While (N-ethyl perfluorooctanesulfonamido ethanol)-based phosphates (SAmPAPs) have been proposed as a group of perfluorooctanesulfonate (PFOS) precursors, investigation of their occurrence and fate has been limited to SAmPAP diester. In this study, SAmPAP diester and triester were simultaneously determined in freshwater sediment from Taihu Lake using a newly developed UPLC-MS/MS method, and their biotransformation to PFOS in lake sediment was investigated. SAmPAP diester and triester were detected in sediments with a detection frequency of 56% and 88%, and their mean concentrations were 0.24 ± 0.11 ng/g dry weight (dw) and 0.12 ± 0.03 ng/g dw, respectively. The SAmPAP diester/triester ratio in sediment was 1.1 ± 4.2, much lower than that (6.7) observed in the technical product, and the positive correlation was found between the concentrations of SAmPAP diester and PFOS in sediments (r² = 0.45, p = 0.01), suggesting that SAmPAP diester would be biotransformed to PFOS in the lake sediment. The microbial degradation test in the lake sediments further clarified that SAmPAP diester was biodegraded to PFOS, but SAmPAP triester was highly recalcitrant to microbial degradation. This study suggests that the occurrence of SAmPAP diester in freshwater lake sediments may be an important precursor of PFOS.

Integrated compensatory responses of physiological systems towards homeostasis are generally overlooked when it comes to analysing alterations in biochemical parameters indicative of such processes. Here an hypothesis-driven multivariate analysis accounting for interactive multibiomarker responses was used to investigate effects of long-term exposure of Carcinus maenas to Hazardous and Noxious Substances (HNS). Adult male crabs were exposed to low and high post-spill levels of acrylonitrile (ACN) or aniline (ANL) for 21d. Bioaccumulation, feeding behaviour, and biomarkers related to mode-of-action (MoA) (detoxification, neurotransmission and energy production) were evaluated over time. Distinct temporal patterns of response to low and high exposure concentrations were depicted, with a main set of interactive multibiomarker predictors identified for each HNS (five for ACN and three for ANL), useful to follow coupled evolvement of biomarker responses. ACN caused peripheral neurotoxic effects coupled with enhanced biotransformation and significant oxidative damage particularly relevant in gills. ANL elicited alterations in central neurotransmission affecting ventilation coupled with very low levels of oxidative damage in gills. Results indicate chronic toxicity data are determinant to improve HNS hazard assessment if the aim is to obtain reliable risk calculations, and develop effective predictive models avoiding overestimation but sufficiently protective. Accounting for multibiomarker interactions brought otherwise overlooked information about C. maenas responses and MoA of ACN and ANL.

Biodegradation of 1,4-dioxane was examined in packed quartz and soil column flow-through systems. The inhibitory effects of co-contaminants, specifically trichloroethene (TCE), 1,1-dichloroethene (1,1-DCE), and copper (Cu²⁺) ions, were investigated in the columns either with or without bioaugmentation with a 1,4-dioxane degrading bacterium Pseudonocardia dioxanivorans CB1190. Results indicate that CB1190 cells readily grew and colonized in the columns, leading to significant degradation of 1,4-dioxane under oxic conditions. Degradation of 1,4-dioxane was also observed in the native soil (without bioaugmentation), which had been previously subjected to enhanced reductive dechlorination treatment for co-contaminants TCE and 1,1-DCE. Bioaugmentation of the soil with CB1190 resulted in nearly complete degradation at influent concentrations of 3–10 mg L⁻¹ 1,4-dioxane and a residence reaction time of 40–80 h, but the presence of co-contaminants, 1,1-DCE and Cu²⁺ ions (up to 10 mg L⁻¹), partially inhibited 1,4-dioxane degradation in the untreated and bioaugmented soil columns. However, the inhibitory effects were much less severe in the column flow-through systems than those previously observed in planktonic cultures, which showed near complete inhibition at the same co-contaminant concentrations. These observations demonstrate a low susceptibility of soil microbes to the toxicity of 1,1-DCE and Cu²⁺ in packed soil flow-through systems, and thus have important implications for predicting biodegradation potential and developing sustainable, cost-effective technologies for in situ remediation of 1,4-dioxane contaminated soils and groundwater.

N-ethyl perfluorooctane sulfonamide (N-EtFOSA) is commonly known as the active ingredient of sulfluramid. It can be degraded to perfluorooctane sulfonic acid (PFOS) in biota and environment. Earthworms (Eisenia fetida) were exposed with N-EtFOSA to examine the bioaccumulation, elimination and metabolism of N-EtFOSA by the earthworms after in vivo and in vitro exposure. N-EtFOSA could be biodegraded in quartz sands to perfluorooctane sulfonamide (FOSA) and PFOS. In the in vivo tests, in addition to parent N-EtFOSA, three metabolites, including perfluorooctane sulfonamide acetate (FOSAA), FOSA and PFOS also accumulated in earthworms as a result of N-EtFOSA biotransformation, with FOSA as the predominant metabolite. The bioaccumulation factor (BAF) and uptake rate coefficient (ku) of N-EtFOSA from sand were 20.4 and 2.41·d−1, respectively. The elimination rate constants (ke) decreased in the order FOSAA (0.130·d−1) > N-EtFOSA (0.118·d−1) > FOSA (0.073·d−1) > PFOS (0.051·d−1). The biotransformation of N-EtFOSA in earthworm was further confirmed by the in vitro test involving incubation of earthworm homogenates with N-EtFOSA. This work provides evidence on the accumulation and transformation of N-EtFOSA in terrestrial invertebrates and will be helpful to explore the indirect sources of FOSA and PFOS in environmental biota.

Propranolol (PRO), a human β-AR (β-adrenergic receptor) antagonist, is considered to result in specific effects in a non-target species, D. magna, based on our previous studies. The present study investigated the effects of β-AR agents, including an antagonist and agonist using pharmacologically relevant endpoints as well as a more holistic gene expression approach to reveal the impacts and potential mode of actions (MOAs) in the model non-target species. Results show that the responses in cardiac endpoints and gene expression in D. magna are partially similar but distinguishable from the observations in different organisms. No effect was observed on heart size growth in PRO and isoprenaline (ISO) exposure. The contraction capacity of the heart was decreased in ISO exposure, and the heart rate was decreased in PRO exposure. Time-series exposures showed different magnitudes of effect on heart rate and gene expression dependent on the type of chemical exposure. Significant enrichment of gene families involved in protein metabolism and biotransformation was observed within the differentially expressed genes, and we also observed differential expression in juvenile hormone-inducible proteins in ISO and PRO exposure, which is suspected of having endocrine disruption potential. Taken together, deviation between the effects of PRO and ISO in D. magna and other organisms suggests dissimilarity in MOAs or attributes of target bio-molecules between species. Additionally, PRO and ISO may act as endocrine disruptors based on the gene expression observation. Results in the present study confirm that it is challenging to predict ecological impact of active pharmaceutical ingredients (APIs) based on the available data acquired through human-focused studies. Furthermore, the present study provided unique data and a case study on the impact of APIs in a non-target organism.

The effect of titanium dioxide nanoparticles (nano-TiO2) on the bioaccumulation and biotransformation of arsenic (As) remains largely unknown. In this study, we exposed two freshwater algae (Microcystis aeruginosa and Scenedesmus obliquus) to inorganic As (arsenite and arsenate) with the aim of increasing our understanding on As bioaccumulation and methylation in the presence of nano-TiO2. Direct evidence from transmission electron microscope (TEM) images show that nano-TiO2 (anatase) entered exposed algae. Thus, nano-TiO2 as carriers boosted As accumulation and methylation in these two algae species, which varied between inorganic As speciation and algae species. Specifically, nano-TiO2 could markedly enhance arsenate (As(V)) accumulation in M. aeruginosa and arsenite (As(III)) accumulation in S. obliquus. Similarly, we found evidence of higher As methylation activity in the M. aeruginosa of As(III) 2 mg L−1 nano-TiO2 treatment. Although this was also true for the S. obliquus (As(V)) treatment, this species exhibited higher As methylation compared to M. aeruginosa, being more sensitive to As associated with nano-TiO2 compared to M. aeruginosa. Due to changes in pH levels inside these exposed algae, As dissociation from nano-TiO2 inside algal cells enhanced As methylation. Accordingly, the potential influence of nanoparticles on the bioaccumulation and biotransformation of their co-contaminants deserves more attention.

Climbazole (CBZ) is an antibacterial and antifungal agent widely used in personal care products. In this study, we investigated the interactions between climbazole (CBZ) and freshwater microalgae Scenedesmus obliquus (S. obliquus). Dose-effect relationships between CBZ concentrations and growth inhibitions or chlorophyll a content were observed. After 12 days of incubation, the algae density and chlorophyll a content in 2 mg/L treatment group was 56.6% and 15.8% of those in the control group, respectively. Biotransformation was the predominant way to remove CBZ in the culture solution, whereas the contribution of bioaccumulation and bioadsorption were negligible. More than 88% of CBZ was removed by S. obliquus across all treatments after 12 days of incubation, and the biotransformation of CBZ followed the first order kinetic model with half-lives of approximately 4.5 days at different treatments. CBZ-alcohol (CBZ-OH) was the only biotransformation product identified in algal solution. Moreover, the toxicity of biotransformation products was much lower than its corresponding precursor compound (CBZ). The results of this study revealed that S. obliquus might have a great impact on the environmental fates of CBZ and could be further applied to remove organic pollutants in aquatic environment.

Chirality is a critical topic in the medicinal and agrochemical fields. One quarter of all agrochemicals was chiral in 1996, and this proportion has increased remarkably with the introduction of new compounds over time. Despite scientists have made great efforts to probe the enantiomeric selectivity of chiral chemicals in the environment since early 1990s, the different behaviours of individual enantiomers in biologically mediated processes are still unclear. In the present review, we highlight state-of-the-knowledge on the stereoselective biotransformation and accumulation of chiral contaminants in organisms ranging from invertebrates to humans. Chiral insecticides, fungicides, and herbicides, polychlorinated biphenyls (PCBs), pharmaceuticals, flame retardants hexabromocyclododecane (HBCD), and perfluorooctane sulfonate (PFOS) are all included in the target compounds. Key findings included: a) Changes in the enantiomeric fractions in vitro and in vivo models revealed that enantioselectivity commonly occurs in biotransformation and bioaccumulation. b) Emerging contaminants have become more important in the field of enantioselectivity together with their metabolites in biological transformation process. c) Chiral signatures have also been regarded as powerful tools for tracking pollution sources when the contribution of precursor is unknown. Future studies are needed in order to understand not only preliminary enrichment results but also detailed molecular mechanisms in diverse models to comprehensively understand the behaviours of chiral compounds.

The emerging insensitive munitions compound (IMC) 3-nitro-1,2,4-triazole-5-one (NTO) is currently being used to replace conventional explosives such as 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), but the environmental fate of this increasingly widespread IMC remains poorly understood. Upon release from unexploded solid phase ordinances, NTO exhibits high aqueous solubility and, hence, potential mobilization to groundwater. Adsorption and abiotic transformation at metal oxide surfaces are possible mechanisms for natural attenuation. Here, the reactions at ferrihydrite and birnessite surfaces of NTO and its biotransformation product, 3-amino-1, 2, 4-triazol-5-one (ATO), were studied in stirred batch reactor systems at controlled pH (7.0). The study was carried out at metal oxide solid to solution ratios (SSR) of 0.15, 1.5 and 15 g kg−1. The samples were collected at various time intervals up to 3 h after reaction initiation, and analyzed using HPLC with photodiode array and mass spectrometric detection. We found no detectable adsorption or transformation of NTO upon reaction with birnessite, whereas ATO was highly susceptible to oxidation by the same mineral, showing nearly complete transformation within 5 min at 15 g kg−1 SSR to urea, CO2(g) and N2(g). The mean surface-area-normalized pseudo-first order rate constant (k) for ATO oxidation by birnessite across all SSRs was 0.05 ± 0.022 h−1 m−2, and oxidation kinetics were independent of dissolved O2 concentration. Both NTO and ATO were resistant to oxidation by ferrihydrite. However, NTO showed partial removal from solution upon reaction with ferrihydrite at 0.15 and 1.5 g kg−1 SSR and complete loss at 15 g kg−1 SSR due to strong adsorption. Conversely, ATO adsorption to ferrihydrite was much weaker than that measured for NTO.

This study investigated the effects of different long-term fertilizations on humic substances (HSs), humic acids (HAs) and humins, functioning as redox mediators for various microbial redox biotransformations, including 2,2′,4,4′,5,5′- hexachlorobiphenyl (PCB₁₅₃) dechlorination, dissimilatory iron reduction, and nitrate reduction, and their electron-mediating natures. The redox activity of HSs for various microbial redox metabolisms was substantially enhanced by long-term application of organic fertilizer (pig manure). As a redox mediator, only humin extracted from soils with organic fertilizer amendment (OF-HM) maintained microbial PCB₁₅₃ dechlorination activity (1.03 μM PCB₁₅₃ removal), and corresponding HA (OF-HA) most effectively enhanced iron reduction and nitrate reduction by Shewanella putrefaciens. Electrochemical analysis confirmed the enhancement of their electron transfer capacity and redox properties. Fourier transform infrared analysis showed that C=C and C=O bonds, and carboxylic or phenolic groups in HSs might be the redox functional groups affected by fertilization. This research enhances our understanding of the influence of anthropogenic fertility on the biogeochemical cycling of elements and in situ remediation ability in agroecosystems through microorganisms’ metabolisms.