Fulvic acid (FA) significantly influences the bioavailability and fate of heavy metals in environments, while its acid-base characters and metal binding processes are still unclear. Here, spectroscopic techniques combined with multiple models (e.g., NICA-Donnan model) and two-dimensional correlation spectroscopy (2D COS) were applied to explore the proton and copper binding properties of FA sub-fractions (FA3-FA13). The charge densities, average contents of carboxylic and phenolic groups, average dissociation constants pKa1 and pKa2 of sub-fractions ranged 0–16 meq∙g∙C−1, 5.03–9.58 meq∙g∙C−1, 2.52–4.67 meq∙g∙C−1, 4.15–4.33 and 8.52–9.72, respectively. FA sub-fractions had a relatively narrow distribution of carboxyl group and a broad distribution of phenolic group. FA sub-fractions also exhibited roughly two phenolic hydroxyl groups per every 1–3 phenyl rings. Differential absorbance spectra (DAS) derived Gaussian bands were associated to the inter-chromophore interactions, the changes of molecular conformations and functional groups with copper addition. Differential spectra slopes (DSlope275-295&325-375) were more significant with higher copper concentration and copper amounts bonded to carboxylic groups. UV–Vis and fluorescence spectra with 2D heterospectral COS revealed the copper binding heterogeneities and sequential orders of chromophores and fluorophores, quantitatively confirming by the order of conditional stability constants (log KCu: 4.64–5.56). Salicylic-/polyhydroxyphenolic, hydroxyl and amino groups were strongly associated to the basic units for fluorophores. Sequential changes followed the order of humic-like→fulvic-like materials for FA3/FA5, humic-like→fulvic-like→tryptophan-like materials for FA7, and humic-like→tryptophan-like→fulvic-like→tyrosine-like materials for FA9/FA13. Spectroscopic techniques combined with various models (especially for 2D COS) are beneficial to elucidate the binding heterogeneity and sensitivity for metal-organic matters at the functional group level.

Sludge from a groundwater treatment plant was used to prepare biochar by pyrolysis. The Fe–Mn rich biochar was used to activate percarbonate for the remediation of polycyclic aromatic hydrocarbons (PAHs) contaminated aquatic sediments. Results showed that the sludge–derived biochar (SBC) produced at a pyrolysis temperature of 700 °C was the most effective in activating percarbonate, which exhibited significant oxidative removal of PAHs. PAHs degradation took place via a Fenton-like oxidation manners, contributed from the Fe³⁺/Fe²⁺ and Mn³⁺/Mn²⁺ redox pairs, and achieved the highest degradation efficiency of 87% at pH₀ 6.0. Reactions between oxygenated functional groups of biochar and H₂O₂ generated of O₂•– and HO• radicals in abundance under neutral and alkaline pH was responsible for the catalytic degradation of PAHs. Our results provided new insights into the environmental applications of SBC for the green sustainable remediation of organics-contaminated sediments and aided in reduction of associated environmental and health risk.

Several populations of the amphipod, Hyalella azteca, have developed resistance to pyrethroid insecticides due to non-target exposure, but the dominance of the resistance trait is unknown. The current study investigated the dominance level of point mutations in natural populations of insecticide-resistant H. azteca and determined whether H. azteca from different clades with and without resistant alleles can hybridize and produce viable offspring. A parent generation (P₀) of non-resistant homozygous wild type H. azteca was crossbred with pyrethroid-resistant homozygous mutant animals and the tolerance of the filial 1 (F₁) generation to the pyrethroid insecticide, permethrin, was measured. Then the genotypes of the F₁ generation was examined to assure heterozygosity. The resistant parents had permethrin LC₅₀ values that ranged from 52 to 82 times higher than the non-resistant animals and both crossbreeding experiments produced heterozygous hybrid offspring that had LC₅₀ values similar to the non-resistant H. azteca parent. Dominance levels calculated for each of the crosses showed values close to 0, confirming that the L925I and L925V mutations were completely recessive. The lack of reproduction by hybrids of the C x D breeding confirmed that these clades are reproductively isolated and therefore introgression of adaptive alleles across these clades is unlikely. Potential evolutionary consequences of this selection include development of population bottlenecks, which may arise leading to fitness costs and reduced genetic diversity of H. azteca.

Despite the large number of studies reporting the phytotoxicity of graphene-based materials, the effects of these materials on nutrient uptake in plants remain unclear. The present study showed that nitrate concentrations were significantly decreased in the roots of wheat plants treated with graphene oxide (GO) at 200–800 mg L⁻¹. Non-invasive microelectrode measurement demonstrated that GO could significantly inhibit the net NO₃⁻ influx in the meristematic, elongation, and mature zones of wheat roots. Further analysis indicated that GO could be trapped in the root vacuoles, and that the maximal root length and the number of lateral roots were significantly reduced. Additionally, root tip whitening, creases, oxidative stress, and weakened respiration were observed. These observations indicate that GO is highly unfavorable for vigorous root growth and inhibits increase in root uptake area. At the molecular level, GO exposure caused DNA damage and inhibited the expression of most nitrate transporters (NRTs) in wheat roots, with the most significantly downregulated genes being NRT1.3, NRT1.5, NRT2.1, NRT2.3, and NRT2.4. We concluded that GO exposure decreased the root uptake area and root activity, and decreased the expression of NRTs, which may have consequently suppressed the NO₃⁻ uptake rate, leading to adverse nitrate accumulation in stressed plants.

In this study, the Songgang River (SR) was selected as a typical tributary that is heavily polluted by rapid urbanization and industrialization. The polycyclic aromatic hydrocarbon (PAH) distribution at five representative sampling sites from different urban functional areas was studied. The chemical and physical properties and spatial and vertical distribution of PAHs in sediments were investigated. PAH source identification and the ecological risks of the sediments were evaluated. The results suggested that the industrial zone and dense residential and commercial areas were the most contaminated areas of the SR, as the chemical and physical properties of total organic carbon content in sediments was the highest at the dense residential and commercial areas (0.1–4.5%); however, the acid volatile sulfide, total nitrogen, and total phosphorus contents were the highest in the industrial zone, with ranges of 700.0–1618.4 mg/kg dw, 22.4–3543.9 mg/kg dw, and 82.3–4550.7 mg/kg dw, respectively. The spatial distribution of residual PAHs in the sediment cores showed a wide variation among different urban functional areas, and the vertical characterization (0–300 cm) depicted a significant decreasing trend with depth and with an abrupt increase at 180 cm. The concentration of ∑16 PAHs ranged from 208.7 to 7709.8 ng/g dw, with the highest concentrations obtained in the industrial zone. The low molecular weight-PAHs (153–6720 ng/g dw) were predominant in the sediments. Furthermore, there were combined sources (biomass burning: 40.3%; fossil fuel combustion: 25.5%; mixed source: 21.5%; oil pollution: 12.7%) and a long term accumulation effect, with anthropogenic activities and industrial pollution as the major contributing sources. The concentrations of Nap, Acy, Ace, Flu, and Ant exceeded the lower limit of the sediment quality criteria, and higher toxic equivalent concentration values of the total carcinogenic PAHs were observed nearby the midstream of the SR, which may cause adverse biological effects and implies a need for regular monitoring.

The increasing availability of water quality datasets has led to a greater focus on hydrologic and water quality analysis, thus requiring more efficient and accurate modelling methods. Data mining techniques have been increasingly used for water quality analysis and prediction of the concentration and load of nitrogen pollutants instead of more traditional simulation methods. In this study, we tested the multilayer perceptron (MLP), k-nearest neighbor (k-NN), random forest, and reduced error pruning tree (REPTree) methods, along with the traditional linear regression, to predict nitrate levels based on long-term data from six watersheds with different land-use practices in the midwestern United States. Both the concentration and load results indicated that REPTree had the best performance, with an R² of 0.61–0.85 and a relative absolute error of <75.8%. The different watershed types, however, influenced the performance of the data mining methods, where all four methods showed a higher accuracy for urban dominant watershed and lower accuracy for agricultural and forest watersheds. Out of these four methods, classification tree methods (REPTree and RF) performed better than cluster methods (MLP and k-NN) for agricultural and forested watersheds. Our results indicated that both the data structure based on the dominant land use and type of algorithmic method should be carefully considered for selecting a data mining method to predict nitrate concentration and load for a watershed.

This study provided a comprehensive characterization on ingestion of different typologies of microplastics in several fish and invertebrate species from the Adriatic Sea, considered as a preferential area of plastic accumulation in the Mediterranean. Almost 500 organisms were sampled in the three sectors of Northern, Central and Southern Adriatic, testing the hypothesis that area of collection, habitat and feeding strategy might influence the occurrence of plastic particles in biota. In this study, the overall characterization considered separately plastic microparticles (MPs) from textile microfibers (MFs) which also included natural and semi-synthetic ones. Ingestion of MPs was a widespread phenomenon, but their number (typically 1 or 2) did not reveal any significant relationship with biometric values, geographical areas or ecological features of the species. Conversely, the frequency of ingestion, ranging from 13 to 35% of organisms containing MPs, appeared a more reliable index to highlight such differences, revealing higher values in species from Central and Southern basins compared to the Northern one, as well as in benthopelagic compared to benthic or pelagic organisms. Geographical differences also occurred in terms of size and typology of ingested particles, suggesting the importance of local river runoffs and surface currents dynamics. Textile microfibers (MFs) were also abundant in Adriatic food webs occurring in all the analyzed species with average numbers (3–10) and frequencies (40–70%) higher than those reported for MPs; further, an elevated percentage of MFs (>80%) was of natural or semi-synthetic origin.Overall, this study provided general insights toward the harmonization of a common biomonitoring strategy, as in the context of MSFD, including the suggestion of a frequency-based index and of a multi-species approach to increase the ecological relevance of assessment, as well as the comparability between different areas and trophic webs.

Arsenic exposure contributed to the development of human diseases. Arsenic exerted multiple organ toxicities mainly by triggering oxidative stress. However, the signaling pathway underlying oxidative stress is unclear. We previously found that the expression of SFPQ, a splicing factor, was positively associated with urinary arsenic concentration in an arsenic-exposed population, suggesting an oxidative stress regulatory role for SFPQ. To test this hypothesis, we established cell models of oxidative stress in human hepatocyte cells (L02) treated with NaAsO₂. Reactive oxygen species (ROS) synthesis displayed a time- and dose-dependent increase with NaAsO₂ treatment. SFPQ suppression resulted in a 36%–53% decrease in ROS generation, leading to enhanced cellular damage determined by 8-OHdG, comet tail moment, and micronucleus analysis. Particularly, SFPQ deficiency attenuated expression of the oxidase genes DUOX1, DUOX2, NCF2, and NOX2. A fluorescent-based RNA electrophoretic mobility shift assay (FREMSA) and dual-luciferase reporter system revealed that miR-92b-5p targeted DUOX2 mRNA degradation. An RNA immunoprecipitation assay showed an interaction between SFPQ and miR-92b-5p of the miRNA-induced silencing complex (miRISC). Notably, NaAsO₂ treatment diminished the interaction between SFPQ and miR92b-5p, accompanied by decreased binding between miR-92b-5p and 3′-UTR of DUOX2. However, SFPQ deficiency suppressed the dissociation of miR-92b-5p from 3′-UTR of DUOX2, indicating that miR-92b-5p regulated the SFPQ-dependent DUOX2 expression. Taken together, we reveal that SFPQ responds to arsenic-induced oxidative stress by interacting with the miRISC. These findings offer new insight into the potential role of SFPQ in regulating cellular stress response.

Mycotoxins are toxic fungal metabolites, contaminating cereal grains in field or during processing and storage periods. These environmental contaminants pose great threats to humans and animals’ health due to their toxic effects. Type A trichothecenes, fumonisins and fusaric acid (FA) are commonly detected mycotoxins produced by various Fusarium species. Trichoderma spp. are promising antagonists in agriculture for their activities against plant pathogens, and also regarded as potential candidates for bioremediation of environmental contaminants. Managing toxigenic fungi by antagonistic Trichoderma is regarded as a sustainable and eco-friendly strategy for mycotoxin control. However, the metabolic activities of Trichoderma on natural occurring mycotoxins were less investigated. Our current work comprehensively explored the activities of Trichoderma against type A trichothecenes, fumonisins and FA producing Fusarium species via co-culture competition and indirect volatile assays. Furthermore, we investigated metabolism of type A trichothecenes and FA in Trichoderma isolates. Results indicated that Trichoderma were capable of bio-transforming T-2 toxin, HT-2 toxin, diacetoxyscirpenol and neosolaniol into their glycosylated forms and one Trichoderma strain could bio transform FA into low toxic fusarinol. These findings proved that Trichoderma isolates could manage toxigenic Fusarium via direct competition and volatile-mediated indirect inhibition. In addition, these antagonists possess defensive systems against mycotoxins for self-protection, which enriches our understanding on the interaction mechanism of Trichoderma spp. on toxigenic fungus.

The presence of organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) was analysed in air particulate matter ≤ 2.5 μm (PM₂.₅) and ≤10 μm (PM₁₀) collected in the Metropolitan Zone of Mexico Valley (MZMV), during 2013 and 2014, respectively. Spatial and seasonal distributions of PM and their organic content named solvent extracted organic matter (SEOM) were determined. PM mass concentration and SEOM/PM ratios were compared with previous studies in 2006 in Mexico City. PM₂.₅ concentration was like found in 2006, however, PM₁₀ decreased ∼43%. The SEOM/PM₁₀ ratio was kept constant, suggesting a decrease in SEOM as well as PM₁₀ emitted from natural sources, probably as a result of changes in the land use due to urban growth. A decrease ∼50% SEOM/PM₂.₅ ratio was observed in the same period, linked to adequate strategies and public policies applied by the local and federal governments to control the organic matter emitted from anthropogenic sources.Seven out of sixteen OCPs and five out of six PBDEs were found. The most common POPs were endosulfan I, endosulfan II, endosulfan sulfate, BDE-47 and BDE-99, present on >90% of the sampling days. OCPs in PM₂.₅ and PBDEs in PM₁₀ showed seasonal variability. Higher PBDEs concentration in both particle sizes were observed at east and southeast of the MZMV, where one of the biggest landfills and wastewater treatment plants are located. OCPs in PM₁₀ were mainly emitted from agricultural areas located to the southwest, southeast and east of the MZMV. OCPs in PM₂.₅ showed a regional contribution from the north and introduced into the valley. OCP degradation products were dominant over native OCPs, indicating no fresh OCP use. POPs comparison with other cities was made. Agreements and commissions created by the Mexican government reduced OCPs emissions, however, more effort must be made to control PBDE emission sources.