Trends in hexabromocyclododecanes in the UK and North America.

Water samples (n = 107) taken from nine English freshwater lakes from a mix of urban, rural, and remote locations on 12 occasions between August 2008 and February 2012, and archived suspended sediment samples (n = 39) collected over the period 1980-2012 at the mouth of the Niagara River in Lake Ontario were analysed to assess the temporal trends in contamination by the three main hexabromocyclododecane (HBCD) diastereomers (α-, ß-, and γ-HBCD). HBCDs (45 to 890 pg L-1, n = 107) were generally equally distributed between the operationally defined freely dissolved and particulate phases in English lake water. Concentrations of HBCDs declined over the sampling period with half-lives of 5.1 years in English water, with a significantly decreasing trend also observed for Niagara River suspended sediments (NRSSs). With respect to seasonal trends, significantly higher concentrations were found in colder compared to warmer periods at 5 out of 9 English lakes, while NRSSs in this study revealed no statistically significant seasonal trends. The maximum HBCD concentration in NRSSs was about 3 orders of magnitude lower than those detected in English lake water, which is plausible given the greater per capita use of HBCD in Europe than North America. While γ-HBCD was consistently dominant (35-86%; mean = 56%) in English lake water samples, and dominated in NRSSs collected prior to 2002 inclusive (13-100%, mean = 73%), the abundance of γ-HBCD was significantly lower (3.5-37%; mean = 23%) in NRSSs from 2003 onwards.

Spatial distributions and temporal trends in polybrominated diphenyl ethers in Detroit River suspended sediments.

Suspended sediments from the Detroit River were collected using sediment traps at sites ranging from western Lake Erie to southern Lake St. Clair to assess spatial distributions and temporal trends of polybrominated diphenyl ethers (PBDEs). The distribution of PBDEs in suspended sediments in the Detroit River appeared influenced by shoreline-based contemporary urban and industrial activities, which stood in contrast to PCBs that were associated with areas of historic industrial activity. Temporal trend data indicate that total PBDE concentrations decreased in the period after 2000 in response to cessation of production of the penta- and octa BDE formulations. Concentrations of total PBDEs ranged from roughly 7 ng g(-1) (4 ng g(-1) BDE 209) in southern Lake St. Clair to several hundred ng g(-1) (60-180 ng g(-1) BDE 209) in the lower reaches of the Detroit River. The widespread occurrence of PBDEs in Detroit River suspended sediments suggests that large urban areas can act as diffuse sources of these chemicals that are used in modern industrial applications and consumer products.

Fate, distribution, and contrasting temporal trends of perfluoroalkyl substances (PFASs) in Lake Ontario, Canada.

Lake Ontario water and sediment collected from tributary, nearshore, and open lake sites were analyzed for perfluoroalkyl substances (PFASs), namely perfluoroalkyl carboxylic acids (PFCAs, F(CF(2))(n)CO(2)(-); n=6-11,13) and perfluoroalkane sulfonic acids (PFSAs, F(CF(2))(n)SO(3)(-); n=6,8,10). Survey results of surface sediment and water indicated that shorter chained PFASs were predominant in and near urban/industrial area watersheds, while longer chained PFASs were predominant in fine-grained sediment from major depositional basins. Niagara River suspended solids (1981-2006) demonstrated temporal trends that may have been influenced by recent changes in North American production and use of PFASs. Perfluorooctane sulfonate (PFOS) reached a peak concentration in 2001 of 1.1 ng/g, followed by a decrease from 2001 to 2006 (half-life=9 years). Perfluorooctanoic acid (PFOA) increased from 2001 to 2006 (doubling time= 2 years) reaching a peak concentration of 0.80 ng/g. In contrast, three sediment cores from western, central, and eastern Lake Ontario showed increasing temporal trends to surface sediment for all PFASs. PFOA and PFOS concentrations increased from 1988 to 2004 (doubling time= ~ 4 years) in the western Lake Ontario core. The observed variations in temporal trends from different environmental compartments may be a result of the physico-chemical properties of PFASs, ongoing emissions, and the environmental transformation and degradation of PFAS precursor compounds.

Dechloranes 602, 603, 604, Dechlorane Plus, and Chlordene Plus, a newly detected analogue, in tributary sediments of the Laurentian Great Lakes.

A chlorinated compound (Chlordene Plus, CP), structurally related to Dechloranes (Dec) 602, 603, 604, and Dechlorane Plus (DP), was identified, and concentrations and spatial trends of Dec 602, 603, 604, CP, and DP in tributary sediments of the Laurentian Great Lakes are reported. The dechloranes were widely detected with their concentrations varying considerably across the Great Lakes basin. Spatial trends of Dec 602, 604, and DP in Canadian tributary sediments were similar to that of BDE 209, which suggested these flame retardant chemicals in tributaries were associated with industrial and urban areas. The highest concentrations of Dec 602, 604, and DP observed in tributaries of the Niagara River confirmed that past or ongoing manufacturing of these compounds at plants along the river were important sources to Lake Ontario. Dec 603 was detected in technical products of aldrin and dieldrin, and its spatial trend was consistent with historic pesticide usage. Similarly, CP was detected in technical products of chlordene and chlordane, and it was found in higher concentrations in sediments near urban areas, possibly related to past chlordane use in home termite control.

Occurrence and sources of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in surficial sediments of Lakes Superior and Huron.

Concentrations and congener profile patterns of 2378-substituted PCDD/Fs and DLPCBs in offshore, nearshore and tributary sediments of Lakes Superior and Huron are reported, and spatial trends and source contributions assessed. PCDD/F concentrations ranged from 5 to 18,000 pg/g dw (Lake Superior) and 3 to 6100 pg/g dw (Lake Huron); DLPCBs ranged from 9 to 11,000 pg/g dw (Lake Superior) and 9 to 27,000 pg/g dw (Lake Huron). Our analysis indicated atmospheric deposition is a primary source to depositional areas of both lakes; however, greater PCDD/F and DLPCB concentrations were observed at several nearshore and tributary sites, and were attributed to corresponding land use in the watershed. Statistical analysis and pattern comparison suggested that industrial inputs mainly associated with wood treatment plants, pulp and paper mills, mining operations, and chlorine-based chemical manufacturing also contributed to contamination by PCDD/Fs and DLPCBs in certain nearshore and offshore areas of Lakes Superior and Huron.

Changes in surface area and concentrations of semivolatile organic contaminants in aging snow.

During the winter of 1999/2000 five snowpacks at Turkey Lake Watershed east of Lake Superior were sampled immediately after falling and again after several days of aging for the analysis of specific snow surface area and the concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The snow surface could be determined with a relative coefficient of variation of 6% using frontal chromatography, measuring the retention of ethyl acetate, a substance with known adsorption coefficient on the ice surface. The snow surface area of fresh snow varied from 1000 to 1330 cm2/g and was higher for snow falling during colder days. The aged snow samples had consistently lower surface areas ranging from 520 to 780 cm2/g, corresponding to an average loss of half of the initial surface area during aging. The rate of loss of surface area was faster at higher temperatures. Dieldrin, alpha-HCH, and gamma-HCH were the most abundant OCPs in snowmelt water, but endosulfan, chlordane-related substances, heptachlor epoxide, pp'-DDT, pp'-DDE, and chlorinated benzenes were also consistently present. Three midwinter snowpacks that aged during relatively cold temperatures generally experienced a loss of PCBs and OCPs that was of the same order of magnitude as the observed loss of snow surface area. However, no relationship between the extent of loss and the strength of a contaminants' sorption to snow was apparent. Few significant changes in snowpack concentrations of OCPs and PCBs were observed in a snowpack that fell at relatively high temperatures and aged under colder conditions. Concentrations of OCPs and PCBs increased in a late-winter snowpack that aged while temperatures rapidly increased to above freezing. Concentrations of pp'-DDE and endosulfan-II that increased in snowpacks that saw simultaneous decreases in the levels of pp'-DDT and endosulfan-I hint at the occurrence of sunlight induced conversions in snow. While surface area decreases clearly contribute to the loss of semivolatile organic compounds from metamorphosing snowpacks, other confounding factors play a role in determining concentration changes, in particular in wet snow.

Polybrominated diphenyl ethers (PBDEs) in human milk from Australia.

Polybrominated diphenyl ethers (PBDEs) are flame retardants added to a multitude of products to reduce flammability. PBDEs have been widely detected and quantified in biota and humans in many industrialised countries from the Northern Hemisphere. However data concerning the levels of these compounds in the Australian population and environment remain limited. The objectives of this study were to determine PBDE concentrations and congener profiles in Australian human milk and compare this to concentrations found in other countries. Pooled human milk samples obtained from mothers residing in 12 regions of Australia were analysed by HRGC/HRMS for 18 PBDE congeners. In total, 157 human milk samples collected in 2002 and 2003 were divided into 17 regional pools. PBDEs were detected in all pools of human milk from Australia. The mean+/-standard deviation and median summation operatorPBDE concentrations were 11.1+/-3.2 and 11.0 ng g(-1) lipid, respectively with a range of 6.1-18.7 ng g(-1) lipid. The congener profile was dominated by BDE-47 followed by BDE-99, -100, -153, -154 and -183. Regional differences were evaluated, but no trends were observed. The data suggest regional differences are likely to be small if they exist at all. The concentrations of PBDEs found in Australian human milk were lower than those reported from North America but higher than those reported from Europe and Asia. Our results suggest that the exposure pathways which contribute to the PBDE body burden in the Australian population require a better understanding in order to determine future policy regarding their use and disposal.