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Decomposition of the peroxydisulfate ion (S2O82−, PS) to sulfate radicals (SO4 −) is a key step in sulfate radical-based advanced oxidation processes (SR-AOPs). In this study, quantum chemical investigations and calculation of activation energy were performed to reveal the decomposition process of S2O82− at the atomic level. Furthermore, the impacts of several main co-existing components (CCs), including inorganic cations, inorganic anions and organic molecules in wastewater, on the activation energy were evaluated. The results revealed that 3 steps were involved in the S2O82− decomposition: 1) the distance between two subgroups of the ground state of S2O82− (PSS0) increases from ∼0.15 to ∼0.215 nm driven by exogenous energy; 2) a transition occurs for S2O82− from PSS0 to the lowest triplet state (PST1); and 3) two subgroups of PST1 separate from each other spontaneously. The energy needed in the first step was demonstrated to be the activation energy. Moreover, two possible routes by which CCs affect the transition from PSS0 to PST1 were proposed. After ascertaining which route would be taken by different types of CCs, various methods of calculation were used to determine their impacts on S2O82− decomposition, i.e. promotion effect for H+, NH4+, Ca2+, Cl− and Br−, and inhibition effect for Na+, K+, Mg2+, NO3−, CO32−, SO42−, and all studied organic molecules, including acetic acid, benzene, bromoethane, 1-propanol and 4-chlorotoluene. The present study provided novel insights into the decomposition of S2O82− to SO4 −, and emphasized the effects of main co-existing inorganic ions and organic molecules in wastewater on SR-AOPs.

Early-life stage (ELS) avian toxicity tests have been proposed as a more ethical alternative to traditional standardized tests with adult birds. At the same time, 'omics approaches are gaining traction in the field of avian toxicology, but little has been done to characterize the metabolome and transcriptome at different life stages. The present study uses 'omics data from toxicity tests of 8 environmental chemicals in ELS and adult Japanese quail (Coturnix japonica) to address this data gap. Previous analyses of these data focused on responses to each of the individual chemicals. Here, we consider data from all studies to describe variation in the metabolome and transcriptome between life stages and across independent experiments, irrespective of chemical treatment. Of the 230 metabolites detected in liver, 163 were shared between the two life stages. However, many of the targeted bile acids that were present in the adult liver were absent from ELS samples. For the transcriptome,90% of the 18,364 detected transcripts were common to both life stages. Based on the 213 genes solely detected in ELS liver, the neuroactive ligand-receptor interaction pathway was significantly enriched. Multivariate and hierarchical clustering analyses revealed that variability among independent experiments was higher for the adult than the ELS studies at both the metabolomic and transcriptomic levels. Our results indicate concordance of the two approaches, with less variation between independent experiments in the ELS metabolome and transcriptome than in adults, lending support for the use of ELS as an alternative toxicity testing strategy.

Polychlorinated diphenyl sulfides (PCDPSs) represent an emerging group of constituents that are persistent, bioaccumulative and toxic (PBT) substances of great concern in terms of human health and ecological integrity. However, little is known about the occurrence, environmental behaviour and ecological risks of PCDPSs in lake environments. In this study, the concentrations of 21 PCDPSs were determined in surface water, suspended particulate matter (SPM), sediments, and 8 fish species from Chaohu Lake, China. Eighteen PCDPS congeners were prevalently detected in the samples, with concentrations ranging from 0.272-1.69 ng/L (water), 0.477-2.03 ng/g d.w. (SPM), 0.719-4.07 ng/g d.w. (sediment) and 0-0.131 ng/g w.w. (fish), respectively. Medium- and high-chlorinated PCDPSs in SPM and sediment were significantly higher than those in water samples. Increased PCDPS concentrations were found in higher trophic level fishes and those with a demersal habitat preference, indicating their bioaccumulation and biomagnification potential. The logBCFs, BSSAFs, and BSAFs of PCDPS congeners in fishes were determined to be 3.91-5.18, 0.0500-2.33, and 0.0360-4.94 L/kg, respectively. The organic carbon normalized partition coefficients (logK

Current ecotoxicity testing programs are impeded as they predominantly rely on slow and expensive animal tests measuring adverse outcomes. Therefore, new approach methodologies (NAMs) increasingly involve short-term mechanistic assays that employ molecular endpoints to predict adverse outcomes of regulatory relevance. This study aimed to elucidate the application of NAMs in adult fathead minnows using fluoxetine (FLX) as a model compound. Fish were exposed to three FLX concentrations (measured: 2.42, 10.7, and 56.7 μgL

Current approaches in chemical hazard assessment face significant challenges because they rely on live animal testing, which is time-consuming, expensive, and ethically questionable. These concerns serve as an impetus to develop new approach methodologies (NAMs) that do not rely on live animal tests. This study explored a molecular benchmark dose (BMD) approach using a 7-day embryo-larval fathead minnow (FHM) assay to derive transcriptomic points-of-departure (tPODs) to predict apical BMDs of fluoxetine (FLX), a highly prescribed and potent selective serotonin reuptake inhibitor frequently detected in surface waters. Fertilized FHM embryos were exposed to graded concentrations of FLX (confirmed at LOD, 0.19, 0.74, 3.38, 10.2, 47.5 μg/L) for 32 days. Subsets of fish were subjected to omics and locomotor analyses at 7 days post-fertilization (dpf) and to histological and biometric measurements at 32 dpf. Enrichment analyses of transcriptomics and proteomics data revealed significant perturbations in gene sets associated with serotonergic and axonal functions. BMD analysis resulted in tPOD values of 0.56 μg/L (median of the 20 most sensitive gene-level BMDs), 5.0 μg/L (tenth percentile of all gene-level BMDs), 7.51 μg/L (mode of the first peak of all gene-level BMDs), and 5.66 μg/L (pathway-level BMD). These tPODs were protective of locomotor and reduced body weight effects (LOEC of 10.2 μg/L) observed in this study and were reflective of chronic apical BMDs of FLX reported in the literature. Furthermore, the distribution of gene-level BMDs followed a bimodal pattern, revealing disruption of sensitive neurotoxic pathways at low concentrations and metabolic pathway perturbations at higher concentrations. This is one of the first studies to derive protective tPODs for FLX using a short-term embryo assay at a life stage not considered to be a live animal under current legislations.

The frequent detection of polychlorinated diphenyl ethers (PCDEs) in aquatic systems has aroused widespread concerns, however, their potential hazard to aquatic ecosystems has been poorly understood. Here the acute toxicity of 12 PCDE congeners was evaluated in three model aquatic organisms representing different trophic levels following OECD test guidelines, including green algae (Scenedesmus obliquus), water flea (Daphnia magna), and zebrafish (Danio rerio). Dose-dependent increases in growth inhibition and mortality were observed for all tested PCDE congeners. Most of the PCDE congeners, in particular 3,3′,4,4′-tetra-CDE, were highly toxic to the three aquatic organisms with EC50 or LC50 values below 1 mg L-1. Their toxicities were generally comparable with those of certain polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Moreover, D. magna was the most sensitive species among the three aquatic organisms. In addition, the EC50 or LC50 values had an extremely significant correlation with the n-octanol-water partition coefficient (logKow) of the PCDE congeners. The established quantitative structure-property relationship (QSPR) models indicated that the molecular polarizability (α) could significantly influence the acute toxicity of PCDEs on Daphnia magna and Danio rerio, and the energy of the lowest unoccupied molecular orbital (ELUMO) is the key factor of the acute toxicity of PCDEs in Scenedesmus obliquus. In addition, even at environmental levels, 3,3′,4,4′-tetra-CDE could induced seveve oxidative damages in the three aquactic species. These findings would contribute to the understanding of adverse effects of PCDEs in aquatic organisms.

Despite the global toxicology community discussing New Approach Methodologies (NAMs) for chemical hazard and risk assessment, such as in vitro, in silico, and ‘omics-based approaches, for some 30 years, their formal adoption by regulators remains limited. Previous research suggests that insufficient validation, complexity of interpretation, and lack of standardization are salient obstacles to adoption. In this paper we aim to better understand the policy challenges associated with adopting NAMs in chemical risk assessment; and to identify actions that could facilitate and accelerate their formal adoption internationally. We conducted a Delphi study – a group communication process that solicits expert judgments through iterative questioning and feedback – with panelists from government, industry, and non-governmental organizations in Europe and North America. Expert panelists identified two key activities to facilitate and accelerate the validation of NAMs internationally: 1) the development of common data collection, reporting and sharing procedures; and 2) the improvement of knowledge about new test methods among members of the regulatory community. Both activities suggest the need for a common regulatory science infrastructure, including international regulatory dialogues, large-scale research collaborations, and coordinated innovation in technological tools, the discourse of scientific validation, and regulatory procedures. To build trust across many sites (laboratories, regulatory agencies, contract research organizations, chemical producers, and the public), stakeholders will need to agree on validation requirements for particular uses (content in relation to context) as well as how results are to be communicated (data format), and measured (metrics). There is also a need for a global orchestrator, who can exert leadership and inspire voluntary cooperation of diverse organizations to address shared validation goals, to play a key role.

Concerns about the estrogenic properties of Bisphenol A (BPA) have led to increased efforts to find BPA replacements. 1,7-bis(4-Hydroxyphenylthio)-3,5-dioxaheptane (DD-70) and 4,4′-(hexafluoroisopropylidene) diphenol (bisphenol AF, BPAF) are two potential chemical substitutes for BPA; however, toxicity data for these chemicals in avian species are limited. To determine effects on avian embryonic viability, development, and hepatic mRNA expression at two distinct developmental periods (mid-incubation [day 11] and term [day 20]), two egg injection studies were performed. Test chemicals were injected into the air cell of unincubated, fertilized chicken eggs at concentrations ranging from 0–88.2 µg/g for DD-70 and 0–114 µg/g egg for BPAF. Embryonic concentrations of DD-70 and BPAF decreased at mid-incubation and term compared to injected concentrations suggesting embryonic metabolism. Exposure to DD-70 (40.9 and 88.2 µg/g) and BPAF (114 µg/g) significantly decreased embryonic viability at mid-incubation. Exposure to DD-70 (88.2 µg/g) decreased embryo mass and increased gallbladder mass, while 114 µg/g BPAF resulted in increased gallbladder mass in term embryos. Expression of hepatic genes related to xenobiotic metabolism, lipid homeostasis, and response to estrogen were altered at both developmental stages. Given the importance of identifying suitable BPA replacements, the present study provides novel, whole animal avian toxicological data for two replacement compounds, DD-70 and BPAF. Data availability Data, associated metadata, and calculation tools are available from the corresponding author (doug.crump@canada.ca).

There is a growing understanding of how oil pollution can affect aquatic ecosystems, including physical and chemical effects. One of the biggest challenges with detecting the effects of oil-related contaminants on biota from resource development is understanding the background levels and potential effects of the exposure of biota to contaminants from various natural and anthropogenic sources prior to large scale oil and gas operations. Seabirds are effective indicators of pollution, and can be useful for tracking oil-related contaminants in the marine environment. We sampled four seabird species (black guillemot, Cepphus grylle; thick-billed murre, Uria lomvia; black-legged kittiwake, Rissa tridactyla; and northern fulmar, Fulmarus glacialis) in the Baffin Bay-Davis Strait region of the Northwest Atlantic and Arctic oceans, an area where natural oil and gas seeps are present but lacking any large-scale oil and gas projects. We found detectable levels of PACs and several trace elements in all species examined. Alkylated PAC levels were higher than parent compounds in all four seabird species examined, with fulmars and murres having the highest levels detected; mean hepatic concentrations of ∑16PAC were 99.05, 46.42, 12.78 and 9.57 ng/g lw, respectively, for guillemots, murres, fulmars and kittiwakes. Overall, PAC concentrations in the seabird species examined were similar to PAC concentrations measured in other bird species in regions with more industrialization. These findings provide data which can be used to assess the current oil-related contaminant exposure of biota in the region. As well, they provide background levels for the region at a time when shipping activity is relatively low, which can used for future comparisons following expected increases in shipping and oil and gas activities in the region.

Organophosphate esters (OPEs) have gained considerable interest from many environmental chemists and toxicologists due to their frequent detection in the environment and potential adverse effects on health. Nuclear hormone receptors (NHRs) were found to mediate many of their adverse effects. However, our knowledge regarding the direct binding and interaction between OPEs and NHRs is limited. In this study, Endocrine Disruptome, an online computational tool based on the technique of inverse docking, was used to calculate the binding affinity score of 25 individual OPEs with 12 different human NHRs. Results showed that 20% of potential binding interactions between the OPEs and NHRs had medium-to-high probabilities. The accuracy, sensitivity and specificity of the predictions were 78.8, 60.0 and 80.9%, respectively. OPEs with a benzene ring were more active than those without, among which, tri-o-tolyl phosphate and tri-m-tolyl phosphate displayed the highest activities, suggesting that they might pose the greatest potential risks for interference with endocrine functions. In addition, the antagonistic conformations of androgen receptor and estrogen receptor β were found to be the two most vulnerable NHR conformations. Our findings can further the understanding about the health risk(s) of OPEs.

The organophosphate flame retardants tris(2-butoxyethyl) phosphate (TBOEP) and triethyl phosphate (TEP) are used in a wide range of applications to suppress or delay the ignition and spread of fire. Both compounds have been detected in the environment and TBOEP was recently measured in free-living avian species. In this study, TBOEP and TEP were injected into the air cell of chicken embryos at concentrations ranging from 0 to 45,400 ng/g and 0 to 241,500 ng/g egg, respectively. Pipping success, development, hepatic mRNA expression of 9 target genes, thyroid hormone levels, and circulating bile acid concentrations were determined. Exposure to the highest doses of TBOEP and TEP resulted in negligible detection of the parent compounds in embryonic contents at pipping indicating their complete metabolic degradation. TBOEP exposure had limited effects on chicken embryos, with the exception of hepatic CYP3A37 mRNA induction. TEP exposure decreased pipping success to 68%, altered growth, increased liver somatic index (LSI) and plasma bile acids, and modulated genes associated with xenobiotic and lipid metabolism and the thyroid hormone pathway. Plasma thyroxine levels were decreased at all TEP doses, including an environmentally-relevant concentration (8 ng/g), and gallbladder hypotrophy was evident at ≥ 43,200 ng/g. Tarsus length and circulating thyroxine concentration emerged as potential phenotypic anchors for the modulation of transthyretin mRNA. The increase in plasma bile acids and LSI, gallbladder hypotrophy, and discoloration of liver tissue represented potential phenotypic outcomes associated with modulation of hepatic genes involved with xenobiotic and lipid metabolism.

1,2-Dibromo-4-(1,2-dibromoethyl)-cyclohexane (DBE-DBCH; formerly abbreviated as TBECH) and tris(methylphenyl) phosphate (TMPP; formerly abbreviated as TCP) are additive flame retardants that are detected in the environment and biota. A recent avian in vitro screening study of 16 flame retardants identified DBE-DBCH and TMPP as important chemicals for follow-up in ovo evaluation based on their effects on cytotoxicity and mRNA expression in avian hepatocytes. In this study, technical mixtures of DBE-DBCH and TMPP were injected into the air cell of chicken embryos at concentrations ranging from 0 to 54,900 ng/g and from 0 to 261,400 ng/g, respectively, to determine effects on pipping success, development, hepatic mRNA expression, thyroid hormone levels, and circulating bile acid concentrations. Both compounds were detectable in embryos at pipping and the β-DBE-DBCH isomer was depleted more rapidly than the α-isomer in tissue samples. DBE-DBCH had limited effects on the endpoints measured, with the exception of the up-regulation of two phase I metabolizing enzymes, CYP3A37 and CYP2H1. TMPP exposure caused embryonic deformities, altered growth, increased liver somatic index (LSI) and plasma bile acid concentrations, and altered mRNA expression levels of genes associated with xenobiotic and lipid metabolism and the thyroid hormone pathway. Overall, TMPP elicited more adverse molecular and phenotypic effects than DBE-DBCH albeit at concentrations several orders of magnitude greater than those detected in the environment. The increase in plasma bile acid concentrations was a useful phenotypic anchor as it was associated with a concomitant increase in LSI, discoloration of the liver tissue, and modulation of hepatic genes involved with xenobiotic and lipid metabolism.

Results of recent studies showed that 2,3,4,7,8-pentachlorodibenzofuran (PeCDF) and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) are equipotent in domestic chicken (Gallus gallus domesticus) while PeCDF is more potent than TCDD in ring-necked pheasant (Phasianus colchicus) and Japanese quail (Coturnix japonica). To elucidate the mechanism(s) underlying these differences in relative potency of PeCDF among avian species, we tested the hypothesis that this is due to species-specific differential binding affinity of PeCDF to the aryl hydrocarbon receptor 1 (AHR1). Here, we modified a cell-based binding assay that allowed us to measure the binding affinity of dioxin-like compounds (DLCs) to avian AHR1 expressed in COS-7 (fibroblast-like cells). The results of the binding assay show that PeCDF and TCDD bind with equal affinity to chicken AHR1, but PeCDF binds with greater affinity than TCDD to pheasant (3-fold) and Japanese quail (5-fold) AHR1. The current report introduces a COS-7 whole-cell binding assay and provides a mechanistic explanation for differential relative potencies of PeCDF among species of birds.

Dreissenid mussels have become important components of the Great Lakes biological community since their introduction in the 1980s, but much remains to be understood regarding their effect on energy and nutrient flows in pelagic systems. Here, we report a new method that tracks incorporation of resources of molluskan origin into food webs used by aquatic birds. Biochemical tracers (fatty acids and stable carbon isotopes) are used to characterize species associated with pelagic and benthic food webs in Lake Ontario. Our focus is on the polymethylene-interrupted fatty acids (PMI-FAs) because previous research identified mollusks as their primary source. We found that PMI-FA mass fractions were greater in organisms associated with benthic (e.g. round goby) versus pelagic (e.g. alewife) food webs. Double-crested cormorants that had recently consumed benthic prey fish, i.e. goby, had greater proportions of PMI-FAs in their blood plasma than birds which showed no signs of recent goby ingestion. We did not detect an increase in mass fractions of PMI-FAs in cryogenically archived cormorant eggs following expansion of dreissenid mussels in Lake Ontario. However, following the introduction and expansion of round goby in the lake, PMI-FAs were detected at greater levels in cormorant eggs. These results illustrate how only after dreissenid mussel-facilitated establishment of round goby was the full extent of exotic species disruption of food webs manifested in fish-eating birds. These food web changes may be contributing to negative impacts on aquatic birds exemplified by the emergence of Botulism Type E as a significant mortality factor in this ecosystem.

Primary cultures of ring-necked pheasant (Phasianus colchicus) and Japanese quail (Coturnix japonica) embryo hepatocytes were used to compare the potencies of highly purified hexachlorobenzne (HCB-P), reagent-grade HCB (RG-HCB) and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as inducers of ethoxyresorufin O-deethylase (EROD) activity, cytochrome P4501A (CYP1A4) messenger ribonucleic acid (mRNA) and CYP1A5 mRNA. HCB-P, RG-HCB and TCDD all induced EROD activity and up-regulated CYP1A4 and CYP1A5 mRNA. Induction was not caused by contamination of HCB with polychlorinated dibenzo-p-dioxins, dibenzofurans or biphenyls. Based upon a comparison of the EC50 and ECthreshold values for EROD and CYP1A4/5 concentration–response curves, the potency of HCB relative to TCDD was 0.001 in ring-necked pheasant and 0.01 in Japanese quail embryo hepatocytes. Differences in species sensitivity to HCB were found to be mainly dictated by differences in species sensitivity to TCDD rather than differences in the absolute potency of HCB. Consequently, ring-necked pheasant and Japanese quail embryo hepatocytes were found to be equally sensitive to HCB exposure. Species sensitivity comparisons were also made with chicken (Gallus gallus domesticus) and revealed that chicken embryo hepatocytes were less responsive to EROD induction (lower maximal response) by HCB compared to the embryo hepatocytes of pheasant and quail.

Some uncertainty exists regarding the purity of hexachlorobenzene (HCB) used in past toxicity studies. It has been suggested that reported toxic and biochemical effects initially attributed to HCB exposure may have actually been elicited by contamination of HCB by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Herein, primary cultures of chicken embryo hepatocytes (CEH) were used to compare the potencies of two lots of reagent-grade hexachlorobenzene (HCB-old [HCB-O] and HCB-new [HCB-N]), highly purified HCB (HCB-P) and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as inducers of ethoxyresorufin O-deethylase (EROD) activity, cytochrome P4501A4 (CYP1A4) messenger ribonucleic acid (mRNA) and CYP1A5 mRNA. The study also compared the EROD- and CYP1A4/5 mRNA-inducing potencies of HCB to the potencies of two mono-ortho substituted polychlorinated biphenyls (PCBs), 2,3,3',4,4'-pentachlorobiphenyl (PCB 105) and 2,3'4,4',5-pentachlorobiphenyl (PCB 118). HCB-O, HCB-N and HCB-P all induced EROD activity and up-regulated CYP1A4 and CYP1A5 mRNAs. Induction was not caused by contamination of HCB with PCDDs or PCDFs. Based upon a comparison of the EC(50) and EC(threshold) values for EROD and CYP1A4/5 mRNA concentration-response curves, the potency of HCB relative to the potency of TCDD was 0.0001, and was similar to that of PCB 105 and PCB 118. The maximal EROD activity and CYP1A4/5 mRNA expression differed greatly between HCB and TCDD, and may contribute to an overestimation of the ReP value calculated for highly purified HCB.

Herring gulls (Larus argentatus) bioaccumulate mercury (Hg) but it is unknown whether they are exposed at levels of neurological concern. Here we studied brain tissues from gulls at five Great Lakes colonies and one non-Great Lakes colony during spring of 2001 and 2003. Total brain Hg concentrations ranged from 0.14 to 2.0 μg/g (dry weight) with a mean of 0.54 μg/g. Gulls from Scotch Bonnet Island, on the easternmost edge of the Great Lakes, had significantly higher brain Hg than other colonies. No association was found between brain Hg concentration and [3H]-ligand binding to neurochemical receptors (N-methyl- d -aspartate, muscarinic cholinergic, nicotinic cholinergic) or nicotinic receptor α-7 relative mRNA expression as previously documented in other wildlife. In conclusion, spatial trends in Hg contamination exist in herring gulls across the Great Lakes basin, and herring gulls accumulate brain Hg but not at levels associated with sub-clinical neurochemical alterations.

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in a wide range of consumer products. Previous studies have suggested that PBDEs can disrupt thyroid hormone homeostasis and the developing central nervous system in rodents, but few studies have determined whether PBDEs cause similar effects in birds. An in vitro method was used to determine effects of a commercial PBDE flame retardant (DE-71) on mRNA expression in primary chicken neuronal cells derived from the cerebral hemisphere. Real-time RT-PCR assays were developed to quantify changes in mRNA abundance of genes associated with the thyroid hormone pathway; thyroid hormone receptors (TRalpha and TRbeta) and transthyretin (TTR). We also used a new differential display PCR methodology, fluorescent RNA arbitrarily primed PCR (FRAP-PCR), to determine additional effects of DE-71 on mRNA expression. Neither of the TRs responded to DE-71 exposure, but TTR mRNA decreased approximately 2-fold following exposure to 0.1, 1 and 3 microM DE-71. Candidate transcripts associated with signal transduction, neurosteroidogenesis, and neurite and axonal growth were up-regulated by DE-71 exposure. Taken together, the findings from this study indicate that this in vitro cell culture method can be used to characterize the effects of PBDEs in the avian brain.