Neonicotinoid insecticides have been widely used throughout the world over the last two decades. In the present study, we investigated the degradation of neonicotinoid insecticides nitenpyram (NIT) and dinotefuran (DIN) by the white-rot fungus Phanerochaete sordida YK-624. While NIT was completely degraded by P. sordida YK-624 under ligninolytic conditions, only a 20% decrease was observed under nonligninolytic conditions. On the other hand, P. sordida YK-624 degraded 31% of DIN under ligninolytic conditions after a 20-day incubation, while it did not degrade DIN under nonligninolytic conditions. We found that cytochromes P450 played a key role in the biotransformation of NIT and DIN by P. sordida YK-624. A novel NIT metabolite (E)-N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N′-hydroxy acetimidamide (CPMHA) and a novel DIN metabolite N-((4aS,7aS,E)-1-methylhexahydrofuro[2,3-d]pyrimidin-2(1H)-ylidene)nitramide (PHPF) were identified in this study. In addition, to evaluate neurotoxicity, the effects of NIT, DIN and their metabolites on the viability of human neuroblastoma cells SH-SY5Y were determined. PHPF showed higher neurological toxicity than DIN, whereas the metabolite of NIT, CPMHA, showed no toxic effect. Our results indicated that the neurological toxicity of NIT could be effectively removed by P. sordida YK-624.

Increasing riverine phosphorus (P) levels in headwaters due to expanded and intensified human activities are worldwide concerns, because P is a well-known limiting nutrient for freshwater eutrophication. Here we adopt the conceptual framework of the SPAtially Referenced Regressions On Watershed attributes (SPARROW) model to describe total phosphorus (TP) sources and transport in a headwater watershed undergoing rapid agricultural expansion in the upper Taihu Lake Basin, China. Our models, which include variables for land cover, river length, runoff depth, and pond density, explain 94% of the spatio-temporal variability in TP loads. Agricultural lands contribute the largest percentage (61%) of the TP loads delivered downstream, followed by forestland (21%) and urban land (18%). Future agricultural expansion to 15% of the total basin area is possible, which could lead to a 50% increase in TP loads. According to our analysis, an average of 24% of the total P export from the watershed landscape was intercepted in ponds. The exported amount was subsequently retained by tributaries and along the mainstem river, accounting for 14% and 43% of their inflowing loads, respectively. The remaining ∼6 tons yr⁻¹ of TP was eventually transported into Tianmu Lake, in Southeastern China. The model identified several sub-catchments as hotspots of TP loss and thus logical sites for targeted management. Our study underscores the significance of agricultural expansion as a factor that can exacerbate headwater TP pollution, highlighting the importance of landscapes to buffer TP losses from sensitive hilly catchments. This also points to a need for an integrated management strategy that considers the spatial-varying P sources and associated transport of TP in precious headwater resources.

Benzo[a]pyrene (BaP), a common environmental pollutant, can modulate the immune-associated signal pathway NF-κB, which is one of the critical signal pathways involved in various immune responses. BaP exposure usually generates reactive oxygen species (ROS), but whether ROS are predominantly involved in the modulation mechanism of the NF-κB pathway has not been clearly understood. In this study, an in vivo examination of Oryzias melastigma demonstrated that BaP exposure led to a down-regulation of the NF-κB pathway and increased levels of ROS. Conversely, in vitro results using the medaka liver cell line DIT-29 and a widely applied H₂O₂ method showed the opposite: up-regulation of the NF-κB pathway. However, the down-regulation of NF-κB upon BaP exposure in vitro was inhibited by the addition of a ROS inhibitor, indicating ROS are involved in the modulation of NF-κB. The discrepancy between in vivo and in vitro results of ROS impacts on NF-κB activation might be related to the concentration and persistence of ROS. Using a modified luminol detection system, BaP was found to generate sustained physiological concentrations of ROS for 24 h, while an H₂O₂ bolus generated ROS for less than 30 min. Furthermore, a steady-state sub-micromolar H₂O₂ system (H₂O₂ss) was developed in parallel as a positive control of ROS, by which H₂O₂ could be maintained for 24 h. Comparative evaluation using H₂O₂, H₂O₂ss and BaP exposures on the medaka cell line with pGL4.32 demonstrated that the persistent physiological concentrations of ROS generated upon BaP exposure or treatment with H₂O₂ss inhibited the NF-κB pathway, but direct H₂O₂ exposure had the opposite effect. Moreover, a western-blot assay and EMSA detection further confirmed the modulation of the NF-κB pathway in DIT-29. Taken together, this study shows that BaP exposure inhibits the NF-κB pathway by generating sustained physiological concentrations of ROS.

The Yangtze River, which is the largest in Euro-Asian, receives tremendous anthropogenic nitrogen input and is typically characterized by severe eutrophication and hypoxia. Two major processes, denitrification and anaerobic ammonium oxidation (anammox), play vital roles for removing nitrogen global in nitrogen cycling. In the current study, sediment samples were collected from both latitudinal and longitudinal transects along the coastal Yangtze River and the East China Sea (ECS). We investigated community composition and distributions of nosZ gene-encoded denitrifiers by high throughput sequencing, and also quantified the relative abundances of both denitrifying and anammox bacteria by q-PCR analysis. Denitrifying communities showed distinct spatial distribution patterns that were impacted by physical (water current and river runoffs) and chemical (nutrient availability and organic content) processes. Both denitrifying and anammox bacteria contributed to the nitrogen removal in Yangtze Estuary and the adjacent ECS, and these two processes shifted from coastal to open ocean with reverse trends: the abundance of nosZ gene decreased from coastal to open ocean while anammox exhibited an increasing trend based on quantifications of hzsB and 16S rRNA genes. Further correspondence correlation analysis revealed that salinity and nutrients were the main factors in structuring composition and distribution of denitrifying and anammox bacteria. This study improved our understanding of dynamic processes in nitrogen removal from estuarine to open ocean. We hypothesize that denitrification is the major nitrogen removal pathway in estuaries, but in open oceans, low nutrient and organic matter concentrations restrict denitrification, thus increasing the importance of anammox as a nitrogen removal process.

During their lifecycle, many engineered nanoparticles (ENPs) undergo significant transformations that may modify their toxicity, behaviour, and fate in the environment. Therefore, understanding the possible environmentally relevant transformations that ENPs may undergo as a result of their surroundings is becoming increasingly important. This work considers industrially produced ceria (CeO2) and focuses on a particle library consisting of seven zirconium-doped variants (Ce1-xZrxO2) where the Zr doping range is x = 0–1. The study assesses their potential transformation in the presence of environmentally relevant concentrations of phosphate. These ENPs have an important role in the operation of automotive catalysts and therefore may end up in the environment where transformations can take place. Samples were exposed to pH adjusted (c. 5.5) solutions made up of either 1 mM or 5 mM each of KH2PO4, citric acid and ascorbic acid and the transformed particles were characterised by means of DLS – size and zeta potential, UV/VIS, TEM, FT-IR, EDX and XRD. Exposure to the phosphate solutions resulted in chemical and physical changes in all ceria-containing samples to cerium phosphate (with the monazite structure). The transformations were dependent on time, ceria concentration in the particles (Ce:Zr ratio) and phosphate to ceria ratio. The presence of Zr within the doped samples did not inhibit these transformations, yet the pure end member ZrO2 ENPs showed no conversion to phosphate. The quite dramatic changes in size, structure and composition observed raise important questions regarding the relevant form of the materials to investigate in ecotoxicity tests, and for regulations based on one or more dimensions in the nanoscale.

The influence of anthropogenic outdoor sources on the geochemical composition of house dust material in large cities is poorly understood. In this study, we investigate the magnetic signature and the concentrations of potentially toxic elements (PTEs) in randomly selected house dust samples from the metropolitan area of Athens, the most populated city in Greece. Environmental magnetic measurements, including isothermal remanent magnetization and thermomagnetism, indicated that the main magnetic mineral is coarse-grained low-coercivity magnetite. Detailed microscopic observations of the magnetically extracted material revealed the presence of three different kinds of Fe-rich particles deriving from both combustion-related and non-exhaust vehicular sources: irregularly-shaped grains and spherules of Fe-oxides, and particles consisting of metallic Fe. Further study of the morphology of single anthropogenic magnetic spherules (size > 30 μm) identified the presence of magnetite spherical particles, typically formed by industrial combustion processes. Enrichment factors (EFs) for the PTEs calculated against the Athens urban soil showed that the house dusts were very highly enriched in Cd, Cu, Zn and significantly enriched in Pb (median EF values of 34.1, 26.2, 25.4 and 10.3, respectively). The oral bioaccessibility of PTEs in the house dust, evaluated using a simulated gastric solution (0.4 M glycine), was in the order Pb > Zn > Mn > Cd > Ni > Cu > Cr > Fe. Concentrations of Pb increased with the house age. Principal component and cluster analysis demonstrated the close association of anthropogenic Cu, Pb and Zn with the magnetic susceptibility of the house dusts. We conclude that both traffic-related and industrial sources trigger the occurrence of magnetic Fe/PTEs- rich particles in house dust. These results reinforce the use of environmental magnetism determinations for assessing anthropogenic contamination of PTEs in the indoor environment in large cities.

Antifouling paint particles (APPs) of between 500 μm and >2 mm in diameter have been identified in silty, intertidal estuarine sediments through a combination of microscopy and x-ray fluorescence spectrometry. APPs were heterogeneously distributed, with maximal concentrations of 430 particles L−1 (0.2 g L−1) near to a facility where boats are regularly maintained and 400 particles L−1 (4.2 g L−1) at a location where old boats had been abandoned, with the majority of particles encountered in the finest size fraction retrieved. APPs contained variable concentrations of Cu, Zn, Sn and Pb, with respective maxima of 562,000, 269,000, 9,970 and 126,000 mg kg−1. These characteristics are attributed to a multitude of contemporary and historic sources of an assortment of formulations and result in significant but heterogeneous metal contamination of local sediments. APPs were also identified in the guts of the deposit-feeding ragworm, Hediste diversicolor, that inhabited sediments impacted by abandoned boats or boating activities. The tissue of H. diversicolor was particularly enriched in Cu where ingested APPs were observed, with a significant correlation between dry weight Cu concentrations in the two media (r = 0.734) presumably reflecting the inability of the animal to regulate this metal. While the toxicity of APPs requires further investigation, there is clearly a need for stricter regulations on antifouling wastes in boatyards and marinas and a requirement to better manage abandoned boats.

Fluoride is a well-known compound for its usefulness in healing dental caries. Similarly, fluoride is also known for its toxicity to various tissues in animals and humans. It causes skeletal fluorosis leading to osteoporosis of the bones. We hypothesized that when bones are affected by fluoride, the skeletal muscles are also likely to be affected by underlying molecular events involving myogenic differentiation. Murine myoblasts C2C12 were cultured in differentiation media with or without NaF (1 ppm-5 ppm) for four days. The effects of NaF on myoblasts and myotubes when exposed to low (1.5 ppm) and high concentration (5 ppm) were assessed based on the proliferation, alteration in gene expression, ROS production, and production of inflammatory cytokines. Changes based on morphology, multinucleated myotube formation, expression of MyHC1 and signaling pathways were also investigated. Concentrations of NaF tested had no effects on cell viability. NaF at low concentration (1.5 ppm) caused myoblast proliferation and when subjected to myogenic differentiation it induced hypertrophy of the myotubes by activating the IGF-1/AKT pathway. NaF at higher concentration (5 ppm), significantly inhibited myotube formation, increased skeletal muscle catabolism, generated reactive oxygen species (ROS) and inflammatory cytokines (TNF-α and IL-6) in C2C12 cells. NaF also enhanced the production of muscle atrophy-related genes, myostatin, and atrogin-1. The data suggest that NaF at low concentration can be used as muscle enhancing factor (hypertrophy), and at higher concentration, it accelerates skeletal muscle atrophy by activating the ubiquitin-proteosome pathway.

To trace the circulation history of aquatic bioavailable Hg in the Antarctic, the species and isotopic compositions of Hg in sediment, Archaeogastropoda (Agas), Neogastropoda (Ngas), and fish collected from King George Island were studied in detail. Positive mass independent fractionation (MIF) was observed and positively correlated with the percentages of methylmercury (MeHg%) in Agas and Ngas, suggesting an effect of MeHg accumulation during trophic transfer on MIF signatures. However, both the ratios of Δ199Hg/δ202Hg and Δ199Hg/Δ201Hg indicated different circulation histories of Hg in Agas, Ngas, and fish. The microbial methylation in sediment was the primary source of MeHg in Agas and Ngas (Δ199Hg/δ202Hg ∼0, Δ199Hg/Δ201Hg ∼1.00). In contrast, the MeHg in fish (Δ199Hg/δ202Hg = 0.55 ± 0.06, Δ199Hg/Δ201Hg = 1.19 ± 0.17) came from the combined sources of residual MeHg which had sunk from the surface water and microbial-methylated MeHg in sediments, and the bioavailable Hg in the sediments contributed to approximately 44% of the total Hg in fish. Subsequently, the Δ199Hg values of bioavailable MeHg and IHg in sediments were quantitatively calculated, which provided key end-member information for future source apportionment in the Antarctic and other pelagic regions. It was also found that the Hg accumulated in Agas and Ngas had no history of MeHg photo-degradation, indicating that the methylated Hg in benthic zones suffered little photo-degradation and thus presented high bioavailability and environmental risk.

Swine waste is a reservoir of microbial pollutants, including pathogens, antibiotic resistance genes (ARGs) and antibiotic resistant bacteria (ARB); therefore, soil fertilized with swine waste is an essential pathway for the dissemination of microbial pollutants from concentrated swine farms to the public. To rationalize the intervals of swine wastes application and investigate the effects of soil type on the occurrences of microbial pollutants and antibiotic resistance, pot experiments were conducted with three typical soils, humic acrisol, calcaric cambisols and histosols, being collected from south, northwest and northeast China (soil-R, soil-Y and soil-B, respectively). The soils were amended with swine slurry, digestate and chemical fertilizers and then conducted for 172 days. The influence of microbial pollutants and antibiotic resistance in soil posed by digestate application was similar to that of the chemical fertilizers, while swine slurry posed high risks to the soil. Soil-B which had the highest organic matter and neutral pH was least influenced by the swine slurry amendment. tetG, tetM and ermF were persistent ARGs in the slurry treated soil, and their decay rates fitted to first-order kinetics in the order soil-B> soil-Y > soil-R. Putative pathogens showed strong correlations with ARGs, suggesting a risk of dissemination. The initial 43–82 days was the active phase of microbial pollution in slurry treated soil, during which time heavy metals, moisture content, total organic carbon and the microbial community were key factors contributing to changes in antibiotic resistance. Fertilization intervals of livestock wastes should be lengthened over the ARG active phase.