The contact assay measuring the inhibition of Arthrobacter globiformis dehydrogenase activity as an endpoint to evaluate the toxicity of solid samples was tested in an international ring-test to validate its performance for ISO standardization (ISO/CD 18187). This work reports the results of the ring-test involving 9 laboratories from six countries. At least 8 valid data sets were obtained for each sample and more than three quarters of the participants attained the validity criteria defined in the standard. The coefficient of variation within (CVr) and between (CVR) laboratories was generally on average <15% and <30% for negative and positive controls, respectively. Regarding solid samples, the laboratories provided a similar ranking of the samples based on their toxicity, despite some variation in the LOEC values. The logarithmic within-lab standard deviation <0.50 for soils and <0.25 for wastes evidenced a good repeatability. The between-lab variability assessed by a CVR <30%, minimum-maximum factor <4 and a reproducibility standard deviation (SDR) <0.13 for a great part of the solid samples, confirmed the test reproducibility. Overall, this assay proved to be robust, sensitive and feasible for routine use towards the quality assessment of soils and wastes.

Biomarkers are frequently used to determine the exposure of fish to petroleum hydrocarbons following an oil spill. These biomarkers must be chosen carefully if they are to be used to determine sublethal toxic impacts as well as oil exposure. Many commonly used biomarkers relate to the metabolism of high molecular weight, typically pyrogenic, polycyclic aromatic hydrocarbons (PAHs), which are not abundant in unweathered crude oil. The goal of this study was to compare the efficacy of different biomarkers, including histological examination and transcriptomic profiling, in showing exposure to oil and the potential for sublethal toxic impacts. To achieve these goals, subadults/adults of the spotted dragonet (Repomucenus calcaratus) were exposed to a representative light, unweathered Australian oil for 96 h, so that the physiological changes that occur with exposure could be documented. Fish were then transferred to clean sediment for 90 h to quantify recovery. Biomarker changes, including PAH metabolites, 7-ethoxyresorufin O-deethylase (EROD), and histopathology, are presented in this work. In addition, a de novo transcriptome for the spotted dragonet was assembled, and differential transcript abundance was determined for the gill and liver of petroleum-exposed fish relative to a control. Increased levels of some biliary phenanthrene metabolites were seen throughout the exposure period. EROD levels showed modest, but not significant, increases. Transcriptomic differences were noted in the abundances of transcripts with a role in inflammation, primary metabolism and cardiac function. The patterns of transcript abundance in the gill and the liver changed in a manner that reflected exposure and recovery. The histology showed elevated prevalence of lesions, most notably vacuolization in liver and heart tissue, multi-organ necrosis, and lamellar epithelial lifting and telangiectasia in the gill. These findings suggest that short-term exposures to low molecular weight PAHs could elicit changes in the health of fish that are well predicted by the transcriptome. Furthermore, when light oil is released into the environment, exposure and subsequent risk would be better estimated using phenanthrene metabolite levels rather than EROD. This study also adds to the weight of evidence that exposure to low molecular weight PAHs may cause cardiac problems in fish. Further study is needed to determine the impact of these changes on reproductive capacity, long-term survival, and other population specific parameters.

Acute and chronic bioassays provide essential basis for establishment of environmental quality standards. The effects of Cu on a pulmonate snail, Physa acuta, were investigated at a number of sublethal and lethal endpoints. Cu exposure suppressed movement and triggered an escape response in P. acuta at low and high concentrations, respectively, exerting acute toxic effects on adult snails exposed to a 96 h LC50 of 23.8 mu g L-1. Following 16 d exposure of Cu to the egg masses, successful hatching decreased with increasing Cu concentration. High Cu concentrations (12.5 and 25 mu g L-1) resulted in inhibition of eye and shell development at the veliger stage, and a deformed shell, abnormal eyes, and different morphological shapes with lesions and hemorrhages were observed after 9 days of exposure. A large number of eggs exposed to 2.5-25 mu g L-1 Cu remained in the veliger and hippo stages for 2-7 days, with no further development. Results from reproduction tests showed that adult snails exposed to various Cu treatments produced more than three broods, with the total number of eggs ranging from 770 to 1,289, revealing little difference between the control and Cu-treated groups (p > 0.05). However, snails exposed to 12.5 and 25 mu g L-1 Cu produced polynuclear eggs in one egg capsule. The hatching success rate and shell length of the filial generation were significantly reduced in a dose-dependent manner (p < 0.05). The shell length of newly hatched snails was shorter in the reproduction test than in the hatching test, indicating inherent Cu toxicity in the filial generation from the exposed parent strain. The present study provides essential data regarding Cu toxicity in pulmonate snail P. acuta. (C) 2017 Elsevier Ltd. All rights reserved.

The use of pyrethroid and neonicotinoid insecticides has increased in Australia over the last decade, and as a consequence, increased concentrations of the neonicotinoid insecticide imidacloprid have been measured in Australian rivers. Previous studies have shown that non-target crustaceans, including commercially important species, can be extremely sensitive to these pesticides. Most shrimp farms in Australia are predominantly located adjacent to estuaries so they can obtain their required saline water, which support multiple land uses upstream (e.g. sugar-cane farming, banana farming, beef cattle and urbanisation). Larval and post-larval shrimp may be most susceptible to the impacts of these pesticides because of their high surface area to volume ratio and rapid growth requirements. However, given the uncertainties in the levels of insecticides in farm intake water and regarding the impacts of insecticide exposure on shrimp larvae, the risks that the increased use of new classes of pesticide pose towards survival of post-larval phase shrimp cannot be adequately predicted. To assess the potential for risk, toxicity in 20day past hatch post-larval Black Tiger shrimp (Penaeus monodon) to modern use insecticides, imidacloprid, bifenthin, and fipronil was measured as decreased survival and feeding inhibition. Post-larval phase shrimp were sensitive to fipronil, bifenthrin, and imidacloprid, in that order, at concentrations that were comparable to those that cause mortality other crustaceans. Bifenthrin and imidacloprid exposure reduced the ability of post-larval shrimp to capture live prey at environmentally realistic concentrations. Concentrations of a broad suite of pesticides were also measured in shrimp farm intake waters. Some pesticides were detected in every sample. Most of the pesticides detected were measured below concentrations that are toxic to post-larval shrimp as used in this study, although pesticides exceed guideline values, suggesting the possibility of indirect or mixture-related impacts. However, at two study sites, the concentrations of insecticides were sufficient to cause toxicity in shrimp post larvae, based on the risk assessment undertaken in this study.

Ferrate(VI) (Fe(VI)) has been known to react with emerging organic contaminants containing electron-rich organic moieties, such as phenols, anilines, olefins, reduced sulfur and deprotonated amines. Oxidation of fluoroquinolone antibiotics, ciprofloxacin (CIP) and enrofloxacin (ENR), by Fe(VI) were investigated for their reaction products and toxicity changes as well as biodegradability of these products. Ten products were identified for both CIP and ENR reactions with Fe(VI) using a high-resolution accurate-mass Orbitrap mass analyzer. Structural changes to the CIP and ENR molecule included dealkylation, formation of alcohols and amides in piperazine ring and oxygen transfer to the double bond in quinolone structure. An enamine formation mechanism was tentatively proposed to facilitate the interpretation of CIP and ENR oxidation pathways. Toxicity evaluation using Microbial Assay for toxicity Risk Assessment (MARA) bioassay indicated that Fe(VI) oxidation products of CIP and ENR contributed negligible antibacterial potency and Fe(VI) oxidation treatment can remove the residual toxicity of CIP and ENR impacted source waters. The Fe(VI) oxidation treatment resulted in formation of relatively more biodegradable products (based on in silico assessment) than their corresponding parent compounds. The results showed that Fe(VI) has a good potential to degrade fluoroquinolone antibiotics and their antimicrobial potency in natural waters.

Removal of a persistent antiepileptic drug carbamazepine (CBZ) in aqueous solutions was investigated by using solar photolysis combined with free available chlorine (FAC). The combination of chlorination with simulated or natural sunlight markedly enhanced removal of CBZ in 10 mM phosphate buffer solution (pH 7.0) and river water (pH 7.0) compared with sunlight or FAC alone. Further analysis indicated that the observed enhancements in CBZ removal can be attributed to the in situ hydroxyl radical (HO) and ozone (O3) production during FAC photolysis. During 70 min simulated sunlight photolysis combined with FAC treatment, HO reaction contributed to 35.8% removal of CBZ and O3 reaction contributed to 40.6% removal, while only 5.3% of CBZ was removed by HOCl reaction. The oxidation products of CBZ, epoxide CBZ, 10,11-dihydro-10,11-dihydroxy CBZ, 1-(2-benzaldehyde)-4-hydro-(1H,3H)-quinazoline-2-one (BQM), 1-(2-benzaldehyde)-(1H,3H)-quinazoline-2,4-dione (BQD) and 4-aldehyde-9-acridone, were mainly formed from the HO and O3 attack at the double bond on the central heterocyclic ring of CBZ. Formation of these oxidation products did not cause any increase or decrease in toxicity to microbial species tested through Microbial Assay for Toxicity Risk Assessment (MARA). The initial FAC concentration and pH had a major influence on the removal process of CBZ during FAC photolysis, while temperature had a minor effect only. The combination of chlorination with natural sunlight could provide an effective approach for removal of CBZ and other contaminants during water treatment.

The contamination of major continental river systems by endocrine-active chemicals (EACs) derived from the discharge of wastewater treatment plant (WWTP) effluents can affect human and ecosystem health. As part of a long-term effort to develop a native fish model organism for assessment of endocrine disruption in Australia's largest watershed, the Murray-Darling River Basin, the present study evaluated endocrine disruption in adult males of the native Australian Murray rainbowfish (Melanotaenia fluviatilis) exposed to effluent from an activated sludge WWTP and water from the Murray River during a 28-d, continuous-flow, on-site experiment. Analysis of the WWTP effluent and river water detected estrone and 17-estradiol at concentrations up to approximately 25ngL(-1). Anti-estrogenicity of effluent samples was detected in vitro using yeast-based bioassays (yeast estrogen screen) throughout the experiment, but estrogenicity was limited to the first week of the experiment. Histological evaluation of the testes indicated significant suppression of spermatogenesis by WWTP effluent after 28d of exposure. Plasma vitellogenin concentrations and expression of vitellogenin messenger RNA in liver were not significantly affected by exposure to WWTP effluent. The combination of low contaminant concentrations in the WWTP effluent, limited endocrine disrupting effects in the Murray rainbowfish, and high in-stream dilution factors (>99%) suggest minimal endocrine disruption impacts on native Australian fish in the Murray River downstream from the WWTP outfall. Environ Toxicol Chem 2015;34:1078-1087. (c) 2015 SETAC

The removal and fate of several indicator endocrine disrupting chemicals (EDCs) at two large municipal wastewater treatment plants (WWTPs) in Adelaide South Australia was investigated. Non-estrogens included the non-ionic surfactant breakdown compounds nonyl phenol mono- and di-ethoxylates, 4-t-octylphenol and 4-nonyl phenol; and, the plasticizer bisphenol A. Estrogens included 17β-estradiol; estrone; and, 17α-ethynylestradiol. Effluent from Bolivar WWTP is polished using stabilisation lagoons followed by coagulation, dissolved air flotation/filtration and chlorination for non-potable reuse. Biosolids from both plants is applied to agricultural land as a soil conditioner. Non-estrogen indicator EDCs were detected at the highest concentration in sewage, effluent and sludge but estrogen indicator EDCs contributed the greatest potential for estrogenicity. The fate of indicator EDCs at various treatment stages is complex and includes biochemical modification/transformation and/or partitioning to either solid or liquid phases. Activated sludge treatment was an important removal barrier achieving moderate-high removal of predicted and YES (a yeast screen assay) measured estrogen equivalent values (EEq). Combined polishing treatment achieved high removal of candidate EDCs (97%). Mass balance indicates that the largest source of estrogenicity discharged from both WWTPs investigated is digested sludge which accounts for 18 and 22% respectively of the combined predicted and YES measured EEq measured in sewage at the two WWTPs.