Pesticides in the Great Barrier Reef catchment area: Plausible risks to fish populations.

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;00:1-24. © 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).

A Pesticide Decision Support Tool to guide the selection of less environmentally harmful pesticides for the sugar cane industry.

Pesticides applied to agricultural land have been shown to decrease the quality of water entering the Great Barrier Reef lagoon. This issue is addressed by the Reef 2050 Water Quality Improvement Plan which includes a pesticide reduction target. As part of a wider educational strategy, one method that could help meet the target is to provide stakeholders with information that assists in the selection and use of pesticide active ingredients (PAIs) that pose a lower risk to aquatic environments compared to those currently used. This study developed a Pesticide Decision Support Tool (PDST) in collaboration with stakeholders for the sugar cane industry. The PDST covers all PAIs registered and applied to sugar cane in Australia and four additional PAIs registered for use on crops grown in rotation with sugar cane. The PDST incorporates both the measure of mobility and persistence of a PAI and the measure of effect, which is based on the PAI application rate and ecotoxicity threshold value. The aquatic risk, which is the product of the measure of effect and the measure of mobility and persistence, is a measure of the likelihood that a PAI will reach the aquatic environment and cause harmful effects. Insecticide active ingredients (e.g., cadusafos, chlorpyrifos) posed the greatest aquatic risk, followed by herbicide active ingredients (e.g., MSMA, metolachlor), while fungicide AIs typically had a lower aquatic risk. An interactive spreadsheet allows characteristics, including application rate and tank mixes, to be considered when assessing the potential risk. While focusing on sugar cane, the results are equally appropriate to other crops that use the same PAIs provided the application rates are corrected to the new crop. In addition, the approach used in the PDST can be applied internationally and to any PAIs with sufficient toxicity, mobility, and persistence data.

Validation of the nickel biotic ligand model for locally relevant species in Australian freshwaters.

Australian freshwaters have relatively low water hardness and different calcium (Ca) to magnesium (Mg) ratios compared with those in Europe. The hardness values of a substantial proportion of Australian freshwaters fall below the application boundary of the existing European nickel biotic ligand models (Ni BLMs) of 2 mg Ca/L. Toxicity testing was undertaken using Hydra viridissima to assess the predictive ability of the existing Ni BLM for this species in extremely soft waters. This testing revealed an increased competitive effect of Ca and Mg with Ni for binding to the biotic ligand in soft water (<10 mg CaCO3 /L) than at higher water hardness. Modifications were made to the Ni BLM by increasing the binding constants for Ca and Mg at the biotic ligand to account for softer waters encountered in Australia and the more important competitive effect of Ca and Mg on Ni toxicity. To validate the modified Ni BLM, ecotoxicity testing was performed on 5 Australian test species in 5 different natural Australian waters. Overall, no single water chemistry parameter was able to indicate the trends in toxicity to all of the test species. The modified Ni BLMs were able to predict the toxicity of Ni to the test species in the validation studies in natural waters better than the existing Ni BLMs. The present study suggests that the overarching mechanisms defining Ni bioavailability to freshwater species are globally similar and that Ni BLMs can be used in all freshwater systems with minor modifications. Environ Toxicol Chem 2018;37:2566-2574. © 2018 SETAC.

An improved method for calculating toxicity-based pollutant loads: Part 1. Method development.

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.

Bioanalytical effect-balance model to determine the bioavailability of organic contaminants in sediments affected by black and natural carbon.

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.

An assessment of endocrine activity in Australian rivers using chemical and in vitro analyses.

Studies on endocrine disruption in Australia have mainly focused on wastewater effluents. Limited knowledge exists regarding the relative contribution of different potential sources of endocrine active compounds (EACs) to the aquatic environment (e.g., pesticide run-off, animal farming operations, urban stormwater, industrial inputs). In this study, 73 river sites across mainland Australia were sampled quarterly for 1 year. Concentrations of 14 known EACs including natural and synthetic hormones and industrial compounds were quantified by chemical analysis. EACs were detected in 88 % of samples (250 of 285) with limits of quantification (LOQ) ranging from 0.05 to 20 ng/l. Bisphenol A (BPA; LOQ = 20 ng/l) was the most frequently detected EAC (66 %) and its predicted no-effect concentration (PNEC) was exceeded 24 times. The most common hormone was estrone, detected in 28 % of samples (LOQ = 1 ng/l), and the PNEC was also exceeded 24 times. 17α-Ethinylestradiol (LOQ = 0.05 ng/l) was detected in 10 % of samples at concentrations ranging from 0.05 to 0.17 ng/l. It was detected in many samples with no wastewater influence, and the PNEC was exceeded 13 times. In parallel to the chemical analysis, endocrine activity was assessed using a battery of CALUX bioassays. Estrogenic activity was detected in 19 % (53 of 285) of samples (LOQ = 0.1 ng/l 17ß-estradiol equivalent; EEQ). Seven samples exhibited estrogenic activity (1-6.5 ng/l EEQ) greater than the PNEC for 17ß-estradiol. Anti-progestagenic activity was detected in 16 % of samples (LOQ = 8 ng/l mifepristone equivalents; MifEQ), but the causative compounds are unknown. With several compounds and endocrine activity exceeding PNEC values, there is potential risk to the Australian freshwater ecosystems.

Persistence of estrogenic activity in soils following land application of biosolids.

Estrogenic compounds may enter the environment when biosolids are applied to land. In the present study, soil samples were collected over 4 mo from a field trial following addition of biosolids. The recombinant yeast estrogen screen bioassay identified estrogenic activity in the soil at all sampling times to concentrations up to 2.3 µg 17ß-estradiol equivalency/kg. The present results indicate the potential for estrogenic compounds to persist in soil following biosolids application.

Selected personal care products and endocrine disruptors in biosolids: an Australia-wide survey.

Personal care products (PCPs) and endocrine disrupting compounds (EDCs) are groups of organic contaminants that have been detected in biosolids around the world. There is a shortage of data on these types on compounds in Australian biosolids, making it difficult to gain an understanding of their potential risks in the environment following land application. In this study, 14 biosolids samples were collected from 13 Australian wastewater treatment plants (WWTPs) to determine concentrations of eight compounds that are PCPs and/or EDCs: 4-t-octylphenol (4tOP), 4-nonylphenol (4NP), triclosan (TCS), bisphenol A (BPA), estrone (E1), 17ß-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2). Concentration data were evaluated to determine if there were any differences between samples that had undergone anaerobic or aerobic treatment. The concentration data were also compared to other Australian and international data. Only 4tOP, 4NP, TCS, and BPA were detected in all samples and E1 was detected in four of the 14 samples. Their concentrations ranged from 0.05 to 3.08 mg/kg, 0.35 to 513 mg/kg, <0.01 to 11.2 mg/kg, <0.01 to 1.47 mg/kg and <45 to 370 µg/kg, respectively. The samples that were obtained from WWTPs that used predominantly anaerobic treatment showed significantly higher concentrations of the compounds than those obtained from WWTPs that used aerobic treatment. Overall, 4NP, TCS and BPA concentrations in Australian biosolids were lower than global averages (by 42%, 12% and 62%, respectively) and 4tOP concentrations were higher (by 25%), however, of these differences only that for BPA was statistically significant. The European Union limit value for NP in biosolids is 50 mg/kg, which 4 of the 14 samples in this study exceeded.

Skeletal morphology and maturation of male Gambusia holbrooki exposed to sewage treatment plant effluent.

Sewage effluent has been identified as a major source of endocrine disrupting chemicals (EDCs) in the aquatic environment. The modified hemal spines (modified skeletal structures important in reproduction) of mosquitofish, Gambusia spp. have been shown to be under androgenic control and to be affected by exposure to estrogen. The current study aimed to investigate the effects of two sewage treatment plants (STPs) in Sydney, Australia on the morphology of hemal spines in populations of Gambusia holbrooki and on the ability of the fish to reach sexual maturity. The effluent from the two STPs had different effects on the hemal spines of males. At St. Marys differences in hemal spine morphology between fish upstream and downstream of the STP were not attributable to effluent from the STP. At Quakers Hill, results suggest that the effluent is generally estrogenic to G. holbrooki. There was a decrease in the proportion of males that were morphologically mature downstream of both STPs indicating potential population level effects that were associated with the presence of the STPs.

The effect of 17beta-estradiol on the development of modified hemal spines in early-life stage Gambusia holbrooki.

The morphologic development of the gonopodium of male mosquitofish, Gambusia holbrooki, is essential for proper reproductive function and has previously been used as a biomarker for the presence of endocrine-disrupting chemicals (EDCs) in freshwater systems. The development of the gonopodium is accompanied by the modification of the hemal spines on the 14th, 15th, and 16th vertebrae. These form an anchor for the movement of the gonopodium, and their normal development is therefore critical. This development is under hormonal control. It has been hypothesized that the modification of the hemal spines may be used as an end point for understanding the effects of exposure of early-life stage fish to EDCs and to add to the understanding of the differential sensitivities of different life stages. Larval fish were exposed to concentrations (0, 20, 100, and 500 ng/L) of 17beta-estradiol (E(2)) in two experiments using a flow-through system for 8 and 12 weeks. There was a general delay in the development of the three hemal spines when exposed to high concentrations of E(2). However, this delay was not observed for all end points on a particular spine nor across all spines. Fish examined at 8 weeks postpartum showed a more extensive delay at high concentrations than those examined at 12 weeks postpartum, suggesting that later in the life cycle, high levels of exogenous E(2) may be overcome by increasing levels of endogenous androgen. There was a decrease in the number of phenotypic male fish present in the 500-ng/L treatment at 12 weeks postpartum and an apparent decrease in the degree of sexual differentiation at high levels of E(2) exposure. The results suggest that effects of EDC exposure begin very early in a fish's life cycle.