not all freshwater sites had higher concentrations compared to marine sites. Dietary tracers [δ(15)N and δ(13)C stable isotopes (SIs)] revealed that PFSA and PFCA exposure is colony dependent. SI signatures suggested that gulls from most marine colony sites were exposed to PFCs via marine prey. The exception was the Mandarte Island colony in Pacific British Columbia, where PFSA and PFCA exposure appeared to be via terrestrial and/or freshwater prey consumption. The same was true for the freshwater sites where egg SIs suggested both aquatic and terrestrial prey consumption as the source for PFC exposure depending on the colony. Both aquatic (marine and freshwater) and terrestrial prey are likely sources of PFC exposure to gulls but exposure scenarios are colony-specific.     

A temporal trend study (1972-2008) of perfluorooctanesulfonate, perfluorohexanesulfonate, and perfluorooctanoate in pooled human milk samples from Stockholm, Sweden

The widespread presence of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorohexanesulfonate (PFHxS) in human general populations and their slow elimination profiles have led to renewed interest in understanding the potential human neonatal exposures of perfluoroalkyls (PFAs) from consumption of human milk. The objective of this study was to evaluate the concentrations of PFOS, PFHxS, and PFOA in pooled human milk samples obtained in Sweden between 1972 and 2008 (a period representing the most significant period of PFA production) and to see whether the time trend of these analytes parallels that indicated in human serum. Chemical analysis of PFOS, PFHxS, and PFOA was performed on pooled Swedish human milk samples from 1972 to 2008 after methodological refinements. The 20 samples which formed the 2007 pool were also analyzed individually to evaluate sample variations. Analyses were performed by HPLC-MS/MS. Due to the complexities of the human milk matrix and the requirement to accurately quantitate low pg/mL concentrations, meticulous attention must be paid to background contamination if accurate results are to be obtained. PFOS was the predominant analyte present in the pools and all three analytes showed statistically significant increasing trends from 1972 to 2000, with concentrations reaching a plateau in the 1990s. PFOA and PFOS showed statistically significant decreasing trends during 2001-2008. At the end of the study, in 2008, the measured concentrations of PFOS, PFHxS, and PFOA in pooled human milk were 75 pg/mL, 14 pg/mL, and 74 pg/mL, respectively. The temporal concentration trends of PFOS, PFHxS, and PFOA observed in human milk are parallel to those reported in the general population serum concentrations.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

Spatial and seasonal variations in atrazine and metolachlor surface water concentrations in Ontario (Canada) using ELISA

Concerns regarding the impacts of pesticides on aquatic species and drinking water sources have increased demands on water quality monitoring programs; however the costs of sample analysis can be prohibitive. In this study we investigated enzyme-linked immunosorbent assay (ELISA) as a cost-effective, high through-put method for measuring pesticide concentrations in surface waters. Seven hundred and thirty-nine samples from 158 locations throughout Ontario were analysed for atrazine and metolachlor from April to October 2007. Concentrations ranged from <0.1 to 3.91 μg L⁻¹ (median = 0.12 μg L⁻¹) for atrazine and from <0.1 to 1.83 μg L⁻¹ (median = 0.09 μg L⁻¹) for metolachlor. Peak concentrations occurred in late spring/early summer, in rural agricultural locations, and decreased over the remainder of the growing season for both herbicides. About 3% of the samples that had ELISA results occurring above the limit of quantification (0.10 μg L⁻¹) were evaluated against gas chromatography-mass spectrometry (GC-MS). Linear regression analysis revealed a R² value of 0.88 and 0.39, for atrazine and metolachlor, respectively. ELISA tended to overestimate concentrations for atrazine and metolachlor, most likely because the ELISA kits also detect their metabolites. Atrazine data suggest that ELISA may be used complementary with GC-MS analysis to enhance the spatial and temporal resolution of a water quality monitoring study. The commercially available metolachlor ELISA kit requires further investigation. ELISA may be used to detect atrazine and metolachlor in surface water samples, but it is not recommended as a quantitative replacement for traditional analytical methods.     

Exposure to moderate concentrations of tropospheric ozone impairs tree stomatal response to carbon dioxide

With rising concentrations of both atmospheric carbon dioxide (CO₂) and tropospheric ozone (O₃), it is important to better understand the interacting effects of these two trace gases on plant physiology affecting land-atmosphere gas exchange. We investigated the effect of growth under elevated CO₂ and O₃, singly and in combination, on the primary short-term stomatal response to CO₂ concentration in paper birch at the Aspen FACE experiment. Leaves from trees grown in elevated CO₂ and/or O₃ exhibited weaker short-term responses of stomatal conductance to both an increase and a decrease in CO₂ concentration from current ambient level. The impairement of the stomatal CO₂ response by O₃ most likely developed progressively over the growing season as assessed by sap flux measurements. Our results suggest that expectations of plant water-savings and reduced stomatal air pollution uptake under rising atmospheric CO₂ may not hold for northern hardwood forests under concurrently rising tropospheric O₃.     

Assessment of heavy metal pollution from a Fe-smelting plant in urban river sediments using environmental magnetic and geochemical methods

Environmental magnetic proxies provide a rapid means of assessing the degree of industrial heavy metal pollution in soils and sediments. To test the efficiency of magnetic methods for detecting contaminates from a Fe-smelting plant in Loudi City, Hunan Province (China) we investigated river sediments from Lianshui River. Both magnetic and non-magnetic (microscopic, chemical and statistical) methods were used to characterize these sediments. Anthropogenic heavy metals coexist with coarse-grained magnetic spherules. It can be demonstrated that the Pollution Load Index of industrial heavy metals (Fe, V, Cr, Mo, Zn, Pb, Cd, Cu) and the logarithm of saturation isothermal remanent magnetization, a proxy for magnetic concentration, are significantly correlated. The distribution heavy metal pollution in the Lianshui River is controlled by surface water transport and deposition. Our findings demonstrate that magnetic methods have a useful and practical application for detecting and mapping pollution in and around modern industrial cities.     

The endocrine disrupting potential of sediments from the Upper Danube River (Germany) as revealed by in vitro bioassays and chemical analysis

Introduction  

The present study was part of a comprehensive weight-of-evidence approach with the goal of identifying potential causes for the declines in fish populations, which have been observed during the past decades in the Upper Danube River.     

Evaluation of hexachlorocyclohexane contamination from the last lindane production plant operating in India

Purpose

??-Hexachlorocyclohexane (HCH), ??-HCH, and lindane (??-HCH) were listed as persistent organic pollutants by the Stockholm Convention in 2009 and hence must be phased out and their wastes/stockpiles eliminated. At the last operating lindane manufacturing unit, we conducted a preliminary evaluation of HCH contamination levels in soil and water samples collected around the production area and the vicinity of a major dumpsite to inform the design of processes for an appropriate implementation of the Convention.

Methods

Soil and water samples on and around the production site and a major waste dumpsite were measured for HCH levels.

Results

All soil samples taken at the lindane production facility and dumpsite and in their vicinity were contaminated with an isomer pattern characteristic of HCH production waste. At the dumpsite surface samples contained up to 450?g?kg^?1 ?? HCH suggesting that the waste HCH isomers were simply dumped at this location. Ground water in the vicinity and river water was found to be contaminated with 0.2 to 0.4?mg?l^?1 of HCH waste isomers. The total quantity of deposited HCH wastes from the lindane production unit was estimated at between 36,000 and 54,000?t.

Conclusions

The contamination levels in ground and river water suggest significant run-off from the dumped HCH wastes and contamination of drinking water resources. The extent of dumping urgently needs to be assessed regarding the risks to human and ecosystem health. A plan for securing the waste isomers needs to be developed and implemented together with a plan for their final elimination. As part of the assessment, any polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) generated during HCH recycling operations need to be monitored.     

Hexachlorocyclohexane (HCH) as new Stockholm Convention POPs��a global perspective on the management of Lindane and its waste isomers

Purpose

Hexachlorocyclohexane (HCH) isomers (??-, ??- and ??- (Lindane)) were recently included as new persistent organic pollutants (POPs) in the Stockholm Convention, and therefore, the legacy of HCH and Lindane production became a contemporary topic of global relevance. This article wants to briefly summarise the outcomes of the Stockholm Convention process and make an estimation of the amount of HCH waste generated and dumped in the former Lindane/HCH-producing countries.

Results

In a preliminary assessment, the countries and the respective amount of HCH residues stored and deposited from Lindane production are estimated. Between 4 and 7 million tonnes of wastes of toxic, persistent and bioaccumulative residues (largely consisting of alpha- (approx. 80%) and beta-HCH) are estimated to have been produced and discarded around the globe during 60 years of Lindane production. For approximately 1.9 million tonnes, information is available regarding deposition. Countries are: Austria, Brazil, China, Czech Republic, France, Germany, Hungary, India, Italy, Japan, Macedonia, Nigeria, Poland, Romania, Slovakia, South Africa, Spain, Switzerland, Turkey, The Netherlands, UK, USA, and former USSR. The paper highlights the environmental relevance of deposited HCH wastes and the related POPs?? contaminated sites and provides suggestions for further steps to address the challenge of the legacy of HCH/Lindane production.

Conclusion

It can be expected that most locations where HCH waste was discarded/stockpiled are not secured and that critical environmental impacts are resulting from leaching and volatilisation. As parties to the Stockholm Convention are legally required to take action to stop further POPs pollution, identification and evaluation of such sites are necessary.     

Effects of perfluorinated compounds on development of zebrafish embryos

Perfluorinated compounds (PFCs) have been widely used in industrial and consumer products and frequently detected in many environmental media. Potential reproductive effects of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) have been reported in mice, rats and water birds. PFOS and PFOA were also confirmed developing toxicants towards zebrafish embryos; however, the reported effect concentrations were contradictory. Polyfluorinated alkylated phosphate ester surfactants (including FC807) are precursor of PFOS and PFOA; however, there is no published information about the effects of FC807 and PFNA on zebrafish embryos. Therefore, this study was conducted to determine the effects of these four PFCs on zebrafish embryos. Normal fertilized zebrafish embryos were selected to be exposed to several concentrations of PFOA, PFNA, PFOS or FC807 in 24-well cell culture plates. A digital camera was used to image morphological anomalies of embryos with a stereomicroscope. Embryos were observed through matching up to 96-h post-fertilization (hpf) and rates of survival and abnormalities recorded. PFCs caused lethality in a concentration-dependent manner with potential toxicity in the order of PFOS > FC807 > PFNA > PFOA based on 72-h LC(50). Forty-eight-hour post-fertilization pericardial edema and 72- or 96-hpf spine crooked malformation were all observed. PFOA, PFNA, PFOS and FC807 all caused structural abnormalities using early stages of development of zebrafish. The PFCs all retarded the development of zebrafish embryos. The toxicity of the PFCs was related to the length of the PFC chain and functional groups.