An integrative approach to define chemical exposure threshold limits for endangered sea turtles.

Environmental contaminants pose serious health threats to marine megafauna species, yet methods defining exposure threshold limits are lacking. Here, a three-pillar chemical risk assessment framework is presented based on (1) species- and chemical-specific lifetime bioaccumulation modelling, (2) non-destructive in vitro and in vivo toxicity threshold assessment, and (3) chemical risk quantification. We used the effects of cadmium (Cd) in green sea turtles (Chelonia mydas) as a proof of concept to evaluate the quantitative mechanistic modelling approach. A physiologically-based kinetic (PBK) model simulated Cd tissue concentrations (liver, kidney, muscle, fat, brain, scute, and 'rest of the body') in C.mydas. The validated PBK model then translated species-specific in vitro results to in vivo effects. The results showed that the resilience of C.mydas towards Cd kidney toxicity is age-dependent and differs with changing physiology and feeding ecology. Using the model in reverse mode, a steady-state exposure threshold of 0.1 µg/g dry weight Cd in forage was derived and compared to real-world exposure scenarios. Three out of the four globally distinct C.mydas populations assessed are exposed to Cd levels above this threshold limit. This approach can be adapted to other marine species and chemicals to prioritize measures for managing potentially harmful chemical exposures.

Simultaneous quantification of humic acid-water and silanized glass-water partition constants for PCBs, PCDDs and OCDF.

Super-hydrophobic organic contaminants (SHOCs) such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and octachlorodibenzofuran (OCDF) can sorb to dissolved hydrophobic materials including humic acids (HAs), enhancing their apparent aqueous solubility and potentially resulting in increased groundwater contamination and offsite transport. To manage risks associated with transport of and contamination by SHOCs, modelling approaches incorporating partitioning data, i.e. dissolved organic carbon-water partition constants (KDOC), are necessary. Measurement of KDOC can however be compromised by SHOC sorption to glassware surfaces leading to an overestimation of experimental values resulting in larger KDOC. A method for simultaneous derivation of KDOC and glass-water partition constants (KGW) is described. It involves a mass balance approach combined with HA as a co-solvent at various concentrations and accounts for SHOC losses to silanized glassware. Measured log KDOC values ranged from 5.28 to 7.64 for tetra- to decachlorinated PCBs, 6.67 to 7.93 for tetra- to octachlorinated PCDDs and 8.20 for OCDF. These data were linear functions of log KOW and consistent with relationships reported for more polar compounds. Log KGW (mm3 mm-2) values (1.62 to 4.06 for PCBs, 2.96 to 3.90 for PCDDs, 3.77 for OCDF) were one order of magnitude greater compared to literature PCB borosilicate glass-water partition constants. Techniques such as those presented in this work present simple, versatile means to provide prediction of the SHOC proportion remaining in aqueous solutions after loss to glassware that was inversely related to container surface area/volume ratio and log KOW in our study.

Transport potential of super-hydrophobic organic contaminants in anionic-nonionic surfactant mixture micelles.

Surfactant mixtures are commonly used in agricultural and soil remediation applications, necessitating an understanding of their micellization behavior and associated impact on the fate of co-existing chemicals in the subsurface. A polymer-water sorption isotherm approach was shown to present an alternative to traditional methods for quantifying, understanding and predicting surfactant mixture properties. Micelle compositions were measured for anionic-nonionic surfactant mixtures. This is important since micelle composition can alter the apparent aqueous solubility of super-hydrophobic organic contaminants (SHOCs) resulting in surfactant facilitated transport (SFT). A key parameter in predicting SFT for SHOCs is their micelle-water partition constant (KMI). These were determined for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated biphenyls (PCBs) with representative anionic-nonionic surfactant mixtures using a polymer depletion method. These previously unreported constants were intermediate between those for pure anionic and nonionic surfactant solutions, with magnitude depending on micelle composition. Separate linear relationships were found between log KMI and log KOW for PCDDs and PCBs. This work provides new methods and preliminary results relating to binary surfactant mixtures (e.g. critical micelle concentration and micelle composition) and SHOCs (KMI) that are important in the evaluation of the fate and transport of SHOCs in the subsurface environment and provide insight into the environmental mobility of these important contaminants.

Multi-residue screening of non-polar hazardous chemicals in green turtle blood from different foraging regions of the Great Barrier Reef.

Green turtles spend a large part of their lifecycle foraging in nearshore seagrass habitats, which are often in close proximity to sources of anthropogenic contaminants. As most biomonitoring studies focus on a limited number of targeted chemical groups, this study was designed to screen for a wider range of hazardous chemicals that may not have been considered in prior studies. Whole blood of sub-adult green turtles (Chelonia mydas) were sampled from three different locations, a remote, offshore 'control' site; and two coastal 'case' sites influenced by urban and agricultural activities on the Great Barrier Reef in North Queensland, Australia. In order to screen blood samples for chemicals across a wide range of KOW's, a modified QuEChER's extraction method was used. The samples were analysed using a multi-residue gas chromatography with tandem mass spectrometry system (GC-MS/MS method that allowed simultaneous quantification of polychlorinated biphenyls (PCBs), polychlorinated diphenyl ethers (PBDES), organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs). While PBDEs, PCBs and OCPS were below the limits of quantification, PAHs were detected in all turtle blood samples. However, PAH levels were relatively low (maximum ΣPAH = 13 ng/mL ww) and comparable to or less than those reported from other green turtles globally. The present study provides the first baseline PAH levels in blood samples from green turtles from nearshore and offshore locations in the Southern Hemisphere.

Evaluating internal exposure of sea turtles as model species for identifying regional chemical threats in nearshore habitats of the Great Barrier Reef.

Marine megafauna that forage in proximity to land can be exposed to a diverse mixture of chemicals that - individually or combined - have the potential to affect their health. Characterizing such complex exposure and examining associations with health still poses considerable challenges. The present study summarizes the development and application of novel approaches to identifying chemical hazards and their potential impacts on the health of coastal wildlife, using green sea turtles as model species. We used an epidemiological study approach to collect blood and keratinized scute samples from free-ranging turtles foraging in nearshore areas and an offshore control site. These were analyzed using a combination of non-targeted, effect-based and multi-chemical analytical screening approaches to assess internal exposure to a wide range of chemicals. The screening phase identified a suite of elements (essential and non-essential) as priority for further investigation. Many of these elements are not commonly analyzed in marine wildlife, illustrating that comprehensive screening is important where exposure is unknown or uncertain. In particular, cobalt was present at highly elevated concentrations, in the order of those known to elicit acute effects across other vertebrate species. Several trace elements, including cobalt, were correlated with clinical indicators of impaired turtle health. In addition, biomarkers of oxidative stress (e.g. 3-indolepropionic acid and lipid peroxidation products) identified in the blood of turtles showed significant correlations with clinical health markers (particularly alkaline phosphatase and total bilirubin), as well as with cobalt. To assist interpretation of trace element blood data in the absence of sufficient information on reptile toxicity, we established exposure reference intervals using a healthy control population. In addition, trace element exposure history was investigated by establishing temporal exposure indices using steady-state relationships between blood and scute. Overall, the data provide a strong argument for the notion that trace element exposure is having an impact on the health of coastal sea turtle populations.

Effect of surfactant application practices on the vertical transport potential of hydrophobic pesticides in agrosystems.

Surfactants have the potential to modify the environmental behavior of hydrophobic pesticides leading to an enhanced or reduced mobility risk. This risk is often overlooked in registration procedures due to a lack of suitable methodologies to quantify the transport potential of pesticides with surfactants. In this study we present a novel methodology designed to study the surfactant facilitated transport of pesticides under controlled equilibrium and dynamic hydrologic conditions. Using this methodology, we investigated the risk of chlorpyrifos enhanced mobility for two common surfactant application practices in agrosystems: pesticide spraying and irrigation with waste water. With the dynamic experiments we showed that a single irrigation event with artificial reclaimed water containing the nonionic surfactant Triton X100 at a concentration of 15 mg/L reduced the leaching of chlorpyrifos by 20% while the presence of the same surfactant in the chlopyrifos spraying formulation reduced the leaching amount by 60%. However, in the first case 90% of the chlropyrifos fraction remaining in soil was retained in the upper 3 cm while in the second cas, 72% was transported to the bottom layers. The presence of Triton X100 in irrigation water or spraying formulation retards the leaching of chlorpyrifos but enhances its downward transport.

Effect-based approach for screening of chemical mixtures in whole blood of green turtles from the Great Barrier Reef.

Organisms are exposed to mixtures of both known and unknown chemicals which are diverse and variable, and thus difficult and costly to characterise and monitor using traditional target analyses. The objective of this study was to validate and apply in vitro effect-based methods by which whole blood can be used to screen internal exposure to such complex chemical mixtures. For this study, we used whole blood of green sea turtles (Chelonia mydas). To ensure the chemical mixture in blood is transferred with minimal losses or bias, we tested a modified QuEChERS extraction method specifically developed for multi- and non-target instrument analysis. The extracts were dosed to a battery of in vitro bioassays (AhR-CAFLUX, AREc32, NFκB-bla, VM7Luc4E2, Microtox), each with a different mode of action (e.g., AhR receptor mediated xenobiotics, NrF2-mediated oxidative stress, NFκB mediated response to inflammation, estrogen activity and baseline toxicity oxidative stress, respectively) in order to cover a wide spectrum of chemicals. Results confirmed the absence of interferences of the blood extract with the responses of the different assays, thus indicating the methods' compatibility with effect-based screening approaches. To apply this approach, whole blood samples were collected from green turtles foraging in agricultural, urban and remote areas of the Australian Great Barrier Reef. The effect-based screening revealed significant differences in exposure, with higher induction of AhR-CAFLUX, AREc32 and Microtox assays in turtles from the agricultural foraging ground. Overall, these results corroborated with concurrent health, target and non-target analyses in the same animals performed as part of a larger program. This study provides evidence that the proposed effect-based approach is suitable for screening and evaluating internal exposure of organisms to chemical mixtures. The approach could be valuable for advancing understanding on multiple levels ranging from identification of priority chemicals in effect-directed investigations to exploring relationships between exposure and disease, not only in sea turtles, but in any organism.

Non-targeted, high resolution mass spectrometry strategy for simultaneous monitoring of xenobiotics and endogenous compounds in green sea turtles on the Great Barrier Reef.

Chemical contamination poses a threat to ecosystem, biota and human health, and identifying these hazards is a complex challenge. Traditional hazard identification relies on a priori-defined targets of limited chemical scope, and is generally inappropriate for exploratory studies such as explaining toxicological effects in environmental systems. Here we present a non-target high resolution mass spectrometry environmental monitoring study with multivariate statistical analysis to simultaneously detect biomarkers of exposure (e.g. xenobiotics) and biomarkers of effect in whole turtle blood. Borrowing the concept from clinical chemistry, a case-control sampling approach was used to investigate the potential influence of xenobiotics of anthropogenic origin on free-ranging green sea turtles (Chelonia mydas) from a remote, offshore 'control' site; and two coastal 'case' sites influenced by urban/industrial and agricultural activities, respectively, on the Great Barrier Reef in North Queensland, Australia. Multiple biomarkers of exposure, including sulfonic acids (n=9), a carbamate insecticide metabolite, and other industrial chemicals; and five biomarkers of effect (lipid peroxidation products), were detected in case sites. Additionally, two endogenous biomarkers of neuroinflammation and oxidative stress were identified, and showed moderate-to-strong correlations with clinical measures of inflammation and liver dysfunction. Our data filtering strategy overcomes limitations of traditional a priori selection of target compounds, and adds to the limited environmental xenobiotic metabolomics literature. To our knowledge this is the first case-control study of xenobiotics in marine megafauna, and demonstrates the utility of green sea turtles to link internal and external exposure, to explain potential toxicological effects in environmental systems.

Medium-Chain Chlorinated Paraffins (CPs) Dominate in Australian Sewage Sludge.

To simultaneously quantify and profile the complex mixture of short-, median-, and long-chain CPs (SCCPs, MCCPs, and LCCPs) in Australian sewage sludge, we applied and further validated a recently developed novel instrumental technique, using quadrupole time-of-flight high resolution mass spectrometry running in the negative atmospheric pressure chemical ionization mode (APCI-qTOF-HRMS). Without using an analytical column the cleaned extracts were directly injected into the qTOF-HRMS followed by quantification of the CPs by a mathematical algorithm. The recoveries of the four SCCP, MCCP and LCCP-spiked sewage sludge samples ranged from 86 to 123%. This APCI-qTOF-HRMS method is a fast and promising technique for routinely measuring SCCPs, MCCPs, and LCCPs in sewage sludge. Australian sewage sludge was dominated by MCCPs with concentrations ranging from 542 to 3645 ng/g dry weight (dw). Lower SCCPs concentrations (<57-1421 ng/g dw) were detected in the Australian sewage sludge, which were comparable with the LCCPs concentrations (116-960 ng/g dw). This is the first time that CPs were reported in Australian sewage sludge. The results of this study gives a first impression on the distribution of the SCCPs, MCCPs, and LCCPs in Australia wastewater treatment plants (WWTPs).

Chlorinated paraffins in the environment: A review on their production, fate, levels and trends between 2010 and 2015.

This review provides an update on information regarding the production volumes, regulations, as well as the environmental levels, trends, fate and human exposure to chlorinated paraffin mixtures (CPs). CPs encompas thousands congeners with varying properties and environmental fate. Based on their carbon chain lengths, CPs are divided into short- (SCCPs; C10-13), medium- (MCCPs; C14-17) and long- (LCCPs; C ≥ 18) chained groups. They are high production volume and persistent chemicals, and their cumulative global production already surpasses that of other persistent anthropogenic chemicals (e.g. PCBs). However, international regulations are still curbed by insufficient information on their levels and fate, including bioaccumulation and toxicity potential. An increasing number of studies since 2010 demonstrate that CPs are detected in almost every compartment in the environment, including remote areas. Consensus on the long range transport and high bioaccumulation potential (BCF > 5000 & TMF > 1) has recently been reached for SCCPs, fulfilling criteria under the Stockholm Convention for designation as a persistent organic pollutant; information on their levels is, however, still sparse for many countries. M/LCCPs have received comparatively little attention in the past, but as replacement chemicals for SCCPs, MCCPs are now considered in an increasing number of studies. The limited data to date suggests MCCPs are widely used. Although data on their bioaccumulation and toxicity are still inconclusive, MCCPs and LCCPs with C<20 may also have a bioaccumulation potential. Considering this and their high production volumes, use, and ubiquitous occurrence in the environment, a better understanding on the levels and fate of all CPs is needed.

Screening of organic and metal contaminants in Australian humpback dolphins (Sousa sahulensis) inhabiting an urbanised embayment.

As a marine mammal species that inhabits shallow nearshore waters, humpback dolphins are likely exposed to a wide range of pollutants from adjacent land-based activities. Increased mortality rates of Australian humpback dolphins (Sousa sahulensis) in waters off a major urbanised centre triggered investigations into the threats to these species, including their contaminant exposure. The present study utilised archived tissues from 6 stranded animals to screen for a range of pollutants (PCDD/Fs, PBDEs, PCBs, organochlorine pesticides, PAHs, organotins, essential and non-essential elements) to inform future biopsy based biomonitoring strategies. Concentrations of PCBs and DDXs in blubber of some of these animals were remarkably high, at levels near or above toxicological thresholds associated with immune- and reproductive toxicity or population declines in other marine mammals. PBDEs, PAHs, HCB, organotins, 'drins' as well as other organic pesticides were not detected, or present at relatively low concentrations. Profiles of elements were similar in epidermis compared to other tissues, and apart from some exceptions (e.g. Fe, Cr, Co, Cu) their concentrations fell within 25th-75th percentiles of cetacean baselines in four of the five animals. Non-essential elements (Al, V, Pb, Ba, Ni, Cd) were notably elevated in one specimen which may have experienced poor health or nutritional status. These data provide a first insight into the contaminant status of a rare and poorly studied population inhabiting an urbanised area. The results highlight a need for future biomonitoring of live populations, and inform on priorities in the typically limited blubber and skin sample volumes obtained through biopsies.

Solubility enhancement of dioxins and PCBs by surfactant monomers and micelles quantified with polymer depletion techniques.

Partitioning of super-hydrophobic organic contaminants (SHOCs) to dissolved or colloidal materials such as surfactants can alter their behaviour by enhancing apparent aqueous solubility. Relevant partition constants are, however, challenging to quantify with reasonable accuracy. Partition constants to colloidal surfactants can be measured by introducing a polymer (PDMS) as third phase with known PDMS-water partition constant in combination with the mass balance approach. We quantified partition constants of PCBs and PCDDs (log KOW 5.8-8.3) between water and sodium dodecyl sulphate monomers (KMO) and micelles (KMI). A refined, recently introduced swelling-based polymer loading technique allowed highly precise (4.5-10% RSD) and fast (<24 h) loading of SHOCs into PDMS, and due to the miniaturisation of batch systems equilibrium was reached in <5 days for KMI and <3 weeks for KMO. SHOC losses to experimental surfaces were substantial (8-26%) in monomer solutions, but had a low impact on KMO (0.10-0.16 log units). Log KMO for PCDDs (4.0-5.2) were approximately 2.6 log units lower than respective log KMI, which ranged from 5.2 to 7.0 for PCDDs and 6.6-7.5 for PCBs. The linear relationship between log KMI and log KOW was consistent with more polar and moderately hydrophobic compounds. Apparent solubility increased with increasing hydrophobicity and was highest in micelle solutions. However, this solubility enhancement was also considerable in monomer solutions, up to 200 times for OCDD. Given the pervasive presence of surfactant monomers in typical field scenarios, these data suggest that low surfactant concentrations may be effective long-term facilitators for subsurface transport of SHOCs.

Experimental Solubility Approach to Determine PDMS-Water Partition Constants and PDMS Activity Coefficients.

Freely dissolved aqueous concentration and chemical activity are important determinants of contaminant transport, fate, and toxic potential. Both parameters are commonly quantified using Solid Phase Micro-Extraction (SPME) based on a sorptive polymer such as polydimethylsiloxane (PDMS). This method requires the PDMS-water partition constants, KPDMSw, or activity coefficient to be known. For superhydrophobic contaminants (log KOW >6), application of existing methods to measure these parameters is challenging, and independent measures to validate KPDMSw values would be beneficial. We developed a simple, rapid method to directly measure PDMS solubilities of solid contaminants, SPDMS(S), which together with literature thermodynamic properties was then used to estimate KPDMSw and activity coefficients in PDMS. PDMS solubility for the test compounds (log KOW 7.2-8.3) ranged over 3 orders of magnitude (4.1-5700 µM), and was dependent on compound class. For polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins (PCDDs), solubility-derived KPDMSw increased linearly with hydrophobicity, consistent with trends previously reported for less chlorinated congeners. In contrast, subcooled liquid PDMS solubilities, SPDMS(L), were approximately constant within a compound class. SPDMS(S) and KPDMSw can therefore be predicted for a compound class with reasonable robustness based solely on the class-specific SPDMS(L) and a particular congener's entropy of fusion, melting point, and aqueous solubility.

Recent developments in capabilities for analysing chlorinated paraffins in environmental matrices: A review.

Concerns about the high production volumes, persistency, bioaccumulation potential and toxicity of chlorinated paraffin (CP) mixtures, especially short-chain CPs (SCCPs), are rising. However, information on their levels and fate in the environment is still insufficient, impeding international classifications and regulations. This knowledge gap is mainly due to the difficulties that arise with CP analysis, in particular the chromatographic separation within CPs and between CPs and other compounds. No fully validated routine analytical method is available yet and only semi-quantitative analysis is possible, although the number of studies reporting new and improved methods have rapidly increased since 2010. Better cleanup procedures that remove interfering compounds, and new instrumental techniques, which distinguish between medium-chain CPs (MCCPs) and SCCPs, have been developed. While gas chromatography coupled to an electron capture negative ionisation mass spectrometry (GC/ECNI-MS) remains the most commonly applied technique, novel and promising use of high resolution time of flight MS (TOF-MS) has also been reported. We expect that recent developments in high resolution TOF-MS and Orbitrap technologies will further improve the detection of CPs, including long-chain CPs (LCCPs), and the group separation and quantification of CP homologues. Also, new CP quantification methods have emerged, including the use of mathematical algorithms, multiple linear regression and principal component analysis. These quantification advancements are also reflected in considerably improved interlaboratory agreements since 2010. Analysis of lower chlorinated paraffins (

Coupling passive sampling with in vitro bioassays and chemical analysis to understand combined effects of bioaccumulative chemicals in blood of marine turtles.

Conventional target analysis of biological samples such as blood limits our ability to understand mixture effects of chemicals. This study aimed to establish a rapid passive sampling technique using the polymer polydimethylsiloxane (PDMS) for exhaustive extraction of mixtures of neutral organic chemicals accumulated in blood of green turtles, in preparation for screening in in vitro bioassays. We designed a PDMS-blood partitioning system based on the partition coefficients of chemicals between PDMS and major blood components. The sampling kinetics of hydrophobic test chemicals (polychlorinated dibenzo-p-dioxins; PCDDs) from blood into PDMS were reasonably fast reaching steady state in <96 h. The geometric mean of the measured PDMS-blood partition coefficients for PCDDs, polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) was 14 L blood kg PDMS(-1) and showed little variability (95% confidence interval from 8.4 to 29) across a wide range of hydrophobicity (logKow 5.7-8.3). The mass transfer of these chemicals from 5 mL blood into 0.94 g PDMS was 62-84%, which is similar to analytical recoveries in conventional solvent extraction methods. The validated method was applied to 15 blood samples from green turtles with known concentrations of PCDD/Fs, dioxin-like PCBs, PBDEs and organochlorine pesticides. The quantified chemicals explained most of the dioxin-like activity (69-98%), but less than 0.4% of the oxidative stress response. The results demonstrate the applicability of PDMS-based passive sampling to extract bioaccumulative chemicals from blood as well as the value of in vitro bioassays for capturing the combined effects of unknown and known chemicals.

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.

Adaptive stress response pathways induced by environmental mixtures of bioaccumulative chemicals in dugongs.

To address the poorly understood mixture effects of chemicals in the marine mammal dugong, we coupled equilibrium-based passive sampling in blubber to a range of in vitro bioassays for screening mixtures of bioaccumulative chemicals. The modes of action included early effect indicators along important toxicity pathways, such as induction of xenobiotic metabolism, and some integrative indicators downstream of the molecular initiating event, such as adaptive stress responses. Activation of aryl hydrocarbon receptor (AhR) and Nrf2-mediated oxidative stress response were found to be the most prominent effects, while the p53-mediated DNA damage response and NF-κB-mediated response to inflammation were not significantly affected. Although polychlorinated dibenzo-p-dioxins (PCDDs) quantified in the samples accounted for the majority of AhR-mediated activity, PCDDs explained less than 5% of the total oxidative stress response, despite their known ability to activate this pathway. Altered oxidative stress response was observed with both individual chemicals and blubber extracts subject to metabolic activation by rat liver S9 fraction. Metabolic activation resulted in both enhanced and reduced toxicity, suggesting the relevance and utility of incorporating metabolic enzymes into in vitro bioassays. Our approach provides a first insight into the burden of toxicologically relevant bioaccumulative chemical mixtures in dugongs and can be applied to lipid tissue of other wildlife species.

Levels of arsenic, cadmium, lead and mercury in the branchial plate and muscle tissue of mobulid rays.

Mobulid rays are targeted in fisheries for their branchial plates, for use in Chinese medicine. Branchial plate and muscle tissue from Mobula japanica were collected from fish markets in Sri Lanka, and muscle tissue biopsies from Manta alfredi in Australia. These were analysed for arsenic, cadmium, lead and mercury and compared to maximum levels (MLs) set by Food Standards Australia and New Zealand (FSANZ), European Commission (EC) and Codex Alimentarius Commission. The estimated intake for a vulnerable human age group was compared to minimal risk levels set by the Agency for Toxic Substances and Disease Registry. The mean inorganic arsenic concentration in M. japanica muscle was equivalent to the FSANZ ML while cadmium exceeded the EC ML. The mean concentration of lead in M. alfredi muscle tissue exceeded EC and Codex MLs. There were significant positive linear correlations between branchial plate and muscle tissue concentrations for arsenic, cadmium and lead.

Historical emissions of octachlorodibenzodioxin in a watershed in Queensland, Australia: estimation from field data and an environmental fate model.

An octachlorodibenzodioxin (OCDD)-dominated contamination is present along the coast of Queensland, Australia. Several findings indicate that this contamination originates from pesticide use, although due to limited information on OCDD levels in the pesticides used, estimating past and current emissions of OCDD solely from pesticide use data is unfeasible. We used all the qualitative and quantitative information available on OCDD in pesticides together with a previously validated chemical fate model for a catchment in the Queensland Wet Tropics to back-calculate the emissions of OCDD from measured soil concentrations. We estimate that under different emission scenarios an average of 2,500 kg of OCDD was emitted within the modelled 1,685 km2 (Tully river) catchment between 1950 and 2010. Because this catchment represents only approximately 0.85% of the whole coast of Queensland under a similar contamination, the total amount of OCDD released in this region is considerably larger. For all emission scenarios, we could show that the OCDD currently present in agricultural soil is a result of historical emissions, and current-day emissions are less important in comparison to past emissions. Overall 18% was lost by degradation and 62% was buried below the agricultural surface soil, as a result of facilitated transport.