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Environmental offsetting has been developed as a mechanism to facilitate the benefits from economic development while avoiding or minimizing environmental harm. This is achieved by compensating for environmental impacts at one location by generating equivalent environmental improvements elsewhere. However, experience with biodiversity and carbon offsetting indicates it can be difficult to ensure the integrity of offsets. Under recent legislation in the catchments of the Great Barrier Reef (GBR), Australia, it is mandatory for water quality emissions from new or expanded point source development to be offset by reducing pollution elsewhere, frequently through reducing non-point source pollution (NPSP). Therefore, informed by experience with biodiversity and carbon offsetting, we summarised sources of uncertainty in NPSP reduction that would influence water quality offset integrity; estimated the maximum potential demand for water quality offsets from sewage treatment plants, the largest point source emitter of total nitrogen (TN) in the GBR catchments, between 2018 and 2050; and discussed the implications of both on the ability of offsetting to counterbalance the impact of economic development in catchments where nitrogen loads have a large influence on the health of important GBR ecosystems. The catchments surrounding the population centres of Cairns and Mackay had both a potentially high future demand for nitrogen water quality offsets and nitrogen loads with a strong influence on the health of the GBR. Consequently, any low integrity water quality offsets in these catchments could jeopardise progress toward the water quality improvements needed to ensure the continued health of the GBR. Water quality offsetting has numerous strengths as a policy instrument however substantial uncertainties remain related to environmental outcomes. Until further research can reduce these uncertainties, water quality offsets that are implemented near increased point source emissions and have a high certainty of effectiveness may provide a balance between scientific rigour and policy workability., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Pesticide active ingredients are frequently detected in the rivers, creeks, wetlands, estuaries, and marine waters of the Great Barrier Reef (GBR) region and are one of the main contributors to poor water quality. Pesticide concentrations detected in the environment through water quality monitoring programs can be compared against estimates of ecologically "safe" concentrations (i.e., water quality guidelines) to assess the potential hazard and risk posed to aquatic ecosystems. Water quality guidelines are also required to estimate the aquatic risk posed by pesticide mixtures, which is used for the Reef 2050 Water Quality Improvement Plan pesticide target. Seventy-four pesticide active ingredients and their degradates are frequently detected in GBR catchment waterways, however many do not have water quality guidelines in the Australian and New Zealand Guidelines for Fresh and Marine Water Quality. The current study derives ecotoxicity threshold values (ETVs) as unendorsed guideline values for active ingredients in two fungicides (4-hydroxychlorothalonil (fungicide degradate) and carbendazim) and two insecticides (dimethoate and methoxyfenozide) that are commonly detected in GBR catchment waterways. The proposed ETVs have been derived using species sensitivity distributions, as recommended in the Australian and New Zealand nationally endorsed method for deriving water quality guidelines for aquatic ecosystem protection. Four ETVs were derived for each chemical with values that should theoretically protect 99, 95, 90 and 80 % of species (i.e., PC99, PC95, PC90, PC80, respectively). The PC99 and PC95 values for 4-hydroxychlorothalonil, carbendazim, dimethoate and methoxyfenozide were 0.49 μg/L and 4 μg/L, 0.029 μg/L and 0.45 μg/L, 0.11 μg/L and 5.8 μg/L and 0.19 μg/L and 2 μg/L, respectively. The ETVs will be used in an ecological hazard and risk assessment across GBR waterways in part two of this study. The ETVs can also be used to assess potential risk across Australia and internationally where monitoring data are available., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2024. Published by Elsevier B.V. All rights reserved.)

Waterways that drain the Great Barrier Reef catchment area (GBRCA) transport pollutants to marine habitats, provide a critical corridor between freshwater and marine habitats for migratory fish species, and are of high socioecological value. Some of these waterways contain concentrations of pesticide active ingredients (PAIs) that exceed Australian ecotoxicity threshold values (ETVs) for ecosystem protection. In this article, we use a "pathway to harm" model with five key criteria to assess whether the available information supports the hypothesis that PAIs are or could have harmful effects on fish and arthropod populations. Strong evidence of the first three criteria and circumstantial weaker evidence of the fourth and fifth criteria are presented. Specifically, we demonstrate that exceedances of Australian and New Zealand ETVs for ecosystem protection are widespread in the GBRCA, that the PAI contaminated water occurs (spatially and temporally) in important habitats for fisheries, and that there are clear direct and indirect mechanisms by which PAIs could cause harmful effects. The evidence of individuals and populations of fish and arthropods being adversely affected species is more circumstantial but consistent with PAIs causing harmful effects in the freshwater ecosystems of Great Barrier Reef waterways. We advocate strengthening the links between PAI concentrations and fish health because of the cultural values placed on the freshwater ecosystems by relevant stakeholders and Traditional Owners, with the aim that stronger links between elevated PAI concentrations and changes in recreationally and culturally important fish species will inspire improvements in water quality. Integr Environ Assess Manag 2024;20:1256-1279. © 2023 Commonwealth of Australia and The Commonwealth Scientific and Industrial Research Organisation. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC)., (© 2023 Commonwealth of Australia and The Commonwealth Scientific and Industrial Research Organisation. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).)

Pesticide active ingredients (PAIs) are regularly detected in the rivers, creeks, wetlands, and inshore waterways that discharge to the Great Barrier Reef (GBR) lagoon. Pesticide active ingredients detected above ecologically protective concentrations may pose a hazard and risk to aquatic species. The ability to assess this hazard and risk is reliant on the availability of water quality guidelines, which are only available for a limited number of PAIs detected in GBR catchment waterways. Unendorsed guideline values, known as ecotoxicity threshold values (ETVs) were developed in part one of this study for active ingredients in two fungicides (4-hydroxychlorothalonil (fungicide degradate) and carbendazim) and two insecticides (dimethoate and methoxyfenozide) that are commonly detected in GBR catchment waterways. In the current study, the hazard and risk posed by these PAIs was assessed by comparing the ETVs to environmental monitoring data from the Great Barrier Reef Catchment Loads Monitoring Program. Exceedances of the concentrations that should protect 99 % of aquatic species (i.e., PC99) were observed for all four pesticides. Detected concentrations of 4-hydroxychlorothalonil, carbendazim and methoxyfenozide exceeded the PC95 ETV, however no exceedances of the PC95 were observed for dimethoate. The hazard quotient (HQ) method was used to identify high hazard sites across the GBR catchment area. In total, six sites were identified as having concentrations that exceeded the PC95 ETVs. For 4-hydroxychlorothalonil, the risk to aquatic species based on the 95th percentile concentrations ranged from 3 to 13 %, 1 to 8 % for carbendazim and 2 to 8 % for methoxyfenozide. Detected concentrations of carbendazim were two orders of magnitude higher than concentrations that are reported to induce behavioural effects in some fish species. Considering that detected concentrations of three of the four PAIs individually pose a potential risk to aquatic species, their contributions to pesticide mixture toxicity should be further assessed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Agricultural run-off in Australia's Mackay-Whitsunday region is a major source of nutrient and pesticide pollution to coastal and inshore ecosystems of the Great Barrier Reef. While the effects of run-off are well documented for the region's coral and seagrass habitats, the ecological impacts on estuaries, the direct recipients of run-off, are less known. This is particularly true for fish communities, which are shaped by the physico-chemical properties of coastal waterways that vary greatly in tropical regions. To address this knowledge gap, we used environmental DNA (eDNA) metabarcoding to examine fish assemblages at four locations (three estuaries and a harbour) subjected to varying levels of agricultural run-off during a wet and dry season. Pesticide and nutrient concentrations were markedly elevated during the sampled wet season with the influx of freshwater and agricultural run-off. Fish taxa richness significantly decreased in all three estuaries (F = 164.73, P = <0.001), along with pronounced changes in community composition (F = 46.68, P = 0.001) associated with environmental variables (largely salinity: 27.48% contribution to total variance). In contrast, the nearby Mackay Harbour exhibited a far more stable community structure, with no marked changes in fish assemblages observed between the sampled seasons. Among the four sampled locations, variation in fish community composition was more pronounced within the wet season (F = 2.5, P = 0.001). Notably, variation in the wet season was significantly correlated with agricultural contaminants (phosphorus: 6.25%, pesticides: 5.22%) alongside environmental variables (salinity: 5.61%, DOC: 5.57%). Historically contaminated and relatively unimpacted estuaries each demonstrated distinct fish communities, reflecting their associated catchment use. Our findings emphasise that while seasonal effects play a key role in shaping the community structure of fish in this region, agricultural contaminants are also important contributors in estuarine systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2024. Published by Elsevier Ltd. All rights reserved.)

Pesticide active ingredients (PAIs) are one of the main contributors affecting water quality in the Great Barrier Reef Catchment Area (GBRCA). While an extensive list of pesticides is monitored in the GBRCA, only a limited number have water quality guideline values (WQGs), meaning it is not possible to know whether these PAIs are present at concentrations that may pose a hazard to the aquatic environment. In the current study, we derived 66 ecotoxicity threshold values (ETVs) for PAIs, the equivalent of WQGs, with a focus on PAIs applied to sugar cane. The hazard posed by PAIs monitored as part of the Great Barrier Reef Catchment Loads Monitoring Program (GBRCLMP) was assessed by comparing the derived ETVs with monitoring data from 2016/2017 to 2021/2022. The derived ETVs included herbicides, insecticides and fungicides, with the values that should protect 99 or 95 % of aquatic species (PC99 or PC95) spanning nine orders of magnitude. The concentrations of 10 PAIs exceeded their respective ETVs, giving a hazard quotient (HQ) >1. Of particular concern were insecticides chlorpyrifos, diazinon and methomyl, which have maximum HQ values >10. However, joint probability plots indicated that the PAIs generally pose a low risk to the aquatic environment, with most samples below the limit of reporting. As PAIs are predominantly found in mixtures in the GBRCA, the hazard posed by PAI mixtures was assessed by summing all individual HQ values in a sample for all PAIs with an ETV or WQG. On average, the insecticide active ingredient imidacloprid and herbicide active ingredients metolachlor, metsulfuron methyl, diuron and imazepic were the drivers of combined mixture hazard. Methomyl was an important contributor at some sites, suggesting that this pesticide should be considered for inclusion in any future PAI mixture hazard and/or risk assessment of the GBRCA., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Bioavailability models, for example, multiple linear regressions (MLRs) of water quality parameters, are increasingly being used to develop bioavailability-based water quality criteria for metals. However, models developed for the Northern Hemisphere cannot be adopted for Australia and New Zealand without first validating them against local species and local water chemistry characteristics. We investigated the applicability of zinc chronic bioavailability models to predict toxicity in a range of uncontaminated natural waters in Australia and New Zealand. Water chemistry data were compiled to guide a selection of waters with different zinc toxicity-modifying factors. Predicted toxicities using several bioavailability models were compared with observed chronic toxicities for the green alga Raphidocelis subcapitata and the native cladocerans Ceriodaphnia cf. dubia and Daphnia thomsoni. The most sensitive species to zinc in five New Zealand freshwaters was R. subcapitata (72-h growth rate), with toxicity ameliorated by high dissolved organic carbon (DOC) or low pH, and hardness having a minimal influence. Zinc toxicity to D. thomsoni (reproduction) was ameliorated by both high DOC and hardness in these same waters. No single trophic level-specific effect concentration, 10% (EC10) MLR was the best predictor of chronic toxicity to the cladocerans, and MLRs based on EC10 values both over- and under-predicted zinc toxicity. The EC50 MLRs better predicted toxicities to both the Australian and New Zealand cladocerans to within a factor of 2 of the observed toxicities in most waters. These findings suggest that existing MLRs may be useful for normalizing local ecotoxicity data to derive water quality criteria for Australia and New Zealand. The final choice of models will depend on their predictive ability, level of protection, and ease of use. Environ Toxicol Chem 2023;42:2614-2629. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (© 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

Pesticides decrease the quality of water reaching the Great Barrier Reef (GBR), Australia. Up to 86 pesticide active ingredients (PAIs) were monitored between July 2015 to end of June 2018 at 28 sites in waterways that discharge to the GBR. Twenty-two frequently detected PAIs were selected to calculate their combined risk when they co-occur in water samples. Species sensitivity distributions (SSDs) for the 22 PAIs to fresh and marine species were developed. The SSDs, the multi-substance potentially affected fraction (msPAF) method, Independent Action model of joint toxicity and a Multiple Imputation method were combined to convert measured PAI concentration data to estimates of the Total Pesticide Risk for the 22 PAIs (TPR 22 ) expressed as the average percentage of species affected during the wet season (i.e., 182 days). The TPR 22 and percent contribution of active ingredients of Photosystem II inhibiting herbicides, Other Herbicides, and Insecticides to the TPR 22 were estimated. The TPR 22 ranged from <1 % to 42 % of aquatic species being affected. Approximately 85 % of the TPR 22 estimates were >1 % - meaning they did not meet the Reef 2050 Water Quality Improvement Plan's pesticide target for waters entering the GBR. There were marked spatial differences in TPR 22 estimates - regions dominated by grazing had lower estimates while those with sugar cane tended to have higher estimates. On average, active ingredients of PSII herbicides contributed 39 % of the TPR 22 , the active ingredients of Other Herbicides contributed ~36 % and of Insecticides contributed ~24 %. Nine PAIs (diuron, imidacloprid, metolachlor, atrazine, MCPA, imazapic, metsulfuron, triclopyr and ametryn) were responsible for >97 % of TPR 22 across all the monitored waterways., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Coastal ecosystems such as those in the Great Barrier Reef (GBR) lagoon, are exposed to stressors in flood plumes including low light (caused by increased turbidity) and agricultural pesticides. Photosystem II (PSII)-inhibiting herbicides are the most frequently detected pesticides in the GBR lagoon, but it is not clear how their toxicity to phototrophic species depends on light availability. This study investigated the individual and combined effects of PSII-inhibiting herbicide, diuron, and reduced light intensity (as a proxy for increased turbidity) on the marine diatom, Phaeodactylum tricornutum. Effective quantum yield (EQY) and cell density were measured to calculate responses relative to the controls over 72-h, in tests with varying stressor intensities. Individually, diuron concentrations (0.1-3 μg l -1 ) were not high enough to significantly reduce growth (cell density), but led to decreased EQY; while, low light generally led to increased EQY, but only reduced growth at the lowest tested light intensity (5 μmol photons m -2 s -1 ) after 48-hours. P. tricornutum was less affected by diuron when combined with low light scenarios, with increased EQY (up to 163% of the controls) that was likely due to increased electron transport per photon, despite lesser available photons at this low light intensity. In contrast, growth was completely inhibited relative to the controls when algae were simultaneously exposed to the highest stressor levels (3 μg l -1 diuron and 5 μmol photons m -2 s -1 ). This study highlights the importance of measuring more than one biological response variable to capture the combined effects of multiple stressors. Management of water quality stressors should consider combined impacts rather than just the impacts of individual stressors alone. Reducing suspended sediment and diuron concentrations in marine waters can decrease harmful effects and bring synergistic benefits to water quality., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

The widely used neonicotinoid insecticide imidacloprid has emerged as a significant risk to surface waters and the diverse aquatic and terrestrial fauna these ecosystems support. While herbicides have been the focus of research on pesticides in Australia's Great Barrier Reef catchment area, imidacloprid has been monitored in catchments across the region since 2009. This study assessed the spatial and temporal dynamics of imidacloprid in 14 waterways in Queensland, Australia over seven years in relation to land use and concentration trends. Imidacloprid could be quantified (i.e., concentrations were greater than the limit of reporting) in approximately 54% of all samples, but within individual waterways imidacloprid was quantified in 0 to 99.7% of samples. The percent of each catchment used to grow bananas, sugar cane and urban explained approximately 45% of the variation in imidacloprid concentrations and waterway discharge accounted for another 18%. In six waterways there were significant increases in imidacloprid concentrations and the frequency and magnitude of exceedances of aquatic ecosystem protection guidelines over time. Overall, the risk posed by imidacloprid was low with 74% of samples protecting at least 99% of species but it was estimated that upto 42% of aquatic species would experience harmful chronic effects. Potential explanations of the changes in imidacloprid were examined. Not surprisingly, the only plausible explanation of the increases was increased use of imidacloprid. While field-based measurement of the effects of imidacloprid are limited in the Great Barrier Reef Catchment Area (GBRCA) the risk assessment indicates that biological harm to aquatic organisms is highly likely. Action to reduce imidacloprid concentrations in the GBRCA waterways is urgently required to reverse the current trends and mitigate environmental impacts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Coastal ecosystems are exposed to multiple anthropogenic stressors. Effective management actions would be better informed from generalized predictions of the individual, combined and interactive effects of multiple stressors; however, few generalities are shared across different meta-analyses. Using an experimental study, we present an approach for analysing regression-based designs with generalized additive models that allowed us to capture nonlinear effects of exposure duration and stressor intensity and access interactions among stressors. We tested the approach on a globally distributed marine diatom, using 72 h photosynthesis and growth assays to quantify the individual and combined effects of three common water quality stressors; photosystem II-inhibiting herbicide exposure, dissolved inorganic nitrogen (DIN) enrichment and reduced light (due to excess suspended sediment). Exposure to DIN and reduced light generally resulted in additivity, while exposure to diuron and reduced light resulted in additive, antagonistic or synergistic interactions, depending on the stressor intensity, exposure period and biological response. We thus find the context of experimental studies to be a primary driver of interactions. The experimental and modelling approaches used here bridge the gap between two-way designs and regression-based studies, which provides a way forward to identify generalities in multiple stressor interactions.

Agriculture within the Great Barrier Reef catchment area has contributed to pesticide contamination of adjacent freshwater ecosystems that flow into the Great Barrier Reef World Heritage Area. A novel multispecies toxicity test was used to assess the toxicity of diuron and hexazinone, 2 herbicides commonly detected within the Great Barrier Reef catchment area, to a community of 3 tropical freshwater microalgae: Monoraphidium arcuatum, Nannochloropsis-like sp., and Pediastrum duplex. Diuron was the most toxic herbicide, with 10% inhibition concentration (IC10) values of 4.3, 7.1, and 29 µg/L for P. duplex, M. arcuatum, and Nannochloropsis-like sp., respectively, followed by hexazinone, with IC10 values of 15, 18, and 450 µg/L, respectively Toxicity testing on 2 commercial formulations (Barrage, 13.2% hexazinone and 48.6% diuron; Diurex, 90% diuron) showed that additives in the commercial formulations did not significantly increase the toxicity of diuron. Direct toxicity assessments were carried out on water samples from the herbicide-contaminated Sandy Creek, which discharges to the Great Barrier Reef lagoon, and a clean reference site, Tully Gorge in the Tully River. Toxicity was observed in several Sandy Creek samples. Artificial herbicide mixtures were assessed in synthetic soft water and natural freshwaters, with toxic responses being observed at environmentally relevant concentrations. The present study successfully applied a novel multispecies tropical microalgal toxicity test, indicating that it is an effective tool for the assessment of herbicide toxicity in both natural and synthetic freshwaters. Environ Toxicol Chem 2021;40:473-486. © 2020 SETAC., (© 2020 SETAC.)

Rivers discharging to the Great Barrier Reef carry complex pesticide mixtures. Here we present a first comprehensive ecotoxicological risk assessment using species sensitivity distributions (SSDs), explore how risk changes with time and land use, and identify the drivers of mixture risks. The analyzed data set comprises 50 different pesticides and pesticide metabolites that were analyzed in 3741 samples from 18 river and creek catchments between 2011 and 2016. Pesticide mixtures were present in 82% of the samples, with a maximum of 23 pesticides and a median of five compounds per sample. Chemical-analytical techniques were insufficiently sensitive for at least seven pesticides (metsulfuron-methyl, terbutryn, imidacloprid, clothianidin, ametryn, prometryn, and thiamethoxam). The classical mixture concepts of concentration addition and independent action were applied to the pesticide SSDs, focusing on environmental threshold values protective for 95% of the species. Both concepts produced almost identical risk estimates. Mixture risk was therefore finally assessed using concentration addition, as the sum of the individual risk quotients. The sum of risk quotients ranges between 0.05 and 122 with a median of 0.66. An ecotoxicological risk (i.e., a sum of individual risk quotients exceeding 1) was indicated in 38.5% of the samples. Sixteen compounds accounted for 99% of the risk, with diuron, imidacloprid, atrazine, metolachlor, and hexazinone being the most important risk drivers. Analysis of land-use patterns in catchment areas showed an association between sugar cane farming and elevated risk levels, driven by the presence of diuron.

Knowledge of the types and impacts of contaminants occurring in the freshwater wetlands of the Great Barrier Reef catchment area (GBRCA) is limited. The present study examined the presence and concentrations of pesticides occurring in 22 floodplain wetlands, situated in moderate to high-intensity land uses in the GBRCA. The dominant land use within 1 km of the wetlands was sugar cane for 12 wetlands, grazing for 6 wetlands, plantation forestry and conservation for 2 wetlands, and one with an equal mix of land uses. Fifty-nine pesticides and pesticide degradates were detected in the wetlands during 2 consecutive early wet seasons. These included 27 herbicides, 11 herbicide degradates, 11 insecticides, 8 fungicides, 1 nematicide, and 1 pesticide synergist. Each wetland sampled contained between 12 and 30 pesticides with an average of 21 pesticides detected per wetland sampling. Temporal differences existed in the number, types, and average concentrations of pesticides detected. No exceedances of Australian and New Zealand water guideline values were found during the first sampling season, while 10 wetlands had concentrations of at least 1 pesticide exceeding the guidelines during the following sampling season. For 1 wetland, concentrations of 4 pesticides were greater than the prescribed guideline values. Individually, the vast majority of aquatic species would be protected, but in some wetlands, diuron would affect 49% of species and atrazine up to 24% of species. Statistically significant correlations between the number of pesticides and the percentage of intensive land use, primarily sugar cane growing in a 1 km radius of the wetlands, were found. Integr Environ Assess Manag 2020;16:968-982. © 2020 SETAC., (© 2020 SETAC.)

Organisms and ecosystems are generally exposed to mixtures of chemicals rather than to individual chemicals, but there have been relatively few detailed analyses of the mixtures of pesticides that occur in surface waters. This study examined over 2600 water samples, analysed for between 21 and 47 pesticides, from 15 waterways that discharge to the lagoon of the Great Barrier Reef in Queensland, Australia between July 1, 2011 and June 30, 2015. Essentially all the samples (99.8%) contained detectable concentrations (>limit of detection) of pesticides and pesticide mixtures. Approximately, 10% of the samples contained no quantifiable (>limit of reporting) pesticides, 10% contained one quantifiable pesticide and 80% contained quantifiable mixtures of 2-20 pesticides. Approximately 82% of samples that contained quantifiable mixtures had more than two modes of action (MoAs), but only approximately 6% had five or more MoAs. The mode, average and median number of quantifiable pesticides in all the samples were 2, 5.1 and 4, respectively. The most commonly detected compounds both individually and in mixtures were the pesticides atrazine, diuron, imidacloprid, hexazinone, 2,4-D, and the degradation product desethylatrazine. The number of pesticides and modes of action of pesticides in mixtures differed spatially and were affected by land use. Waterways draining catchments where sugar cane was a major land use had mixtures with the most pesticides., (Crown Copyright © 2020. Published by Elsevier Ltd. All rights reserved.)

Increased frequency of summer heatwaves and poor water quality are two of the most prevalent and severe pressures faced by coral reefs. While these pressures often co-occur, their potential risks to tropical marine species are usually considered independently. Here, we extended the application of multisubstance-Potentially Affected Fraction (ms-PAF) to a nonchemical stressor, elevated sea surface temperature. We then applied this method to calculate climate-adjusted water quality guideline values (GVs) for two reference toxicants, copper and the herbicide diuron, for tropical marine species. First, we developed a species sensitivity distribution (SSD) for thermal stress based on published experimental data for 41 tropical benthic marine species using methods adapted from water quality GV derivation. This enabled quantitative predictions of community effects as temperatures exceeded acclimation values. The resulting protective temperature values (PTx) were similar to temperatures known to initiate coral bleaching and are therefore relevant for application in multistressor risk assessments. The extended ms-PAF method enabled the adjustment of current water quality GVs to account for thermal stress events. This approach could be applied to other ecosystems and other non-contaminant stressors (e.g., sediment, low salinity, anoxia, and ocean acidification), offering an alternative approach for deriving environmental GVs, reporting and assessing the risk posed by multiple stressors.

Microalgae are commonly used in ecotoxicity testing due to their ease of culturing and rapid cell division rates. These tests generally utilise a single species of algae; however, microalgae occur in the environment as complex communities of multiple species. To date, routine multispecies toxicity tests using tropical microalgae have not been available. This study investigated four tropical freshwater microalgal species for use in a chronic multispecies toxicity test based on the population growth (cell division) rate: Pediastrum duplex, Monoraphidium arcuatum, Nannochloropsis-like sp. and Chlorella sp. 12. Flow cytometric analysis identified the different fluorescence and light scattering properties of each algal species and quantified each species within multispecies mixtures. Following optimisation of test media nutrients and pH, a toxicity testing protocol was developed with P. duplex, M. arcuatum and Nannochloropsis-like sp. There were no significant differences in growth rates of each alga when tested over 72 h as single species or in multispecies mixtures. Atrazine and imazapic, two herbicides with different modes of action, were used to assess the sensitivity of the multispecies toxicity test. Atrazine was toxic to all species with 72-h IC10 values of 7.2, 63 and 280 μg/L for P. duplex, M. arcuatum and Nannochloropsis-like sp. respectively, while imazapic was not toxic to any species at concentrations up to 1100 μg/L. The toxicity of atrazine and imazapic to each microalgal species in the multispecies toxicity test was the same as that determined from single-species toxicity tests indicating that the presence of these microalgae in a mixture did not affect the toxicity of these two herbicides. This study is the first to develop a multispecies tropical microalgal toxicity test for application in freshwaters. This time- and cost-effective tool can be utilised to generate data to assist environmental decision making and to undertake risk assessments of contaminants in tropical freshwater environments., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Increased water demands due to population growth and increased urbanisation have driven adoption of various water reuse practices. The irrigation of greywater (water from all household uses, except toilets) has been proposed as one potential sustainable practice. Research has clearly identified environmental harm from the presence of micro-pollutants in soils, groundwater and surface water. Greywater contains a range of micro pollutants yet very little is known about their potential environmental fate when greywater is irrigated to soil. Therefore, this study assessed whether organic micro-pollutants in irrigated greywater were transferred to shallow groundwater and an adjacent surface waterway. A total of 22 organic micro-pollutants were detected in greywater. Six of these (acesulfame, caffeine, DEET, paracetamol, salicylic acid and triclosan) were selected as potential tracers of greywater contamination. Three of these chemicals (acesulfame, caffeine, DEET) were detected in the groundwater, while salicylic acid was also detected in adjacent surface water. Caffeine and DEET in surface water were directly attributable to greywater irrigation. Thus the practice of greywater irrigation can act as a source of organic micro-pollutants to shallow groundwater and nearby surface water. The full list of micro-pollutants that could be introduced via greywater and the risk they pose to aquatic ecosystems is not yet known., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Barramundi (Lates calcarifer) were collected at the beginning (1st sampling) and end (2nd sampling) of the wet season from Sandy Creek, an agriculturally impacted catchment in the Mackay Whitsundays region of the Great Barrier Reef catchment area, and from Repulse Creek, located approximately 100 km north in Conway National Park, to assess the impacts of pesticide exposure. Gill and liver histology, lipid class composition in muscle, and the hepatic transcriptome were examined. The first sample of Repulse Creek fish showed little tissue damage and low transcript levels of xenobiotic metabolism enzymes. Sandy Creek fish showed altered transcriptomic patterns, including those that regulate lipid metabolism, xenobiotic metabolism, and immune response; gross histological alterations including lipidosis; and differences in some lipid classes. The second sampling of Repulse Creek fish showed similar alterations in hepatic transcriptome and tissue structure as fish from Sandy Creek. These changes may indicate a decrease in health of pesticide exposed fish., (Copyright © 2018. Published by Elsevier Ltd.)

There are over 40,000 chemical compounds registered for use in Australia, and only a handful are monitored in the aquatic receiving environments. Their effects on fish species in Australia are largely unknown. Mosquitofish (Gambusia holbrooki) were sampled from six river sites in Southeast Queensland identified as at risk from a range of pollutants. The sites selected were downstream of a wastewater treatment plant discharge, a landfill, two agricultural areas, and two sites in undeveloped reaches within or downstream of protected lands (national parks). Vitellogenin analysis, histopathology of liver, kidney and gonads, morphology of the gonopodium, and chemical body burden were measured to characterize fish health. Concentrations of trace organic contaminants (TrOCs) in water were analyzed by in vitro bioassays and chemical analysis. Estrogenic, anti-estrogenic, anti-androgenic, progestagenic and anti-progestagenic activities and TrOCs were detected in multiple water samples. Several active pharmaceutical ingredients (APIs), industrial compounds, pesticides and other endocrine active compounds were detected in fish carcasses at all sites, ranging from <4-4700ng/g wet weight, including the two undeveloped sites. While vitellogenin protein was slightly increased in fish from two of the six sites, the presence of micropollutants did not cause overt sexual endocrine disruption in mosquitofish (i.e., no abnormal gonads or gonopodia). A correlation between lipid accumulation in the liver with total body burden warrants further investigation to determine if exposure to low concentrations of TrOCs can affect fish health and increase stress on organs such as the liver and kidneys via other mechanisms, including disruption of non-sexual endocrine axes involved in lipid regulation and metabolism., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Environmental risk assessment of chemical mixtures is challenging because of the multitude of possible combinations that may occur. Aquatic risk from chemical mixtures in an agricultural landscape was evaluated prospectively in 2 exposure scenario case studies: at field scale for a program of 13 plant-protection products applied annually for 20 yr and at a watershed scale for a mixed land-use scenario over 30 yr with 12 plant-protection products and 2 veterinary pharmaceuticals used for beef cattle. Risk quotients were calculated from regulatory exposure models with typical real-world use patterns and regulatory acceptable concentrations for individual chemicals. The results could differentiate situations when there was concern associated with single chemicals from those when concern was associated with a mixture (based on concentration addition) with no single chemical triggering concern. Potential mixture risk was identified on 0.02 to 7.07% of the total days modeled, depending on the scenario, the taxa, and whether considering acute or chronic risk. Taxa at risk were influenced by receiving water body characteristics along with chemical use profiles and associated properties. The present study demonstrates that a scenario-based approach can be used to determine whether mixtures of chemicals pose risks over and above any identified using existing approaches for single chemicals, how often and to what magnitude, and ultimately which mixtures (and dominant chemicals) cause greatest concern. Environ Toxicol Chem 2018;37:674-689. © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC., (© 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.)

Triazine and urea herbicides are two groups of photosystem II inhibiting herbicides frequently detected in surface, ground and marine waters. Yet, there are few water quality guidelines for herbicides. Ecotoxicity thresholds (ETs) for ametryn, hexazinone and simazine (triazine herbicides) and diuron (a urea herbicide) were calculated using the Australian and New Zealand method for deriving guideline values to protect fresh and marine ecosystems. Four ETs were derived for each chemical and ecosystem that should theoretically protect 99, 95, 90 and 80% of species (i.e. PC99, PC95, PC90 and PC80, respectively). For all four herbicides, the phototrophic species were significantly more sensitive than non-phototrophic species, and therefore, only the former data were used to calculate the ETs. Comparison of the ET values to measured concentrations in 2606 samples from 15 waterways that discharge to the Great Barrier Reef (2011-2015) found three exceedances of the simazine PC99, regular exceedances (up to 30%) of the PC99 in a limited number of rivers for ametryn and hexazinone and frequent (> 40%) exceedances of the PC99 and PC95 ETs in at least four waterways for diuron. There were no exceedances of the marine ETs in inshore reef areas. Further, ecotoxicity data are required for ametryn and hexazinone to fresh and marine phototrophic species, for simazine to marine phototrophic species, for tropical phototrophic species, repeated pulse exposures and long-term (2 to 12 months) exposures to environmentally relevant concentrations.

Resource managers need to differentiate between sites with and without contaminants and those where contaminants cause impacts. Potentially, transcriptomes could be used to evaluate sites where contaminant-induced effects may occur, to identify causative stressors of effects and potential adverse outcomes. To test this hypothesis, the hepatic transcriptomes in Barramundi, a perciforme teleost fish, (Lates calcarifer) from two reference sites, two agriculturally impacted sites sampled during the dry season, and an impacted site sampled during the wet season were compared. The hepatic transcriptome was profiled using RNA-Seq. Multivariate analysis showed that transcriptomes were clustered based on site and by inference water quality, but not sampling time. The largest differences in transcriptomic profile were between reference sites and a site sampled during high run-off, showing that impacted sites can be identified via RNA-Seq. Transcripts with altered abundance were linked to xenobiotic metabolism, peroxisome proliferation and stress responses, indicating putative stressors with the potential for adverse outcomes in barramundi., (Copyright © 2017. Published by Elsevier Ltd.)

Pollutant loads are a means for assessing regulatory compliance and setting targets to reduce pollution entering receiving waterbodies. However, a pollutant load is often comprised of multiple chemicals, which may exert joint toxicity on biota. When the ultimate goal for assessing pollutant loads is to protect ecosystems from adverse effects of toxicants, then the total pollutant load needs to be calculated based on the principles of mixture toxicology. In this article, an improved method is proposed to convert a pollutant load to a toxicity-based load (toxic load) using a modified toxic equivalency factor (TEF) derivation method. The method uses the relative potencies (RePs) of multiple species to represent the response of the ecological community. The TEF is calculated from a percentile of a cumulative distribution function (CDF) fitted to the RePs. The improvements permit the determination of which percentile of the CDF generates the most environmentally relevant and robust toxic loads. That is, environmental relevance ensures that a reduction in the toxic load is likely to result in a corresponding improvement in ecosystem health and robustness ensures that the calculation of the toxic loads is not biased by the reference chemical used. The improved methodology will therefore ensure that correct management decisions will be made and ultimately, a reduction in the toxic load will lead to a commensurate improvement in water quality. Integr Environ Assess Manag 2017;13:746-753. © 2016 SETAC., (© 2016 SETAC.)

Pollutant loads are widely used to set pollution reduction targets and assess regulatory compliance for the protection of receiving waterbodies. However, when a pollutant load consists of a mixture of chemicals, reducing the overall load (mass) will not necessarily reduce the toxicity by a similar amount. This can be overcome by setting targets based on toxicity-based loads (toxic loads, TLs), where the load is modified according to the relative toxicity (expressed as toxic equivalency factors [TEFs]) of each toxicant. Here, we present the second article of a 2-part series in which a case study is used to demonstrate the application of the toxic load method proposed in Part 1. The toxic load method converts a pollutant load, comprised of multiple chemicals, to a toxic load, using a modified TEF approach. The modified approach uses a cumulative distribution of relative potency (ReP) estimates of multiple species to determine a TEF. It further improves upon previously published methods by including two tests to select the optimal percentile of the ReP distribution to determine the TEF. The first test is a test for environmental relevance that compares results against an independent mixture method, identifying the percentile that produces the most environmentally relevant TEFs and TLs. The second is a test for robustness which ensures the results are independent of the ReP of the selected reference chemical. Here, the TL method is applied to mixtures of pesticides that are discharged from agricultural land to the Great Barrier Reef (GBR) to test its utility. In this case study, the most environmentally relevant and robust TLs were generated using the 75th percentile of the ReP cumulative distribution. The results demonstrate that it is essential to develop pollution reduction targets based on toxic loads and making progress to meeting them will lead to a commensurate reduction in toxic effects caused by toxicants in waters of the GBR. Integr Environ Assess Manag 2017;13:754-764. © 2016 SETAC., (© 2016 SETAC.)

Increased water demands in dry countries such as Australia, have led to increased adoption of various water reuse practices. Irrigation of greywater (all water discharged from the bathrooms, laundry and kitchen apart from toilet waste) is seen as a potential means of easing water demands; however, there is limited knowledge of how greywater irrigation impacts terrestrial and aquatic environments. This study compared four greywater irrigated residential lots to adjacent non-irrigated lots that acted as controls. Accumulation and potential impacts of metals in soil, groundwater and surface water, as a result of greywater irrigation, were assessed by comparing measured concentrations to national and international guidelines. Greywater increased concentrations of some metals in irrigated soil and resulted in As, B, Cr and Cu exceeding guidelines after only four years of irrigation. Movement of metals from the irrigation areas resulted in metal concentrations in groundwater (Al, As, Cr, Cu, Fe, Mn, Ni and Zn) and surface water (Cu, Fe and Zn) exceeding environmental quality guidelines again within four years. These results are unlikely to be universally applicable but indicate the need to consider metals in greywater in order to minimize potential adverse environmental effects from greywater irrigation., (Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.)

In sediments several binding phases dictate the fate and bioavailability of organic contaminants. Black carbon (BC) has a high sorptive capacity for organic contaminants and can limit their bioavailability, while the fraction bound to organic carbon (OC) is considered to be readily desorbable and bioavailable. We investigated the bioavailability and mixture toxicity of sediment-associated contaminants by combining different extraction techniques with in vitro bioanalytical tools. Sediments from a harbour with high fraction of BC, and sediments from remote, agricultural and urban areas with lower BC were treated with exhaustive solvent extraction, Tenax extraction and passive sampling to estimate total, bioaccessible and bioavailable fractions, respectively. The extracts were characterized with cell-based bioassays that measure dioxin-like activity (AhR-CAFLUX) and the adaptive stress response to oxidative stress (AREc32). Resulting bioanalytical equivalents, which are effect-scaled concentrations, were applied in an effect-balance model, consistent with a mass balance-partitioning model for single chemicals. Sediments containing BC had most of the bioactivity associated to the BC fraction, while the OC fraction played a role for sediments with lower BC. As effect-based sediment-water distribution ratios demonstrated, most of the bioactivity in the AhR-CAFLUX was attributable to hydrophobic chemicals while more hydrophilic chemicals activated AREc32, even though bioanalytical equivalents in the aqueous phase remained negligible. This approach can be used to understand the fate and effects of mixtures of diverse organic contaminants in sediments that would not be possible if single chemicals were targeted by chemical analysis; and make informed risk-based decisions concerning the management of contaminated sediments., (Copyright © 2016 Elsevier Ltd. All rights reserved.)