Polychlorinated dibenzodioxins/furans and dioxin-like polychlorinated biphenyls in fish and crustaceans of a recreationally fished estuary, following targeted remediation.

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) are a suite of harmful chemicals (hereafter collectively referred to as 'dioxins'), and their emission into aquatic habitats leads to persistent contamination of sediments, aquatic food-webs, and seafoods. Quantifying contaminant levels in seafood species is important for the ongoing management of exposure risk by fishers, particularly after any remediation actions. We present dioxin concentrations in four seafood species (Yellowfin Bream Acanthopagrus australis, Sea Mullet Mugil cephalus, Eastern School Prawn Metapenaeus macleayi, and Eastern King Prawn Penaeus plebejus) in a recreationally fished estuary, in relation to a contaminated site that has undergone a remediation process, partially removing contaminated sediments (Homebush Bay, Port Jackson, New South Wales, Australia). Dioxin concentrations in these species were measured before (2005/6) and after (2015/16) remediation at a range of locations in and around the remediated site. Dioxin concentrations and congener profiles differed substantially among taxa, and concentrations were frequently higher than Australian screening criteria. The two prawn species showed evidence of a decline in dioxin concentrations after remediation, but the fish species only showed a declining dioxin concentration with distance from the contaminated site (not between periods). There were some minor changes in the congener profile for some species following remediation. While there was evidence for greatly reduced dioxin concentrations in prawn species following remediation, the complex patterns for fish were likely affected by environmental changes, species-specific and temporal changes in lipid content, and animal movement patterns. Future monitoring may aid interpretation of the patterns and modelling of exposure risk associated with seafood consumption into the future.

Per- and polyfluoroalkyl substances (PFAS) in little penguins and associations with urbanisation and health parameters.

Per- and Polyfluoroalkyl substances (PFAS) are increasingly detected in wildlife and present concerning and unknown health risks. While there is a growing body of literature describing PFAS in seabird species, knowledge from temperate Southern Hemisphere regions is lacking. Little penguins (Eudyptula minor) can nest and forage within heavily urbanised coastal environments and hence may be at risk of exposure to pollutants. We analysed scat contaminated nesting soils (n = 50) from 17 colonies in lutruwita/Tasmania for 16 PFAS, plasma samples (n = 45) from nine colonies, and three eggs for 49 PFAS. We detected 14 PFAS across the sample types, with perfluorooctanesulfonic acid (PFOS) and perfluorohexanesulfonic acid (PFHxS) most commonly detected. Mean concentration of PFOS in plasma was 2.56 ± 4.3 ng/mL (

Application of in-source fragmentation to the identification of perfluoropentanoic acid and perfluorobutanoic acid in environmental matrices and human serum by isotope dilution liquid chromatography coupled with tandem mass spectrometry.

Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is the most common analytical technique for per- and polyfluoroalkyl substances (PFASs) research and monitoring. The PFAS identification requires a minimum of two multiple reaction monitoring (MRM) transition ions as quantifier transition ion and qualifier transition ion, respectively. The second transition ion abundance for perfluoropentanoic acid (PFPeA) and perfluobutanoic acid (PFBA) is too low for practical use. A method using the in-source fragment ions as the precursor ion for MRM or pseudo-MRM has been developed and evaluated for PFPeA and PFBA identification in various environmental abiotic and biotic samples including water, soil, sediment, WWTP sludge, fruits, vegetables, egg, macrophytes, fish, dolphin liver and human serum. The PFPeA qualifier MRM transition ion (m/z = 219 > 69) has been successfully applied in all the matrices with spike recoveries (90-125%), signal to noise ratios (>10) and transition ions ratio variation (80-120%). The PFBA qualifier pseudo-MRM transition ion (m/z = 169 > 169) works well in all the matrices except dolphin liver sample. The interpretation of pseudo-MRM results should be with cautions due to lower specificity compared to MRM. In addition, this project indicated under typical chromatographic conditions the MRM isobaric interference does happen frequently to PFPeA quantifier transition ion (m/z = 263 > 219) in serum and fish composite samples, and to PFBA quantifier transition ion (m/z = 213 > 169) in macrophytes, fish composite and dolphin liver samples.

Laboratory batch representation of PFAS leaching from aged field soils: Intercomparison across new and standard approaches.

Relating laboratory leaching methods to partitioning and transport of per- and poly-fluoroalkyl substances (PFAS) in field soils is challenging, making estimation of fluxes to groundwater and surface water uncertain. Existing laboratory leaching methods have limitations when assessing field leaching. For 37 aged field soils from five sites historically contaminated with PFAS over decades, we assess PFAS leaching using new and existing laboratory leaching methods to provide alternative methods better reflecting PFAS risks posed by its leaching and movement. Dominant PFAS in the soils were perfluorooctane sulfonic acid, perfluorohexane sulfonic acid, and perfluorohexanoic acid and to a lesser extent perfluorooctanoic acid. Leaching from intact soil cores (Exp 1) was taken to reflect field conditions. These were compared to two new laboratory batch tests, saturate-spin (Exp 2) and saturate-tumble-spin (Exp 3), and two standard approaches; Australian Standard Leaching Procedure (ASLP, Exp 4) and the Leaching Environmental Assessment Framework (LEAF, Exp 5). The tests varied in terms of liquid:soil ratio, tumbling time and pH of the starting solution, with LEAF-1313 conducted across seven pHs (2-12). Correlations between leachate and soil concentrations were highest for Exp 4 and Exp 5 (R2 = 0.72-0.98) and lowest for Exp 3 (R2 = 0.53). The PFAS mass leached as a fraction of the total increased such that: soil core leaching (27 %) < saturate-spin (30 %) < saturate-tumble-spin (65 %) ≤ LEAF-1313 (65 to 88 % at pH 5-9) < ASLP (90 %). As a fraction of individual PFAS compounds in leachate compared with soil, the shorter chain PFAS (e.g., perfluorobutanoic acid) were higher in the leachate in all tests. Across all tests, the saturate-spin batch test most closely represented intact soil core leaching and therefore potentially provides a measure more analogous of in situ soil leaching at field sites. Other methods would apply to broader applications such as landfill disposal.

Per and polyfluoroalkyl substances (PFAS) at high concentrations in neonatal Australian pinnipeds.

Per and polyfluorinated substances (PFAS) exposure was investigated in Australian pinnipeds. Concentrations of 16 PFAS were measured in the livers of Australian sea lion (Neophoca cinerea), Australian fur seal (Arctocephalus pusillus doriferus) and a long-nosed Fur Seal (Arctocephalus forsteri) pup sampled between 2017 and 2020 from colonies in South Australia and Victoria. Findings reported in this study are the first documented PFAS concentrations in Australian pinnipeds. Median and observed range of values in ng/g wet weight were highest for perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) in the liver of N. cinerea (PFOS = 7.14, 1.00-16.9; PFOA = 2.73, 0.32-11.2; PFNA = 2.96, 0.61-8.22; n = 28), A. forsteri (PFOS = 15.98, PFOA = 2.02, PFNA = 7.86; n = 1) and A. p. doriferus (PFOS = 27.4, 10.5-2119; PFOA = 0.98, 0.32-52.2; PFNA = 2.50, 0.91-44.2; n = 20). PFAS concentrations in A. p. doriferus pups were significantly greater (p < 0.05) than in N. cinerea pups for all PFAS except PFOA and were of similar magnitude to those reported in northern hemisphere marine animals. These results demonstrate exposure differences in both magnitude and PFAS profiles for N. cinerea in South Australia and A. p. doriferus in Victoria. This study reports detectable PFAS concentrations in Australian pinniped pups indicating the importance of maternal transfer of these toxicants. As N. cinerea are endangered and recent declines in pup production has been reported for A. p. doriferus at the colony sampled, investigation of potential health impacts of these toxicants on Australian pinnipeds is recommended.

Biological and behavioral responses of European honey bee (Apis mellifera) colonies to perfluorooctane sulfonate exposure.

Bees provide pollination services to managed and wild ecosystems but are threatened globally due to multiple stressors, including exposure to contaminants. Perfluorooctane sulfonate (PFOS) is a widely detected and persistent contaminant that accumulates and biomagnifies in food chains. In this exposure effect study, small whole colonies of Apis mellifera (1000 bees) were exposed to PFOS using a purpose-built cage system over a 4-week period. The PFOS exposure concentrations were provided to bees in sugar syrup at concentrations detected in the environment, ranging from 0 to 1.6 mg L-1 . A range of biological and behavioral responses were monitored. Bee tissue, honey, and fecal matter were analyzed using isotope dilution combined with liquid chromatography-tandem mass spectrometry adapted for bee and honey matrix analysis. Bee mortality increased significantly with PFOS exposure at 0.8 mg L-1  or greater, and brood development ceased entirely at 0.02 mg L-1  or greater. Colony activity, temperament, hive maintenance, and defense were adversely affected in all PFOS exposure treatments compared with the control, even at the lowest PFOS exposure of 0.02 mg L-1 . Perfluorooctane sulfonate was detected in bee tissue with a mean bioaccumulation factor of 0.3, and it was also identified in honey and in feces collected from the hive cages. These findings provide the first evidence that PFOS exposure adversely affects honey bee colonies and may transfer to honey. With PFOS contaminating thousands of sites worldwide, our study has implications for exposed bee populations under natural conditions, pollination services, the honey industry, and human health. Integr Environ Assess Manag 2021;17:673-683. © 2021 SETAC.

Evaluation of Residues in Hen Eggs After Exposure of Laying Hens to Water Containing Per- and Polyfluoroalkyl Substances.

Per- and polyfluoroalkyl substances (PFAS) have been used in aqueous film-forming foams used in firefighting, resulting in soil and groundwater contamination and leading to human exposure via animal products grown in contaminated areas. The present study reports the relationship between PFAS intake by hens and the PFAS concentrations in the edible parts of eggs. Laying hens were exposed via drinking water to different concentrations of 4 PFAS compounds (perfluorooctane sulfonate [PFOS], perfluorohexane sulfonate [PFHxS], perfluorooctanoic acid [PFOA], and perfluorohexanoic acid) over 61 d. Egg PFAS residues were assessed for a further 30 d after exposure ceased. The target concentrations of PFAS were 0, 0.3, 3, 30, and 300 µg/L for the treatment groups T1-T5, respectively; and PFAS residues were determined from the eggs collected every second day. There was a linear correlation between the PFAS concentrations in the drinking water of hens and those detected in the egg, which could be useful in estimating PFAS concentrations in the egg by measuring water concentrations. Exposure of hens to drinking water with PFAS concentrations below the Australian Government Department of Health limits (PFOS and PFHxS, 0.07 µg/L; PFOA, 0.56 µg/L), and with no other sources of PFAS exposure, is unlikely to result in egg PFAS concentrations that would exceed the 10% limit set by Food Standards Australia New Zealand for human consumption. Environ Toxicol Chem 2021;40:735-743. © 2020 SETAC.

GAPS-megacities: A new global platform for investigating persistent organic pollutants and chemicals of emerging concern in urban air.

A pilot study was initiated in 2018 under the Global Atmospheric Passive Sampling (GAPS) Network named GAPS-Megacities. This study included 20 megacities/major cities across the globe with the goal of better understanding and comparing ambient air levels of persistent organic pollutants and other chemicals of emerging concern, to which humans residing in large cities are exposed. The first results from the initial period of sampling are reported for 19 cities for several classes of flame retardants (FRs) including organophosphate esters (OPEs), polybrominated diphenyl ethers (PBDEs), and halogenated flame retardants (HFRs) including new flame retardants (NFRs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDD). The two cities, New York (USA) and London (UK) stood out with ∼3.5 to 30 times higher total FR concentrations as compared to other major cities, with total concentrations of OPEs of 15,100 and 14,100 pg/m3, respectively. Atmospheric concentrations of OPEs significantly dominated the FR profile at all sites, with total concentrations in air that were 2-5 orders of magnitude higher compared to other targeted chemical classes. A moderately strong and significant correlation (r = 0.625, p < 0.001) was observed for Gross Domestic Product index of the cities with total OPEs levels. Although large differences in FR levels were observed between some cities, when averaged across the five United Nations regions, the FR classes were more evenly distributed and varied by less than a factor of five. Results for Toronto, which is a 'reference city' for this study, agreed well with a more in-depth investigation of the level of FRs over different seasons and across eight sites representing different urban source sectors (e.g. traffic, industrial, residential and background). Future sampling periods under this project will investigate trace metals and other contaminant classes, linkages to toxicology, non-targeted analysis, and eventually temporal trends. The study provides a unique urban platform for evaluating global exposome.

Concentrations of some legacy pollutants have increased in South Australian bottlenose dolphins from 1989 to 2014.

Information about pollution and its potential impact in Australian marine wildlife is scarce. To fill this knowledge gap, our study investigated concentrations of legacy pollutants as well as naturally produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in blubber, liver, kidney and muscle of Indo-Pacific bottlenose dolphins (Tursiops aduncus) from two large inverse estuaries in South Australia from 1989 to 1995 and 2009-2014. Our results show that concentrations of most pollutant classes are relatively low compared to the literature but at the higher end of the ranges reported for marine mammals in Australia. Results for some individuals exceed toxicity thresholds indicative of immunotoxicity in marine mammals. It is important to note that concentrations of some compound classes, particularly PBDEs and polychlorinated biphenyls (PCBs), increased over a time interval of 20 years thereby placing more individuals at risk in recent years. Some of the highest concentrations of persistent organic pollutants (POPs) were measured in juveniles, which may jeopardize their development and the success of future generations. These results indicate that legacy pollutants may play a role in the long-term health of T. aduncus and should be included in biomonitoring efforts.

Emerging and legacy contaminants across land-use gradients and the risk to aquatic ecosystems.

Information on potentially harmful emerging and legacy chemicals is essential to understand the risks to the environment and inform regulatory actions. The objective of this study was to assess the occurrence, concentration, and distribution of emerging and legacy contaminants across a gradient of land-use intensity and determine the risk posed to aquatic ecosystems. The land-use intensity gradient considered was: background/undeveloped < low-intensity agriculture < high-intensity agriculture < urban residential < urban industrial. Twenty-five sites were sampled for surface water, sediment, and soil. A total of 218 chemicals were analyzed: pesticides, per- and poly-fluoroalkyl substances (PFAS), polybrominated biphenyls and polybrominated diphenyl ethers (PBDEs), phthalates, and short-chain chlorinated paraffins (SCCPs). The risk posed by the analyzed chemicals to the aquatic environment was measured using hazard quotients (HQs), which were calculated by dividing the maximum measured environmental concentration by a predicted no-effect concentration for each chemical. A HQ > 1 was considered to indicate a high risk of adverse effects from the given chemical. A total of 68 chemicals were detected: 19 pesticides, 18 PFAS, 28 PBDEs, two phthalates, and SCCPs (as total SCCPs). There were no significant differences in the overall chemical composition between land uses. However, the insecticide bifenthrin, PFAS, PBDEs, and phthalates were more frequently found in samples from residential and/or industrial sites, suggesting urban land uses are hotspots and potential large-scale sources of these chemicals. Nineteen chemicals had a HQ > 1; most had a restricted spatial distribution limited to high-intensity agriculture and industrial sites in Melbourne. Bifenthrin and the perfluorooctanesulfonic acid (PFOS) had the highest HQs in residential and industrial sites, suggesting an increased risk to aquatic ecosystems in urban settings. The results of this study will enhance future research, predictive methods, and effective targeting of monitoring, and will help guide regulatory management actions and mitigation solutions.

First observations of perfluorooctane sulfonate occurrence and depuration from Sydney Rock Oysters, Saccostrea glomerata, in Port Stephens NSW Australia.

Following the discovery of potential chronic perfluoroalkyl substances (PFAS) contamination of Tilligerry Creek, Port Stephens (New South Wales Australia), sampling was undertaken to confirm the presence, extent and levels of contamination in commercial oyster crops of Sydney Rock Oyster (Saccostrea glomerata) and Pacific Oyster (Crassostrea gigas) grown within the estuary. Among a range of PFAS tested, only perfluorooctane sulfonate (PFOS) was detected. Concentrations of PFOS in oyster tissues for S. glomerata ranged from 1.6µgkg-1 ww (wet weight) to below the limit of reporting of 0.3µgkg-1 ww, with concentrations generally decreasing toward the lower reaches of the estuary. The sample of C. gigas tested had a PFOS concentration of 0.71µgkg-1 ww that was consistent with concentrations observed in nearby S. glomerata. For harvest size (50-60g) S. glomerata, both holding contaminated oysters in a depuration system, and relocation to a non-contaminated area, saw significant reductions in the tissue PFOS concentrations. For oysters held in a depuration system, PFOS depurated at a rate of 0.008h-1 (0.004-0.019h-1; 90% CI), which corresponded with a depuration half-life of 87h (35-155h; 90%). A more conservative model (fitted to data that assumed concentrations

Utility of fur as a biomarker for persistent organic pollutants in Australian fur seals (Arctocephalus pusillus doriferus).

Persistent Organic Pollutants (POPs) can cause toxic effects in many species which include endocrine dysfunction, immunotoxicity, developmental defects and neoplasia. Species dominating the upper trophic level are vulnerable to these effects due to bioaccumulation. In Bass Strait, the Australian fur seal (Arctocephalus pusillus doriferus) is an important top order predator and sentinel species for ecosystem health. An alopecia syndrome is seen at high prevalence in juvenile, female Australian fur seals at Lady Julia Percy Island, Victoria, Australia. Previous investigations suggest causality could be due to an endocrine-like toxicant. The alopecia syndrome has significance for thermoregulation and is a likely risk factor for mortality. Fur collected from case (alopecic) and control (unaffected) seals sampled at Lady Julia Percy Island were analysed for POPs. To investigate the utility of fur for monitoring POPs concentrations in pinnipeds, a comparison of POPs concentrations in the fur and blubber of Australian fur seals stranded along the Victorian coast was undertaken. The concentration of selected POPs including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), polybrominated diphenyl ethers (PBDEs) and perfluorooctane sulfonate/perfluorooctanoic acid (PFOS/PFOA) were determined in fur using either High Resolution Gas Chromatography-Mass Spectrometry or Liquid Chromatography-Mass Spectrometry. Results indicate detectable, and in some individuals, elevated levels of dl-PCBs, PCDD/Fs and PBDEs in juvenile fur seals sampled on Lady Julia Percy Island, with significantly higher levels of dl-PCBs in case compared to control seals. Elevated levels of dl-PCBs and PCDD/Fs were found in blubber samples collected from stranded fur seals with significant correlations between blubber and fur concentrations seen, particularly for dl-PCBs. This study discusses the significance of POPs concentrations in relation to the causality of an alopecia syndrome in the Australian fur seal, and assesses the utility of fur as a non-invasive biomarker to monitor POPs exposure in this sentinel species.

Isomer-specific investigation of PCDD/F mobility and other fate processes in deep soil cores.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are highly hydrophobic compounds with low migration potential in soil-water. Nevertheless, they have been occasionally reported in subsurface soils hypothesised as the result of facilitated transport processes with colloids or surfactants, or yet unidentified in-situ formation processes. To date, however, the prevalence of deep soil contamination, involved processes and their kinetics remain poorly understood. This study investigated PCDD/F concentrations and isomer profiles through deep soil cores (to 20 m) from agricultural, industrial and urban sites in Queensland, Australia. Based on isomer profiles, a unique source common to all core soils (regardless of depth) was identified, dominated by octachlorodibenzo-p-dioxin (OCDD). The source was consistent with contamination resulting from pesticide impurities. Elevated PCDD concentrations (µg/kg range) to depths up to ∼4-17 m and a continuous increase of peri-chlorinated (1,4,6,9-substituted) isomers through the cores suggested that vertical transport and lateral dechlorination were key post-depositional processes at these sites. The mobility of PCDDs in the present study is far greater than previously reported in soils in general. High estimated mass transport rates for OCDD in four agricultural cores (3.0-6.2% year(-1)) likely reflect significant levels of facilitating species, including surfactants, and intensive rainfall at these sites. The implications of such extensive subsurface transport of PCDD/Fs for groundwater contamination and load estimates may be significant. If the cores of the present study are assumed representative of the region, a total PCDD/F load in the order of 800 tonnes (1.6 tonnes TEQ) could be present in subsurface Queensland coastal soils.

Polycyclic aromatic hydrocarbons in road-deposited sediments, water sediments, and soils in Sydney, Australia: Comparisons of concentration distribution, sources and potential toxicity.

Sixteen polycyclic aromatic hydrocarbons (PAHs) considered as priority environmental pollutants were analysed in surface natural soils (NS), road-deposited sediments (RDS), and water sediments (WS) at Kogarah in Sydney, Australia. Comparisons were made of their concentration distributions, likely sources and potential toxicities. The concentrations (mg/kg) in NS, RDS, and WS ranged from 0.40 to 7.49 (mean 2.80), 1.65 to 4.00 (mean 2.91), and 0.49 to 5.19 (mean 1.76), respectively. PAHs were dominated by relatively high molecular weight compounds with more than three fused benzene rings, indicating that high temperature combustion processes were their predominant sources. The proportions of high molecular weight PAHs with five or six fused benzene rings were higher in NS than in RDS, whereas the low molecular weight PAHs were higher in RDS. Concentrations of all PAHs compounds were observed to be the lowest in WS. The concentrations of most of the high molecular weight PAHs significantly correlated with each other in RDS and WS. All PAHs (except naphthalene) were significantly correlated in NS suggesting a common PAH source. Ratios for individual diagnostic PAHs demonstrated that the primary source of PAHs in WS and NS was of pyrogenic origin (combustion of petroleum (vehicle exhaust), grass, and wood) while in RDS it was petrogenic (i.e. unburned or leaked fuel and oil, road asphalt, and tyre particles) as well as pyrogenic. The potential toxicities of PAHs calculated using a toxicity equivalent quotient (TEQ) were all low but higher for NS compared to WS and RDS.

In vivo measurement, in vitro estimation and fugacity prediction of PAH bioavailability in post-remediated creosote-contaminated soil.

In this study, PAH bioavailability was assessed in creosote-contaminated soil following bioremediation in order to determine potential human health exposure to residual PAHs from incidental soil ingestion. Following 1,000 days of enhanced natural attenuation (ENA), a residual PAH concentration of 871 ± 8 mg kg(-1) (∑16 USEPA priority PAHs in the <250 µm soil particle size fraction) was present in the soil. However, when bioavailability was assessed to elucidate potential human exposure using an in vivo mouse model, the upper-bound estimates of PAH absolute bioavailability were in excess of 65% irrespective of the molecular weight of the PAH. These results indicate that a significant proportion of the residual PAH fraction following ENA may be available for absorption following soil ingestion. In contrast, when PAH bioavailability was estimated/predicted using an in vitro surrogate assay (FOREhST assay) and fugacity modelling, PAH bioavailability was up to 2000 times lower compared to measured in vivo values depending on the methodology used.

Concentrations of polybrominated diphenyl ethers (PBDEs) in residential dust samples from Western Australia.

Polybrominated diphenyl ethers (PBDEs) are one of the most common types of brominated flame retardants applied to foams, plastics and textiles to prevent fires. These flame retardants are now regulated and are either banned or being voluntarily phased. However, as these chemicals are persistent humans continue to be exposed. Dust has been identified as an important source of exposure and hence residential concentrations are of interest. The aim of this paper was to determine the concentrations of PBDEs in samples of residential dust from the homes of pregnant women in Western Australia. Thirty residential dust samples were analysed for concentrations of 32 PBDE congeners. Samples were collected from urban and rural areas. PBDEs were detected in all residential dust samples with the sum of the most common PBDEs (Σ(7) of BDEs 47, 99, 100, 153, 154, 183 and 209) ranging from 60.4 to 82400 ng g(-1) (median 571 ng g(-1)). DecaBDE makes up the highest proportion of PBDEs in residential dust, on average 66% of Σ(32)PBDEs. We did not find a relationship between housing characteristics nor the presence of appliances and PBDE concentrations. Dust from urban areas had significantly higher concentrations of BDE-209 and Σ(32)PBDEs than dust from rural areas of Western Australia (p values 0.01 and 0.03 respectively). PBDEs were present in residential dust in Western Australia at concentrations higher than reported previously in Australia. Further investigation of sources with a larger sample size is required to determine associations between PBDE concentrations and potential exposure sources and geographical regions.

Formation of dioxins during exposure of pesticide formulations to sunlight.

Chlorinated pesticides can contain impurities of dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and their precursors, as a result of various manufacturing processes and conditions. As precursor formation of PCDD/Fs can also be mediated by ultraviolet light (UV), this study investigated whether PCDD/Fs are formed when currently used pesticides are exposed to natural sunlight. Formulations containing pentachloronitrobenzene (PCNB; n=2) and 2,4-dichlorophenoxyacetic acid (2,4-D; n=1) were exposed to sunlight in quartz tubes, and the concentration of 93 PCDD/F congeners were monitored over time. Considerable formation of PCDD/Fs was observed in both PCNB formulations (by up to 5600%, to a maximum concentration of 57000 µg ∑PCDD/F kg(-1)) as well as the 2,4-D formulation (by 3000%, to 140 µg ∑PCDD/F kg(-1)). TEQ also increased by up to 980%, to a maximum concentration of 28 µg kg(-1) in PCNB, but did not change in the 2,4-D formulation. Assuming similar yields as observed in the present study as a worst case scenario the use of PCNB in Australia may result in the formation of 155 g TEQ annum(-1), contributed primarily by OCDD formation. This warrants detailed evaluations on the contemporary release of PCDD/Fs to the environment after the use of pesticides. Changes in congener profiles (including the ratio of PCDDs to PCDFs (DF ratio)) suggest that pesticide sources of PCDD/Fs after sunlight exposure may not be recognized based on matching source fingerprints established from manufacturing impurities. These changes also provide preliminary insights into the possible formation routes and types of precursors involved.

Facilitated transport of dioxins in soil following unintentional release of pesticide-surfactant formulations.

Colloids such as surfactant micelles can act as transport facilitators for highly lipophilic, generally immobile contaminants in soil. Following a fire at a pesticide facility, this study investigated vertical and lateral migration of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in heterogeneous soil beneath bunded ponds, where contaminated wastewater containing high surfactant loads was stored until remediation. Initially, surface and subsurface soil was obtained during excavation, and subsequently intact cores to 5.7 m were collected. ΣPCDD/F concentrations were elevated in the wastewater (15-81 ng/L) and correspondingly in pond surface soils (6.1-61 ng/g). Maximum ΣPCDD/F concentrations were, however, observed at 2-2.5 m depth (68-130 ng/g), far below their expected mobility range based on physicochemical properties. Congener specific analysis further indicated that PCDD/F mobility was reversed, with the least water-soluble congener migrating to the greatest extent. The presence of higher chlorinated PCDD/Fs throughout a core collected in the direction of groundwater flow indicated subsequent lateral transport. These results provide field evidence for rapid vertical migration (2.4 m in <4 months) of highly lipophilic PCDD/Fs and suggest surfactant facilitated transport as the dominant transport mechanism. Quantification and evaluation of such fundamental changes in contaminant transport and fate in the presence of surfactants is required to identify areas at risk of groundwater contamination.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) impurities in pesticides: a neglected source of contemporary relevance.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) may be formed during the manufacture of chlorinated pesticides, and can remain in the products as impurities. However, the contemporary release of PCDD/Fs to the environment from pesticide use is poorly understood. For this study, 27 pesticide formulations were analyzed for PCDD/Fs (n = 23 registered for use in Australia). PCDD/F impurities were present in all samples, ranging from 0.020 to 2100 ng SigmaPCDD/F g(-1) active ingredient (AI). Among current use pesticides, pentachloronitrobenzene (PCNB) contained the highest impurity levels (up to 2000 ng SigmaPCDD/F g(-1) AI and 5.6 ng TEQ g(-1) AI). The quantity of pesticide used in Australia and associated release of PCDD/Fs was estimated for PCNB and phenoxy herbicides (2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenoxybutyric acid (2,4-DB)) using a probabilistic approach. Input parameters to model pesticide use contributed the highest proportions to the variability of the estimated PCDD/F release, and were considered to have the highest uncertainty. Preliminary estimates of PCDD/F release suggest that contaminated pesticides represent an important ongoing PCDD/F source to the Australian environment (10th-90th percentiles for PCNB = 14-42 and 2,4-D/2,4-DB = 0.35-1.6 g TEQ annum(-1)). These results may have global relevance given that many of the pesticides analyzed were imported into Australia, and are used in high volumes in other countries.

Investigating the distribution of polybrominated diphenyl ethers through an Australian wastewater treatment plant.

The aim of this study was to quantify the amount of polybrominated diphenyl ethers (PBDEs) released into the environment (biosolids, effluent) from a conventional Australian activated sludge treatment wastewater treatment plant (WWTP). The concentration of PBDE congeners was measured at various treatment stages and included four aqueous samples (raw, primary, secondary and tertiary effluents) and three sludges (primary, secondary and lime stabilized biosolids), collected at three sampling events over the course of the experiment (29 days). Semi-permeable membrane devices (SPMDs) were also installed for the duration of the experiment, the first time that SPMDs have been used to measure PBDEs in a WWTP. Over 99% of the PBDEs entering the WWTP were removed through the treatment processes, principally by sedimentation. The main congeners detected were BDE 47, 99 and 209, which are characteristic of the two major commercial formulations viz penta-BDE and deca-BDE. All the PBDE congeners measured were highly correlated with each other, suggesting a similar origin. In this case, the PBDEs are thought to be from domestic sources since domestic wastewater is the main contribution to the in-flow (approximately 95%). The mean concentration of SigmaPBDEs in chemically stabilized sewage sludge (biosolids) was 300microg kg(-1) dry weight. It is calculated that 2.3+/-0.3kg of PBDEs are disposed of each year with biosolids generated from the WWTP. If all Australian sewage sludge is contaminated to at least this concentration then at least 110kg of PBDEs are associated with Australian sewage sludge annually. Less than 10g are released annually into the environment via ocean outfall and field irrigation; this level of contamination is unlikely to pose risk to humans or the environment. The environmental release of treated effluent and biosolids is not considered a large source of PBDE environmental emissions compared to the quantities used annually in Australia.