Development and calibration of a passive sampler for perfluorinated alkyl carboxylates and sulfonates in water.

Perfluorinated chemicals (PFCs) are emerging environmental contaminants with a global distribution. Due to their moderate water solubility, the majority of the environmental burden is assumed to be in the water phase. This work describes the application of the first passive sampler for the quantitative assessment of concentrations of perfluorinated alkylcarboxylates (PFCAs) and sulfonates (PFSAs) in water. The sampler is based on a modified Polar Organic Chemical Integrative Sampler (POCIS) with a weak anion exchange sorbent as a receiving phase. Sampling rates were between 0.16 and 0.37 L d(-1), and the duration of the kinetic sampling stage was between 2.2 and 13 d. A field deployment in the most urbanized estuary in Australia (Sydney Harbour) showed trace level concentrations from passive samplers (0.1-12 ng L(-1)), in good agreement with parallel grab sampling (0.2-16 ng L(-1)). A separate field comparison of the modified POCIS with standard POCIS suggests the latter may have application for PFC sampling, but with a more limited range of analytes than the modified POCIS which contains a sorbent with a mixed mode of action.

Indicators of environmental stress: cellular biomarkers and reproductive responses in the Sydney rock oyster (Saccostrea glomerata).

We measured a suite of common biomarker responses for the first time in the Sydney rock oyster Saccostrea glomerata to evaluate their utility as biological effects measures for pollution monitoring. To examine the relationship between biomarker responses and population level effects, fertilisation and embryo development assays were also conducted. Adult oysters were deployed in two contaminated estuaries and a reference estuary in Sydney, Australia. The concentrations of various contaminants (metals and polycyclic aromatic hydrocarbon, PAHs) were quantified in oyster's tissue from each site and both metals and total PAHs were significantly elevated in contaminated estuaries relative to the reference estuary. Lysosomal membrane destabilisation, lipid peroxidation levels and glutathione (GSH) concentrations were measured in the digestive gland of oysters. Of all biomarkers measured, lysosomal membrane destabilisation proved to be the most useful indicator of oysters facing anthropogenic stress and we suggest this may be an especially useful biomarker for incorporation into local environmental monitoring programs. Moreover, lysosomal membrane destabilisation showed good correlations with fertilisation, normal embryo development and estuary status. GSH and lipid peroxidation were not as valuable for distinguishing between estuaries exposed to differing levels of anthropogenic stress, but did provide additional valuable information regarding overall health status of the oysters.

Recolonisation of translocated metal-contaminated sediments by estuarine macrobenthic assemblages.

A recolonisation experiment was performed using sediments from three locations (Nords Wharf, Cockle Bay and Warners Bay) along a metal contamination gradient (Lake Macquarie, Australia). The study aimed to determine whether the source of the sediments would influence the recolonisation of benthic assemblages, providing additional information regarding the ecological risks associated with the more contaminated sediments. Sediments were translocated to two locations within the lake and retrieved after 22 weeks along with benthic samples from the surrounding sediments (ambient). Total abundance was greater in the reference treatment (Nords Wharf), with this difference being driven by polychaetes, especially capitellids. In general, univariate metrics were similar among the recolonised treatments, although evenness and diversity patterns were complex due to significant location-treatment interactions. PERMANOVA analysis demonstrated that the Nords Wharf treatments were significantly different from the more contaminated treatments (Cockle Bay and Warner's Bay) and the ambient assemblages, with no differences being detected among Cockle Bay and Warners Bay assemblages. Collectively, the findings showed that the source of the sediments influenced the composition of the recolonised assemblages, with the described approach being a powerful tool for examining the effects of location-specific sediments under environmentally relevant conditions.

Levels of PCDD/Fs and dioxin-like PCBs in seafood from Sydney Harbour, Australia.

Sydney Harbour, Australia is contaminated with polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) due to a historical Union Carbide chemical manufacturing facility. We measured levels of PCDD/Fs and dl-PCBs in over 400 seafood samples (covering 20 species) collected throughout Sydney Harbour. Concentrations ranged from 0.1 to 193 pg total TEQ (WHO05)/g wet weight. These concentrations were above those considered safe for human consumption in many cases. Dioxin accumulation varied among species and was associated with life history traits. Mobile species had elevated concentrations throughout Sydney Harbour whereas accumulation in species likely to move less widely was dependent on the distance they were caught from the point source. This large scale study on multiple species of recreationally caught seafood resulted in the implementation of human consumption advisories for recreational fishing based on individual species and distance from point source. In addition, all forms of commercial fishing in Sydney Harbour were banned.

A biomarker of contaminant exposure is effective in large scale assessment of ten estuaries.

Cost-effective and sensitive measures of anthropogenic stress are necessary tools in any environmental monitoring program. When implementing new monitoring tools in a region, rigorous laboratory and field studies are essential for characterizing the sensitivity and efficacy of the approach. We exposed the oyster Saccostrea glomerata to various individual contaminants through multiple exposure pathways (water- and food-borne) in the laboratory and measured two biomarker responses, lysosomal membrane stability (LMS) and lipid peroxidation (LPO). LMS was sensitive to both contaminant exposure pathways. We subsequently measured this biomarker in oysters which had been experimentally deployed at multiple sites in each of ten estuaries with varying levels of contamination associated with re-suspended sediments. There was a strong association between LMS and metal exposure, despite substantial natural variation in water quality parameters. Our results illustrate the potential use of LMS as a pragmatic indicator of biotic injury in environmental monitoring programs for re-suspended contaminated sediments.

Next generation sequence analysis of the transcriptome of Sydney rock oysters (Saccostrea glomerata) exposed to a range of environmental stressors.

Sydney rock oysters (Saccostrea glomerata) were exposed to environmental stressors at contaminated field sites or in a controlled laboratory setting. RNA seq transcriptome data were generated for the gill and digestive gland using Roche's 454 pyrosequencing technology. 28,685 contigs were de novo assembled which encoded 11,671 different protein products. The data will act as a reference for future studies in ecology, immunology and environmental toxicology.

Lifetime PCB 153 bioaccumulation and pharmacokinetics in pilot whales: Bayesian population PBPK modeling and Markov chain Monte Carlo simulations.

Physiologically based pharmacokinetic (PBPK) models for wild animal populations such as marine mammals typically have a high degree of model uncertainty and variability due to the scarcity of information and the embryonic nature of this field. Parameters values used in marine mammals models are usually taken from other mammalian species (e.g. rats or mice) and might not be entirely suitable to properly explain the kinetics of pollutants in marine mammals. Therefore, several parameters for a PBPK model for the bioaccumulation and pharmacokinetics of PCB 153 in long-finned pilot whales were estimated in the present study using the Bayesian approach executed with Markov chain Monte Carlo (MCMC) simulations. This method uses 'prior' information of the parameters, either from the literature or from previous model runs. The advantage is that this method uses such 'prior' parameters to calculate probability distributions to determine 'posterior' values that best explain the field observations. Those field observations or datasets were PCB 153 concentrations in blubber of long-finned pilot whales from Sandy Cape and Stanley, Tasmania, Australia. The model predictions showed an overall decrease in PCB 153 levels in blubber over the lifetime of the pilot whales. All parameters from the Sandy Cape model were updated using the Stanley dataset, except for the concentration of PCB 153 in the milk. The model presented here is a promising and preliminary start to PBPK modeling in long-finned pilot whales that would provide a basis for non-invasive studies in these protected marine mammals.

Assessing levels of halogenated organic compounds in mass-stranded long-finned pilot whales (Globicephala melas) from Australia.

Pollution is a threat to the health of marine mammals worldwide. Mass-strandings are poorly understood, but often involve pilot whales. However, there is limited information regarding pollution in long-finned pilot whales from Australia. Consequently, the profiles and levels of several pollutant classes were investigated in blubber of Tasmanian long-finned pilot whales. DDX levels were highest in all groups, followed by PCBs or MeO-PBDEs and lowest for PBDEs. The concentrations of all pollutants decreased with age in males. This is at least partly due to the growth dilution effect although it might also be caused by decreasing levels of PCBs, PBDEs, DDXs, HCB and CHLs in the environment. Fetus/mother ratios of higher chlorinated PCBs increased with the duration of pregnancy suggesting a preference for offloading via gestation rather than through lactation. Overall, the highest pollutant levels were found in the youngest animals.

Effects of a chelating resin on metal bioavailability and toxicity to estuarine invertebrates: divergent results of field and laboratory tests.

Benthic invertebrates can uptake metals through diffusion of free ion solutes, or ingestion of sediment-bound forms. This study investigated the efficacy of the metal chelating resin SIR 300 in adsorbing porewater metals and isolating pathways of metal exposure. A field experiment (Botany Bay, Sydney, Australia) and a laboratory toxicity test each manipulated the availability of porewater metals within contaminated and uncontaminated sediments. It was predicted that within contaminated sediments, the resin would adsorb porewater metals and reduce toxicity to invertebrates, but in uncontaminated sediments, the resin would not significantly affect these variables. Whereas in the laboratory, the resin produced the predicted results, in the field the resin increased porewater metal concentrations of contaminated sediments for at least 34 days and decreased abundances of four macroinvertebrate groups, and richness in all sediments. These contrasting findings highlight the limits of extrapolating the results of laboratory experiments to the field environment.

Using SPMDs to monitor water column concentrations of PCDDs, PCDFs and dioxin-like PCBs in Port Jackson (Sydney Harbour), Australia.

Semipermeable membrane devices (SPMDs) were deployed on two occasions throughout Sydney Harbour, Australia, along a 25 km transect. They were used to measure spatial and temporal variation in the available concentrations of 7 polychlorinated dibenzo-p-dioxins (PCDDs) and 10 polychlorinated dibenzofurans (PCDFs) and 12 dioxin-like polychlorinated biphenyls (PCBs) in the water column. The relative percent difference (%RPD) among spatially replicated cages (within 0.13-0.41 km) ranged from less than 8% to greater than 66% across all congeners and was greater for WHO(05)-TEQ(DFP) (average=36%), PCDFs (average=34%) and PCDDs (average=33%) than PCBs (average=23%). Total PCDD (SigmaPCDDs) concentrations ranged between 2.7 and 84 pg L(-1), SigmaPCDF concentrations ranged from 0.15 to 7.2 pg L(-1), SigmaPCB concentrations ranged between 21 and 540 pg L(-1) and WHO(05)-TEQ(DFP) ranged from 0.069 to 1.85 pg L(-1). Highest concentrations were measured in SPMDs deployed in Homebush Bay and concentrations generally declined with distance from Homebush Bay. SPMDs detected changes in congener profiles downstream with OCDD, 2,3,7,8-TCDF and PCBs 189, 157, 167, and 126 increasing in proportion with distance from Homebush Bay. There was a large increase in the daily accumulation of the analytes from winter to summer resulting in an average 3.9-fold increase in the predicted concentration at one site with matched SPMDs.

Toxicity of selenomethionine- and seleno-contaminated sediment to the amphipod Corophium sp.

The acute toxicity of four chemical species of selenium to juvenile amphipods (Corophium sp.) was assessed in water-only tests. The seleno-amino acid compounds seleno-L-methionine and seleno-DL-cystine were found to be more toxic (96-h LC(50) values of 1.5 and 12.7 microg Se/L) than the inorganic selenite and selenate (96-h NOEC values of 58 and 116 microg Se/L). New marine sediment testing procedures were developed using juvenile and adult Corophium sp. Both life stages were highly sensitive to seleno-L-methionine-spiked sediment. The juveniles were approximately five times more sensitive, with a 10-day LC(50) of 1.6 microg Se/g (dry weight) compared to 7.6 microg Se/g (dry weight) for the adults. Sediment collected from three sites in Lake Macquarie, a marine barrier lagoon with elevated concentrations of total selenium, had no effect on the survival of adult Corophium over 10 days. The toxicity of seleno-L-methionine to other amphipod species occurring in Lake Macquarie was assessed in water-only tests, with Paracalliope australis being highly sensitive (96-h LC(50) 2.58 microg Se/L).