Time Trends of Polybrominated Diphenyl Ethers (PBDEs) in Antarctic Biota.

Polybrominated diphenyl ethers (PBDEs) are "emerged" contaminants that were produced and used as flame retardants in numerous consumer and industrial applications for decades until banned. They remain ubiquitously present in the environment today. Here, a unique set of >200 biotic samples from the Antarctic was analyzed for PBDEs, including phytoplankton, krill, fish, and fur seal milk, spanning several sampling seasons over 14 years. PBDE-47 and -99 were the dominant congeners determined in all samples, constituting >60% of total PBDEs. A temporal trend was observed for ∑7PBDE concentrations in fur seal milk, where concentrations significantly increased (R2 = 0.57, p < 0.05) over time (2000-2014). Results for krill and phytoplankton also suggested increasing PBDE concentrations over time. Trends of PBDEs in fur seal milk of individual seals sampled 1 or more years apart showed no clear temporal trends. Overall, there was no indication of PBDEs decreasing in Antarctic biota yet, whereas numerous studies have reported decreasing trends in the northern hemisphere. Similar PBDE concentrations in perinatal versus nonperinatal milk implied the importance of local PBDE sources for bioaccumulation. These results indicate the need for continued assessment of contaminant trends, such as PBDEs, and their replacements, in Antarctica.

Persistent organic pollutants in the Atlantic and southern oceans and oceanic atmosphere.

Persistent organic pollutants (POPs) continue to cycle through the atmosphere and hydrosphere despite banned or severely restricted usages. Global scale analyses of POPs are challenging, but knowledge of the current distribution of these compounds is needed to understand the movement and long-term consequences of their global use. In the current study, air and seawater samples were collected Oct. 2007-Jan. 2008 aboard the Icebreaker Oden en route from Göteborg, Sweden to McMurdo Station, Antarctica. Both air and surface seawater samples consistently contained α-hexachlorocyclohexane (α-HCH), γ-HCH, hexachlorobenzene (HCB), α-Endosulfan, and polychlorinated biphenyls (PCBs). Sample concentrations for most POPs in air were higher in the northern hemisphere with the exception of HCB, which had high gas phase concentrations in the northern and southern latitudes and low concentrations near the equator. South Atlantic and Southern Ocean seawater had a high ratio of α-HCH to γ-HCH, indicating persisting levels from technical grade sources. The Atlantic and Southern Ocean continue to be net sinks for atmospheric α-, γ-HCH, and Endosulfan despite declining usage.

Polychlorinated biphenyls and organochlorine pesticides as intrinsic tracer tags of foraging grounds of bluefin tuna in the northwest Atlantic Ocean.

Researchers have utilized chemical fingerprints in the determination of habitat utilization and movements of the aquatic animals. In the present effort, we analyzed polychlorinated biphenyl (PCB) congeners and organochlorine pesticides in the samples of juvenile bluefin tuna caught offshore of Virginia, and in larger bluefin tuna from the Gulf of Maine and near Nova Scotia. For a given specimen, or a given location, PCB concentrations were highest, followed by DDTs, and chlordanes. Average contaminant concentrations from fish captured from the three locations were not significantly different; and PCBs, DDTs, and chlordanes correlated well with each other. Trans-nonachlor/PCB 153 ratios in bluefin tuna of eastern Atlantic (i.e., Mediterranean) origin are low compared to the corresponding ratios in fish in the western Atlantic. As the former migrate to the western Atlantic, these ratios gradually turnover due to the accumulation of biomass from forage contaminated with higher trans-nonachlor/PCB 153 ratio reflecting dissimilar use of chlordane pesticides on two sides of the Atlantic Ocean. The trans-nonachlor/PCB 153 ratio indicated that one juvenile bluefin tuna from offshore of Virginia and one large bluefin tuna from Gulf of Maine in the present study originated from foraging grounds in the Mediterranean Sea, and that they have made the trans-Atlantic migrations. The remaining individuals were determined to be either spawned in the Gulf of Mexico or the trans-nonachlor/PCB 153 ratio for the putative Mediterranean bluefin tuna was completely turned over to resemble the ratio characteristic to the western Atlantic. Based on the turnover time for trans-nonachlor/PCB 153 ratio previously determined, the residence time of juvenile bluefin tuna offshore Virginia was estimated to be at least 0.8 to 1.6years. A discriminant function analysis (DFA) plot of total PCB normalized signatures of PCB congeners showed three separate clusters, which suggested that bluefin tuna from offshore Virginia, Gulf of Maine, and Nova Scotia could have had extended residences and foraging within the areas of capture to be able to sustain the stable signatures of PCB congeners. The DFA cluster results supported the concept of metapopulation theory of spatial ecology comprising discrete aggregates of local populations of bluefin tuna where the desired prey species are likely to be abundant. Despite their highly migratory trait and endothermic advantage of foraging in broader and colder habitats, the movements and mixing across the aggregation ranges related to feeding did not appear to be extensive. Advancement in the understanding of bluefin tuna population dynamics beyond the coarse concept of trans-Atlantic migrations to the metapopulation hypothesis provides a novel exploratory tool in the stock assessment and resource management. As the chemical tracer tags are fortified naturally and document the time- and space-integrated foraging history, they promise to serve as the low-cost alternatives to the high-cost electronic data recording tags employed for addressing the migratory movements of bluefin tuna. Between the different potential chemical tracer tags, a distinct advantage of PCB/pesticide analysis over the otolith micro-constituent analysis is that the muscle tissue of a given individual bluefin tuna can be sampled repeatedly for PCB/pesticide analysis over different spatial and temporal scales in a non-lethal manner.

Inter-annual variation of persistent organic pollutants (POPS) in an Antarctic top predator Arctocephalus gazella.

Persistent organic pollutants (POPs), contaminants that may bioaccumulate in upper trophic level organisms, were detected in the milk of a top predator, the Antarctic fur seal (Arctocephalus gazella). Multiparous females had significantly lower concentrations of certain POPs (trans-nonachlor, p,p'-DDE, and several PCBs) in their milk than primiparous females, likely due to the annual lactational transfer of the POP burden from mother to pup. Furthermore, there were significant interannual differences in POP concentrations in multiparous females' milk from five breeding seasons between 2000 and 2011. Decreasing trends in concentrations of certain POPs over the recent decade coincide with declining global emissions, yet atmospheric concentrations in the Antarctic are not always consistent with global trends, suggesting that additional factors may contribute to temporal trends of POPs in fur seals. Climate shifts and corresponding availability of krill over the past decade were not consistent with trends observed in POP concentrations in fur seal milk, suggesting that climate may not be a key factor. Additional mechanisms, such as variability in the geographic ranges of individual seals during overwintering migrations are discussed and should be explored further.

Aerosol-mediated transport and deposition of brominated diphenyl ethers to Antarctica.

Brominated diphenyl ethers (BDE47, 99, 100, and 209) were measured in air, snow and sea ice throughout western Antarctica between 2001 and 2007. BDEs in Antarctic air were predominantly associated with aerosols and were low compared to those in remote regions of the northern hemisphere, except in Marguerite Bay following the fire at Rothera research station in Sept 2001, indicating that this event was a local source of BDE209 to the Antarctic environment. Aerosol BDE47/100 reflects a mixture of commercial pentaBDE products; however, BDE99/100 is suggestive of photodegradation of BDE99 during long-range atmospheric transport (LRAT) in the austral summer. BDEs in snow were lower than predicted based on snow scavenging of aerosols indicating that atmospheric deposition events may be episodic. BDE47, -99, and -100 significantly declined in Antarctic sea ice between 2001 and 2007; however, BDE209 did not decline in Antarctic sea ice over the same time period. Significant losses of BDE99 and -100 from sea ice were recorded over a 19 day period in spring 2001 demonstrating that seasonal ice processes result in the preferential loss of some BDEs. BDE47/100 and BDE99/100 in sea ice samples reflect commercial pentaBDE products, suggesting that photodegradation of BDE99 is minimal during LRAT in the austral winter.

Atlantic bluefin tuna (Thunnus thynnus) population dynamics delineated by organochlorine tracers.

Atlantic bluefin tuna (ABFT) are highly valued and heavily exploited, and critical uncertainties regarding their population structure hinder effective management. Evidence supports the existence of two breeding populations of ABFT; a western population in the Gulf of Mexico and an eastern population in the Mediterranean Sea; both of which migrate and mix in the North Atlantic. Conventional tagging studies suggest low rates of trans-Atlantic migrations; however, electronic tagging and stable isotopes in otoliths indicate stock mixing up to 57% between management zones delineated by 45 degrees W longitude. Here we show that organochlorine pesticides and polychlorinated biphenyls (PCBs) can be used as tracers of bluefin tuna foraging grounds in the North Atlantic and confirm that stock mixing of juvenile tuna within the U.S. Mid Atlantic Bight is indeed high (33-83% eastern origin), and is likely spatially and temporally variable. We further demonstrate that >10% of the Mediterranean population is migratory, that young bluefin tuna migrate from the Mediterranean to western Atlantic foraging grounds as early as age 1, and then return to the Mediterranean Sea as young as age 5, presumably to breed. The tracer method described here provides a novel means for distinguishing bluefin tuna populations and ontogenetic shifts in migration in the North Atlantic.

Changes in sediment and organic carbon accumulation in a highly-disturbed ecosystem: the Sacramento-San Joaquin River Delta (California, USA).

We used the Sacramento-San Joaquin River Delta CA (Delta, hereafter) as a model system for understanding how human activities influence the delivery of sediment and total organic carbon (TOC) over the past 50-60 years. Sediment cores were collected from sites within the Delta representing the Sacramento River (SAC), the San Joaquin River (SJR), and Franks Tract (FT), a flooded agricultural tract. A variety of anthropogenic tracers including (137)Cs, total DDE (Sigma DDE) and brominated diphenyl ether (BDE) congeners were used to quantify sediment accumulation rates. This information was combined with total organic carbon (TOC) profiles to quantify rates of TOC accumulation. Across the three sites, sediment and TOC accumulation rates were four to eight-fold higher prior to 1972. Changes in sediment and TOC accumulation were coincident with completion of several large reservoirs and increased agriculture and urbanization in the Delta watershed. Radiocarbon content of TOC indicated that much of the carbon delivered to the Delta is "pre-aged" reflecting processing in the Delta watershed or during transport to the sites rather than an input of predominantly contemporary carbon (e.g., 900-1400 years BP in surface sediments and 2200 yrs BP and 3610 yrs BP at the base of the SJR and FT cores, respectively). Together, these data suggest that human activities have altered the amount and age of TOC accumulating in the Delta since the 1940s.

Organochlorine pesticide air-water exchange and bioconcentration in krill in the Ross Sea.

Mean hexachlorobenzene (HCB) and hexachlorocyclohexane (HCH) concentrations, measured in seawater and air samples, confirmed the decline in levels of these compounds in Antarctic air and water. However, low alpha/gamma-HCH ratios in air at the beginning of the sampling period suggest a predominance of fresh lindane entering the Antarctic atmosphere during the Austral spring probably due to current use in the Southern Hemisphere. Water-air fugacity ratios demonstrate the potential for HCH gas deposition to coastal Antarctic seas, while the water-air fugacity ratios for HCB imply that volatilization does not account for the observed decrease of HCB in surface seawater. HCH concentrations found in krill samples were correlated with seawater concentrations indicative of bioconcentration of HCHs from seawater.

Melting glaciers: a probable source of DDT to the Antarctic marine ecosystem.

Persistent organic pollutants reach polar regions by long-range atmospheric transport and biomagnify through the food web accumulating in higher trophic level predators. We analyzed Adélie penguin (Pygoscelis adeliae) samples collected from 2004 to 2006 to evaluate current levels of sigmaDDT (p,p'-DDT + p,p'-DDE) in these birds, which are confined to Antarctica. Ratios of p,p'-DDT to p,p'-DDE in Adélie penguins have declined significantly since 1964 indicating current exposure to old rather than new sources of sigmaDDT. However, sigmaDDT has not declined in Adélie penguins from the Western Antarctic Peninsula for more than 30 years and the presence of p,p'-DDT in these birds indicates that there is a current source of DDT to the Antarctic marine food web. DDT has been banned or severely restricted since peak use in the 1970s, implicating glacier meltwater as a likely source for DDT contamination in coastal Antarctic seas. Our estimates indicate that 1-4 kg x y(-1) sigmaDDT are currently being released into coastal waters along the Western Antarctic Ice Sheet due to glacier ablation.

Atmospheric concentrations and air-water flux of organochlorine pesticides along the Western Antarctic Peninsula.

Air, seawater, sea ice, and snow were collected during the austral winter (September-October 2001) and summer (January-February 2002) along the Western Antarctic Peninsula. Hexachlorobenzene (HCB) > heptachlor > alpha- and gamma-hexachlorocyclohexane (HCH) and heptachlor epoxide, were the most frequently detected organochlorine pesticides in air. HCB and HCH levels declined over the past 20 years, with a half-life of 3 years for sigmaHCH in Antarctic air. However, heptachlor epoxide levels have not declined in Antarctic air over the past decade, possibly due to continued use of heptachlor in the southern hemisphere. Peak heptachlor concentrations in air were measured coincident with air masses moving into the region from lower latitudes. Levels of lindane were 1.2-200 times higher in annual sea ice and snow compared to alpha-HCH, likely due to greater atmospheric input of gamma-HCH. The ratio of alpha/gamma-HCH in Antarctic air, sea ice and snow was <1, illustrative of a predominance of influx of lindane versus technical HCH to the regional environment. However, alpha/gamma-HCH in seawater was >1, likely due to more rapid microbial degradation of gamma- versus alpha-HCH. Water/air fugacity ratios for HCHs demonstrate continued atmospheric influx of HCHs to coastal Antarctic seas, particularly during late summer.

Polycyclic aromatic hydrocarbons in a highly industrialized urban estuary: inventories and trends.

The abundance and composition of polycyclic aromatic hydrocarbons (PAHs) in sediments of the main stem and southern branch of the Elizabeth River (VA, USA), a highly industrialized urban estuary in the Chesapeake Bay (USA) watershed, were examined relative to historical and toxic effects levels. Total PAH concentrations in Elizabeth River sediments exceeded those observed in Baltimore Harbor and the Anacostia River, two other regions of concern in the Chesapeake Bay. The sigmaPAH concentrations from samples collected in the vicinity of two former wood-treatment facilities in the Elizabeth River had the highest sigmaPAH when compared to coastal and estuarine systems around the world. Using a linearized diffusion model equation, as much as 69% of the variability in channel sediment sigmaPAH distribution could be ascribed to inputs associated with former wood-treatment facilities along the southern branch of the Elizabeth River. Comparison of PAH levels measured in channel samples to data collected during the early 1980s demonstrated a general trend toward reduction in contaminant concentrations for most regions of the Elizabeth River channel; however, steady-state and increased sediment PAH concentrations in the vicinity of the former wood-treatment facilities were observed. Based on examination of the contaminant levels in Elizabeth River sediments using established sediment-quality criteria, the southern branch of the river remains a clear hazard to benthic and pelagic organisms.

Fractionation of stable isotope-labeled organic pollutants as a potential tracer of atmospheric transport processes.

To test the potential for using stable isotope fractionation to examine the atmospheric transport of semivolatile organic compounds (SOCs), we conducted simplified distillation experiments in the laboratory and a tracer-release experiment using mixtures of stable isotope-labeled (D and 13C) and unlabeled SOCs. Perdeuterated phenanthrene and alpha-hexachlorocyclohexane were transported more slowly via air-water gas exchange in our laboratory experiments, resulting in significant isotope fractionation of perdeuterated/unlabeled compound mixtures. In contrast, isotope fractionation of 13C6-labeled SOCs was much lower. A field tracer-release study was then conducted by spiking a seawater retention pond with a mixture of D10-labeled, 13C2-labeled, and unlabeled phenanthrene and examining isotope fractionation of the mixture after air-water gas exchange. No preferential fractionation of D10-vs 13C2-labeled phenanthrene was observed in the pond water; however, greater fractionation of D10-vs 13C2-labeled phenanthrene was observed in air samples collected within a 1-100 m radius of the pond. Thus, stable isotope tracers may provide a means of examining the atmospheric transport and air-earth exchange rates of POPs in an environmental realistic setting.

Persistent organic pollutants at the base of the Antarctic marine food web.

Various organochlorine pesticides and brominated diphenyl ethers (BDE-47, -99, and -100) were measured in sea ice algae, water column plankton, and juvenile and adult krill collected in the Palmer Long-Term Ecological Research (LTER) region west of the Antarctic Peninsula during late austral winter and midsummer, 2001-2002. BDEs were 100-1000 times higher in ice algae and 2-10 times higher in phytoplankton than the most abundant organochlorine pesticide, hexachlorobenzene (HCB), reflecting the current production and use of BDEs versus organochlorine pesticides. However, concentrations of HCB and BDEs were significantly lower in summer plankton than in ice algae indicating lower atmospheric inputs, removal from the water column, and/or biodilution of persistent organic pollutants at the base of the food web during summer. Concentrations of HCB (juvenile and adult krill) and BDEs (juvenile krill) were not significantly different from their primary food source (ice algae, phytoplankton), and BDEs were significantly lower in adult krill versus phytoplankton, indicating no biomagnification of HCB or BDEs during transfer from plankton to krill. The high concentrations of BDEs and HCB in ice algae and associated juvenile krill illustrate the importance of sea ice as a vector for entry of POPs into the Antarctic marine ecosystem.

Variations in alpha-hexachlorocyclohexane enantiomer ratios in relation to microbial activity in a temperate estuary.

Changes in the enantiomer ratios (ERs) of chiral pollutants in the environment are often considered evidence of biological alteration despite the lack of data on causal or mechanistic relationships between microbial parameters and ER values. Enantiomer ratios that deviate from 1:1 in the environment provide evidence for the preferential microbial degradation of one enantiomer, whereas ER values equal to 1 provide no evidence for microbial degradation and may mistakenly be interpreted as evidence that biodegradation is not important. In an attempt to link biological and geochemical information related to enantioselective processes, we measured the ERs of the chiral pesticide alpha-hexachlorocyclohexane (alpha-HCH) and bacterial activity (normalized to abundance) in surface waters of the York River (VA, USA) bimonthly throughout one year. Despite lower overall alpha-HCH concentrations, alpha-HCH ER values were unexpectedly close to 1:1 in the freshwater region of the estuary with the highest bacterial activity. In contrast, ER values were nonracemic (ER double dagger 1) and alpha-HCH concentrations were significantly higher in the higher salinity region of the estuary, where bacterial activity was lower. Examination of these data may indicate that racemic environmental ER values are not necessarily reflective of a lack of biodegradation or recent input into the environment, and that nonenantioselective biodegradation may be important in certain areas.

Spatial and temporal variation in hexachlorocyclohexane isomers in a temperate estuary.

Hexachlorocylcohexanes (HCHs) are pesticides that persist in air and water of the Northern hemisphere. To understand the spatial and temporal variability in HCH levels in estuarine surface waters we measured concentrations of two HCH isomers (alpha-HCH and gamma-HCH) at six sites in the York River estuary at bimonthly intervals for a year. Bacterial abundance and activity were also monitored using acridine orange direct counts and uptake of tritiated substrates, respectively. Alpha-HCH was consistently observed to be significantly higher in marine water compared to river water entering the estuary, suggesting that the Chesapeake Bay or Atlantic Ocean is a larger source of this compound to the York River estuary compared to riverine input. Moreover, following periods of high freshwater flow into the estuary during spring and early summer, both alpha- and gamma-HCH mixing curves indicated an additional source of these pollutants to the estuary such as land-derived runoff or groundwater discharge. In contrast, during low freshwater flow (late summer and fall) the estuary was a sink for HCHs, with y-HCH more rapidly removed from the estuary than alpha-HCH. During the period of low freshwater flow, concentrations of both alpha- and gamma-HCH were negatively correlated with bacterial activity. Bacterial activity as opposed to abundance appears to control HCH degradation in estuarine surface waters.