Source apportionment of polychlorinated biphenyls in the sediment of the Newtown Creek superfund site.

Polychlorinated biphenyls (PCBs) are a primary contaminant of potential concern at the Newtown Creek superfund site. Measurements of PCBs in hundreds of samples of sediment (surface and cores) within Newtown Creek and at nearby reference locations were obtained from the Remedial Investigation (RI) databases. This data set was analyzed using Positive Matrix Factorization (PMF). A weight-of-evidence approach was used to attribute the PMF-generated fingerprints to sources. The PMF analysis generated eight factors (fingerprints or sources) that represent primary sources, such as Aroclors, as well as secondary sources, including the East River and Combined Sewer Outfalls (CSOs). In addition to the high-production volume Aroclors (1016/1242, 1248, 1254, and 1260), some less-widely used Aroclors (1232 and 1268) were found in Newtown Creek sediment. Aroclor 1268 is disproportionately abundant in the deepest sediments, while PCBs likely from CSOs are relatively more abundant in surface sediment.

Isolating different natural and anthropogenic PAHs in the sediments from the northern Bering-Chukchi margin: Implications for transport processes in a warming Arctic.

Polycyclic aromatic hydrocarbons (PAHs) have become the dominating burden in the Arctic ecosystems, but their transport pathways and relative importance of different sources in the Arctic remained unclear, and this would be further complicated by climate change. Here we interpreted 27 PAHs in 34 surface sediments from the northern Bering-Chukchi margin. We integrated source apportionment methods (including diagnostic ratios, principal component analysis, hierarchical analysis, and positive matrix factorization (PMF) model) together with geochemistry parameters, which reveal a gradually clear picture of the spatial patterns of different sources. The total PAH concentrations (50.4 to 896.0 ng/g dw) exhibited a "hilly" shape with the increase of latitude, showing the highest level of PAHs in the northeast Chukchi Sea. The total BaP toxic equivalent quotient (TEQ) for carcinogenic compounds was from 1.06 to 33.3 ng TEQ/g. Most PAHs showed positive correlations with silt content, total organic carbon, stable carbon isotopes and black carbon (p < 0.01 or 0.05). Generally, source apportionment methods revealed an increasing petrogenic source of PAHs with latitudes. The PMF model further differentiated two petrogenic (36.7%), two pyrogenic (softwood and fossil fuel combustion, 35.5%) and one in-situ biogenic source (Perylene, 27.8%). An extremely high petrogenic signal was captured in the Canada Basin margin, possibly originating from the Mackenzie River via ice drifting with Beaufort Gyre, while another petrogenic source may come from coal deposit erosion by deglaciation. Softwood combustion (characterized by Retene) exhibited exclusively higher contribution in the northeast Chukchi Sea and might result from the increasing wildfire in Alaska due to climate change, whereas fossil fuel combustion exhibited similar contributions across different latitudes. Our results revealed natural PAHs as important "inside sources" in the Arctic, which are highly sensitive to global warming and deserves more attention.

Sources of polychlorinated biphenyls to Upper Hudson River sediment post-dredging.

The Upper Hudson River (UHR) has been contaminated with polychlorinated biphenyls (PCBs) since the 1940s due to the manufacture of capacitors at two plants near Hudson Falls and Fort Edward, NY by General Electric (GE). Dredging of portions of the UHR was conducted from 2009 to 2015 as a partial remedy for this contamination. In 2017, the New York State Department of Environmental Conservation undertook a comprehensive post-dredging survey of sediment contamination in the UHR. Thousands of samples were collected, and 130 of these were analyzed for PCBs using EPA method 1668A. This data set was analyzed using Positive Matrix Factorization. Six factors were observed. One factor resembled the dominant Aroclors used by GE with little alteration. Three factors represented different pathways and/or extents of microbial dechlorination. One factor resembled a mixture of microbial dechlorination products and a higher molecular weight Aroclor used by GE. The congener patterns of the dechlorination factors suggest that removal of chlorines at the ortho position does occur in the UHR sediment, in agreement with several laboratory studies showing that such ortho dechlorination is possible. This ortho dechlorination could theoretically lead to complete dechlorination of PCBs to biphenyl in UHR sediment. Only one factor was not attributable to GE. It represents inputs of PCBs from tributaries and urban areas and explains 1.7% of the PCB mass in the sediments. The small contribution from the non-GE PCB source suggests that recontamination of the sediment after dredging was minor.

Perfluoroalkyl substances in sediments from the Bering Sea to the western Arctic: Source and pathway analysis.

Although perfluoroalkyl substances (PFASs) are ubiquitous in the Arctic, their dominant pathways to the Arctic remain unclear. Most modeling studies support major oceanic transport for PFASs in the Arctic seawater, but this conclusion contradicts the rapid response of PFASs to global emissions in some biota species. Sediments, which act as important PFAS sinks for seawater and potential PFAS source to the benthic food web, are important for interpreting the fate of PFASs in the Arctic. Here we investigate the occurrence of 9 PFASs in one core (1945-2014) and 29 surface sediments from the Bering Sea to the western Arctic. Total PFAS concentrations (0.06-1.73 ng/g dw) in surface sediments were dominated by perfluorooctane sulfonate (PFOS), perfluorononanoic acid (PFNA) and perfluorobutyl sulfonate (PFBS), with higher levels in the Bering Sea slope and the northeast Chukchi Sea. Historical trends in PFASs varied among individuals, with PFOS declining in the early 2000s while PFNA showing an increasing up-core trend. Analysis of positive matrix factorization model identified that the major PFAS sources in the sediment core were dominated by the atmospheric oxidation of consumer use of PFOS precursor-based products (45.0%), while the oceanic transport of fluoropolymer manufacture of polyvinylidene fluoride (mainly PFNA) exhibited an increasing trend over time, becoming dominant in surface sediments (42.8%). Besides, local input of possible aqueous fire-fighting foams (mainly PFOS and PFBS) also acted as an important source currently (30.1%) and historically (34.9%). Our study revealed that the pathways of PFASs in Arctic sediments varied greatly for individuals and the conclusion of PFOS originating from mainly atmospheric oxidation was different from seawater modeling results. This, together with the high possibility of sediments as direct source to Arctic food web (supported by similar PFAS compositions and temporal variations), help provide additional evidence regarding PFAS pathways to the Arctic.