The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available.

Microplastic fibers (MP) from textile weathering and washing are increasingly being recognized as environmental pollutants. The majority of studies on the bioavailability and effects of microplastic focused on small polystyrene spherical plastic particles, while less data are available for fibers and for other materials besides polystyrene. We investigated the ingestion and effects of ground polyethylene terephthalate (PET) textile microfibers (length range: 62–1400 μm, width 31–528 μm, thickness 1–21.5 μm) on the freshwater zooplankton crustacean Daphnia magna after a 48 h exposure and subsequent 24 h of recovery in MP free medium and algae. The majority of ingested fibers by D. magna were around 300 μm, but also some very large twisted MP fibers around 1400 μm were found inside the gut. Exposure to these fibers results in increased mortality of daphnids after 48 h only in the case where daphnids were not pre-fed with algae prior to experiment, but no effect was found when daphnids were fed before the experiments. Regardless of the feeding regime, daphnids were not able to recover from MP exposure after additional 24 h incubation period in a MP free medium with algae. The uptake and effects of PET textile MP on D. magna are presented here for the first time.

Presence of microorganisms in soils strongly affects mobility of metals. This fact is often excluded when mobile metal fraction in soil is studied using extraction procedures. Thus, the first objective of this paper was to evaluate strain Aspergillus niger’s exometabolites contribution on aluminium mobilization. Fungal exudates collected in various time intervals during cultivation were analyzed and used for two-step bio-assisted extraction of alumina and gibbsite. Oxalic, citric and gluconic acids were identified in collected culture media with concentrations up to 68.4, 2.0 and 16.5 mmol L−1, respectively. These exometabolites proved to be the most efficient agents in mobile aluminium fraction extraction with aluminium extraction efficiency reaching almost 2.2%. However, fungal cultivation is time demanding process. Therefore, the second objective was to simplify acquisition of equally efficient extracting agent by chemically mimicking composition of main organic acid components of fungal exudates. This was successfully achieved with organic acids mixture prepared according to medium composition collected on the 12th day of Aspergillus niger cultivation. This mixture extracted similar amounts of aluminium from alumina compared to culture medium. The aluminium extraction efficiency from gibbsite by organic acids mixture was lesser than 0.09% which is most likely because of more rigid mineral structure of gibbsite compared to alumina. The prepared organic acid mixture was then successfully applied for aluminium extraction from soil samples and compared to standard single step extraction techniques. This showed there is at least 2.9 times higher content of mobile aluminium fraction in soils than it was previously considered, if contribution of microbial metabolites is considered in extraction procedures. Thus, our contribution highlights the significance of fungal metabolites in aluminium extraction from environmental samples, but it also simplifies the extraction procedure inspired by bio-assisted extraction of aluminium by common soil fungus A. niger.

Sand beaches are highly dynamic habitats that can experience considerable impacts from oil spills. This review provides a synthesis of the scientific literature on major oil spills and their impacts on sand beaches, with emphasis on studies documenting effects and recoveries of intertidal invertebrate communities. One of the key observations arising from this review is that more attention has generally been given to studying the impacts of oil spills on invertebrates (mostly macrobenthos), and not to documenting their biological recovery. Biological recovery of sand beach invertebrates is highly dynamic, depending on several factors including site-specific physical properties and processes (e.g., sand grain size, beach exposure), the degree of oiling, depth of oil burial, and biological factors (e.g., species-specific life-history traits). Recovery of affected communities ranges from several weeks to several years, with longer recoveries generally associated with physical factors that facilitate oil persistence, or when cleanup activities are absent on heavily oiled beaches. There are considerable challenges in quantifying impacts from spills on sand beach invertebrates because of insufficient baseline information (e.g., distribution, abundance and composition), knowledge gaps in their natural variability (spatial and temporal), and inadequate sampling and replication during and after oil spills. Thus, environment assessments of impacts and recovery require a rigorous experimental design that controls for confounding sources of variability. General recommendations on sampling strategies and toxicity testing, and a preliminary framework for incorporating species-specific life history traits into future assessments are also provided.

The presence of pharmaceuticals in the environment has triggered concern among the general population and received considerable attention from the scientific community in recent years. However, only a few publications have focused on anticancer drugs, a class of pharmaceuticals that can exhibit cytotoxic, genotoxic, mutagenic, carcinogenic and teratogenic effects. The present study investigated the photodegradation, biodegradation, bacterial toxicity, mutagenicity and genotoxicity of cyclophosphamide (CP) and 5-fluorouracil (5-FU). The photodegradation experiments were performed at a neutral to slight pH range (7–7.8) using two different lamps (medium-pressure mercury lamp and a xenon lamp). The primary elimination of the parent compounds was monitored by means of liquid chromatography tandem mass spectrometry (LC-IT-MS/MS). NPOC (non-purgeable organic carbon) analyses were carried out in order to assess mineralization rates. The Closed Bottle Test (CBT) was used to assess ready biodegradability. A new method using Vibrio fischeri was adopted to evaluate toxicity. CP was not degraded by any lamp, whereas 5-FU was completely eliminated by irradiation with the mercury lamp but only partially by the Xe lamp. No mineralization was observed for the experiments performed with the Xe lamp, and a NPOC removal of only 18% was registered for 5-FU after 256 min using the UV lamp. Not one of the parent compounds was readily biodegradable in the CBT. Photo transformation products (PTPs) resulting from photolysis were neither better biodegradable nor less toxic than the parent compound 5-FU. In contrast, the results of the tests carried out with the UV lamp indicated that more biodegradable and non-toxic PTPs of 5-FU were generated. Three PTPs were formed during the photodegradation experiments and were identified. The results of the in silico QSAR predictions showed positive mutagenic and genotoxic alerts for 5-FU, whereas only one of the formed PTPs presented positive alerts for the genotoxicity endpoint.

The Three Gorges Reservoir (TGR) is one of the world's largest man-made hydropower projects, which has posed great challenges to the aquatic environment of the Yangtze River since the impoundment of water. As a non-essential toxic metalloid, information on the bioavailability of Antimony (Sb) in TGR sediments is lacking. Four sediment cores were collected from a tributary and the mainstream in the TGR to investigate the distribution and remobilization of Sb using the diffusive gradients in thin films (DGT) technique. The results showed that the concentrations of Sb obtained by DGT (CDGT-Sb) at all of the sampling stations were low (below 0.30 μg/L), compared to the relatively high Sb concentrations in the sediments. The lateral and vertical distributions of CDGT-Sb revealed different tendencies in overlying water and sediments at all of the sampling sites in the TGR, which may be attributed to anthropogenic impacts, the heterogeneity of sediments and the unevenness of the sediment-water interface (SWI) during the deployment of DGT probes. In addition, CDGT-Sb in the surface sediments were lower than those in the overlying water, and concentration gradients were found near the SWI, demonstrating that Sb has the potential to diffuse from the overlying water into the sediment. In the sediment cores, different peaks were discovered in the DGT probes and the remobilization of Sb simultaneously appeared in the vicinity of −10 cm. Correlation analysis showed that CDGT-Sb had no or negative correlation with CDGT-Fe and CDGT-Mn in all of the DGT probes, suggesting that the release of Sb was unassociated with Fe and Mn in the sediments in the study area.

Silver nanoparticles (nAg) are widely used in consumer products and the risk associated with their potential release into freshwater ecosystems needs to be addressed using environmentally realistic exposure concentrations. Here, the effects of low concentrations (0.5–5 μg L⁻¹) of two different sized nAg (10 and 60 nm) and a silver nitrate positive control were evaluated in Gammarus roeseli following exposure for 72 h. Cellular, individual and functional endpoints were independently studied and the most striking results were reported for functional endpoints. Indeed, without a change in their feeding activity, the gammarids produced significantly fewer fine particles of organic matter when exposed to nAg, even at 0.5 μg L⁻¹ of 10 nm nAg. These functional endpoints seem to be efficient markers for detecting the early effects of nAg on G. roeseli.

To explore the mechanisms and influence factors on the production of 2,4,6-trichloroanisole (2,4,6-TCA) in surface waters, the 2,4,6-TCA formation potential (FP) test was conducted by incubating the real lake water with the addition of 2,4,6-trichlorophenol (2,4,6-TCP) precursor. Besides bacteria and fungi, two common cyanobacteria and algae species, i.e., Chlorella vulgaris and Anabaena flos-aquae, have been proved to have strong capabilities to produce 2,4,6-TCA, which may contribute the high 2,4,6-TCA FP (152.2 ng/L) of lake water. The microbial O-methylation of 2,4,6-TCP precursor is catalyzed by chlorophenol O-methyltransferases (CPOMTs), and their characteristics were identified by adding inductive methyl donors or excluding microorganisms via ultrafiltration. The results indicated both S-adenosyl methionine (SAM) dependent and non-SAM dependent CPOMTs played important roles; extracellular CPOMTs also participated in the biosynthesis of 2,4,6-TCA. Moreover, investigating the effects of various environmental factors revealed initial 2,4,6-TCP processor concentration, temperature, pH and some divalent metal cations (i.e., Mn2+, Mg2+ and Zn2+) had obvious effects on the production of 2,4,6-TCA.

The fate of hydrophobic organic compounds in aquatic environment are largely determined by their exchange at sediment-water interface, which is highly dynamic and subject to rapidly evolving environmental conditions. In turn, environmental conditions may be governed by both physicochemical parameters and anthropogenic events. To examine the importance of various impact factors, passive sampling devices were deployed at the seafloor of Hailing Bay, an urbanized estuarine bay in Guangdong Province of South China to measure the sediment-water diffusion fluxes of several metabolites of dichlorodiphenyltrichloroethane (DDT), p,p′-DDE, p,p′-DDD and o,p′-DDD. The physicochemical properties of water (temperature, pH, salinity and dissolved oxygen) and surface sediment (sediment organic matter, physical composition, pH, water content, colony forming unit and catalase activity) were also measured. The results showed that the diffusion fluxes of o,p′-DDD, p,p′-DDD and p,p′-DDE at sites A1 and A2 near a fishing boat maintenance facility ranged from 0.42 to 4.73 ng m−2 d−1 (from sediment to overlying water), whereas those at offshore sites varied between −0.03 and −3.02 ng m−2 d−1 (from overlying water to sediment), implicating A1 and A2 as the sources of the target compounds. The distribution patterns of the diffusion fluxes of the target compounds were different from those of water and sediment parameters (water temperature, salinity, sediment texture, pH, colony forming unit and catalase activity) at six sampling sites. This finding suggested that none of these parameters were critical in dictating the sediment-water diffusion fluxes. Besides, decreases in the contents of kerogen and black carbon by 6.7% and 11% would enhance the diffusion fluxes of the target compounds by 11–14% and 12–23%, respectively, at site A1, indicating that kerogen and black carbon were the key factors in mediating the sediment–water diffusion fluxes of DDT-related compounds in field environments.

Polycyclic aromatic hydrocarbons (PAHs) are often detected in the environment and are regarded as endocrine disruptors. We here designated mixtures of PAHs in the environment as environmental PAHs (ePAHs) to discuss their effects collectively, which could be different from the sum of the constituent PAHs. We first summarized the biological impact of environmental PAHs (ePAHs) found in the atmosphere, sediments, soils, and water as a result of human activities, accidents, or natural phenomena. ePAHs are characterized by their sources and forms, followed by their biological effects and social impact, and bioassays that are used to investigate their biological effects. The findings of the bioassays have demonstrated that ePAHs have the ability to affect the endocrine systems of humans and animals. The pathways that mediate cell signaling for the endocrine disruptions induced by ePAHs and PAHs have also been summarized in order to obtain a clearer understanding of the mechanisms responsible for these effects without animal tests; they include specific signaling pathways (MAPK and other signaling pathways), regulatory mechanisms (chromatin/epigenetic regulation, cell cycle/DNA damage control, and cytoskeletal/adhesion regulation), and cell functions (apoptosis, autophagy, immune responses/inflammation, neurological responses, and development/differentiation) induced by specific PAHs, such as benz[a]anthracene, benzo[a]pyrene, benz[l]aceanthrylene, cyclopenta[c,d]pyrene, 7,12-dimethylbenz[a]anthracene, fluoranthene, fluorene, 3-methylcholanthrene, perylene, phenanthrene, and pyrene as well as their derivatives. Estrogen signaling is one of the most studied pathways associated with the endocrine-disrupting activities of PAHs, and involves estrogen receptors and aryl hydrocarbon receptors. However, some of the actions of PAHs are contradictory, complex, and unexplainable. Although several possibilities have been suggested, such as direct interactions between PAHs and receptors and the suppression of their activities through other pathways, the mechanisms underlying the activities of PAHs remain unclear. Thus, standardized assay protocols for pathway-based assessments are considered to be important to overcome these issues.