Photoaging is an important reaction for waste plastics in the aquatic environment and plays a key role in the lifetime of plastics. Nevertheless, when natural photosensitive substances such as nitrate participate in this process, the physiochemical changes in plastics and the corresponding reaction mechanisms are not well-understood. In this work, the photochemical behavior of polyethylene terephthalate (PET) bottles in deionized water and nitrate solution was systematically investigated under ultraviolet (UV) irradiation. The analyses of the surface physicochemical properties of the photoaged PET bottles indicated that, after 20 days of photo-irradiation, the presence of nitrate reduced the contact angle from 69.8 ± 0.9° to 60.0 ± 0.3°, and increased the O/C ratio from 0.23 to 0.32, respectively. The leaching rate of dissolved organic carbon (DOC), which was 0.0193 mg g⁻¹·day⁻¹ in nitrate solution, was twice that of 0.00941 mg g⁻¹·day⁻¹ in deionized water. Furthermore, fluorescence spectroscopy revealed that the increasing DOC had aromatic rings with hydroxyl on the side-chain formed after UV irradiation. The positive effect of nitrate on the degradation of PET bottles was mainly through the generation of hydroxyl radicals that were produced through the photolysis of nitrate. In addition, two-dimensional correlation spectroscopy analysis showed that the chain scission of PET plastics could be initiated by nitrate-induced ·OH attacking the carbon-oxygen bonds instead of forming peroxides with oxygen. This work elucidates the mechanism of photodegradation of plastics that was induced by nitrate and highlights the important role of natural photosensitive substances in the photoaging process of plastics.

Forest management can alter the mobilization of mercury (Hg) into headwater streams and its conversion to methylmercury (MeHg), the form that bioaccumulates in aquatic biota and biomagnifies through food webs. As headwater streams are important sources of organic materials and nutrients to larger systems, this connectivity may also increase MeHg in downstream biota through direct or indirect effects of forestry on water quality or food web structure. In this study, we collected water, seston, food sources (biofilm, leaves, organic matter), five macroinvertebrate taxa and fish (slimy sculpin; Cottus cognata) at 6 sites representing different stream orders (1–5) within three river basins with different total disturbances from forestry (both harvesting and silviculture). Methylmercury levels were highest in water and some food sources from the basin with moderate disturbance (greater clearcutting but less silviculture). Water, leaves, stoneflies and fish increased in MeHg or total Hg along the river continuum in the least disturbed basin, and there were some dissipative effects of forest management on these spatial patterns. Trophic level (δ¹⁵N) was a significant predictor of MeHg (and total Hg in fish) within food webs across all 18 sites, and biomagnification slopes were significantly lower in the basin with moderate total disturbance but not different in the other two basins. The elevated MeHg in lower trophic levels but its reduced trophic transfer in the basin with moderate disturbance was likely due to greater inputs of sediments and of dissolved organic carbon that is more humic, as these factors are known to both increase transport of Hg to streams and its uptake in primary producers but to also decrease MeHg bioaccumulation in consumers. Overall, these results suggest that the type of disturbance from forestry affects MeHg bioaccumulation and trophic transfer in stream food webs and some longitudinal patterns along a river continuum.

The popular paradigm in trophic dynamic theory is that contemporary autochthonous organic matter (e.g., phytoplankton) sustains consumer growth, whereas aged allochthonous organic matter is conceptually considered recalcitrant resources that may only be used to support consumer respiration but suppress consumer growth. This resource-age paradigm has been challenged by a growing body of recent evidence that ancient (radiocarbon depleted) organic carbon (OC) released from glaciers and permafrost can be incorporated by consumers in aquatic systems. However, little information is available regarding the food quality of ancient terrestrial OC and how it impacts the growth of consumers in lakes. Here, ancient dissolved organic carbon (DOC) was extracted from frozen soils in an alpine lake catchment. The contents of polyunsaturated fatty acids (PUFAs) in soil DOC increased significantly after bioconversion by heterotrophic bacteria. The utilization of soil DOC by heterotrophic bacteria also increased the total phosphorus concentration in the systems. Gammaproteobacteria and Betaproteobacteria showed a strong negative correlation with the percentage contents of fluorescent components, including humic-like and tyrosine-like components. Daphnia magna were fed Auxenochlorella vulgaris and ancient DOC plus heterotrophic bacteria. The contents of PUFAs and the growth of zooplankton were influenced by the pre-conversion time of ancient DOC by bacteria. When ancient DOC was pre-converted by bacteria for 27 days, D. magna fed on the mixed diets showed the highest body length (3.40 mm) and intrinsic rate of increase in population (0.49 d⁻¹). Our findings provide direct evidence that ancient terrestrial OC can be an important subsidy for lake secondary production, which have important implications for food webs in high-altitude and polar lakes.

Antimony (Sb) and arsenic (As) are chemical analogs, but their behaviors in plants are different. To investigate the Sb uptake, translocation and speciation in As-hyperaccumulator P. cretica, a hydroponic experiment was conducted. In this study, P. cretica was exposed to 0.2-strength Hoagland nutrient solution, which contained 0.5 or 5 mg/L antimonite (SbIII) or antimonate (SbV). After 14 d exposure, P. cretica took up 1.4–2.8 times more SbIII than SbV. Since P. cretica was unable to translocate Sb, its roots accumulated >97% Sb with the highest at 7965 mg/kg. In both SbIII and SbV treatments, SbIII was the predominant species in P. cretica, with 90–100% and 46–100% SbIII in the roots. As the first barrier against Sb to enter plant cells, more Sb was accumulated in cell wall than cytosol or organelles. The results suggest that P. cretica may detoxify Sb by reducing SbV to SbIII and immobilizing it in root cell walls. Besides, the presence of SbIII significantly reduced the concentrations of dissolved organic C including organic acids in P. cretica root exudates. Further, increasing Sb levels promoted P accumulation in the plant, especially in the fronds, which may help P. cretica growth. The information from this study shed light on metabolic transformation of Sb in As-hyperaccumulators P. cretica, which helps to better understand Sb uptake and detoxification by plants.

This study examined the effect of tetracycline addition on arsenic (As) mobilization and biotransformation in two contrasting soils (upland soil and paddy soil) under flooded conditions. The soils with added tetracycline (0–50 mg kg⁻¹) were incubated for 30 days, and soil properties and microbial functional genes over time were quantified. Tetracycline significantly promoted As reduction and As release into porewater in both soils. The enhancement had resulted from an increase in the concentration of dissolved organic carbon and a decrease in soil redox potential. Tetracycline also increased the abundances of As-reducing genes (arsC and arrA) and the relative abundances of As-reducing bacteria Streptomyces, Bacillus, Burkholderia, Clostridium and Rhodococcus, all of which have been found resistant to tetracycline. These genera play a key part in stimulating As reduction in the presence of tetracycline. The study indicated the significance of tetracycline in the biochemical behavior of As in flooded soils and provided new insights into the potential effects of tetracycline on the quality and safety of agricultural products in the future.

Biochar-oxalic acid composite application (BCOA) have shown to be efficient in the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soil, but the functional degraders and the mechanism of improving biodegradation remains unclear. In this study, with the help of stable isotope probing technology of phenanthrene (Phe), we determined that BCOA significantly improved Phe mineralization by 2.1 times, which was ascribed to the increased numbers and abundances of functional degraders. The BCOA increased contents of dissolved organic carbon and available nutrients and decreased pH values in soil, thus promoting the activity, diversity and close cooperation of the functional Phe-degraders, and stimulating their functions associated with Phe degradation. In addition, there is a relay activity among more and diverse functional Phe-degraders in the soil with BCOA. Specifically, Pullulanibacillus persistently participated in Phe-degradation in the soil with BCOA throughout the incubation period. Moreover, Pullulanibacillus, Blastococcus, Alsobacter, Ramlibacter, and Mizugakiibacter were proved to be potential Phe-degraders in soil for the first time. The specific Phe degraders and their relay and cooperation activity in soils as impacted by BCOA were first identified with DNA-stable isotope probing technology. Our findings provided a novel perspective to understand the efficient degradation of PAH in the BCOA treatments, revealed the potential of soil native microbes in the efficient bioremediation of PAH-contaminated natural soil, and provided a basis for the development of in-situ phytoremediation technologies to remediate PAH pollution in future.

Sediment dissolved organic matter (DOM) in inland waters is commonly affected by environmental changes. However, knowledge about how sediment DOM responds to eutrophication and the associations between sediment DOM and bacterial communities requires further investigation. We selected a sediment core from Dianchi Lake (China) that was dated from 1864 to 2019 by the activity of radionuclides (²¹⁰Pb and ¹³⁷Cs). δ¹³CDOC changes fit well with the historical record that heavy eutrophic status in Dianchi Lake were observed since 1980s. Large amounts of dissolved organic carbon (DOC), chromophoric (CDOM) and fluorescent (FDOM) DOM accumulated at the top of the sediments during the eutrophication period (1982-present). The additional algae sources with a higher degradation rate altered the composition, aromaticity and humification of DOM. After long-term mineralization, the remaining DOM became more and more recalcitrant and kept a relatively stable level at older sediments. A co-occurrence network analysis revealed that Proteobacteria, Chloroflexi, Acidobacteriota, Bacteroidota and Desulfobacterota were the most abundant species at the phylum level and clustered into three primary modules. Different microbes shared unique preferences for niches, causing a heterogeneous bacterial distribution at different depths. We conducted Spearman's correlation and redundancy analysis (RDA) to explore potential interactions between bacterial community and sediment DOM. The richness and diversity of bacterial communities were positively related to DOM content, suggesting abundant DOM can produce more available resources for bacteria. RDA results showed some specific species might modify DOM composition and structure. This study suggests that sediment DOM properties were regulated by source transformation during eutrophication, and emphasizes the importance of microbial role on sediment biogeochemical process.

Straw and biochar amendments have been shown to increase soil organic carbon (SOC) stocks in arable land; however, their effects on hydrological fluxes of dissolved organic carbon (DOC), which may offset the benefits of C sequestration amounts remain uncertain. Therefore, we conducted a three-year field study that included four treatments (CK, control with no fertilizer; NPK, synthetic N fertilizer; RSDNPK, synthetic N fertilizer plus crop residues; BCNPK, synthetic N fertilizer plus biochar of crop straw) to investigate the effects of straw and biochar amendment on DOC losses through hydrological pathways of overland flow and interflow from a wheat-maize rotation system in the subtropical montane agricultural landscape. We detected substantial intra- and inter-annual variations in runoff discharge, DOC concentration, and DOC fluxes for both overland flow and interflow pathways, which were primarily attributed to variations in rainfall amount and intensity. On average, the DOC concentrations for interflow (2.98 mg C L⁻¹) were comparable with those for overland flow (2.71 mg C L⁻¹) throughout the three-year experiment. However, average annual DOC fluxes for interflow were approximately 2.60 times greater than those for overland flow, which probably related to higher runoff discharges of interflow than overland flow. Compared to the control, on average, the N fertilization treatments significantly decreased the annual DOC fluxes of overland flow and significantly increased annual DOC fluxes of interflow. Relative to the application of synthetic N fertilizer only, on average, crop straw amendment practice significantly increased annual DOC fluxes of interflow by 28.7%, while decreasing annual DOC fluxes of overland flow by 12.0%; in contrast, biochar amendment practice decreased annual DOC fluxes of interflow by 25.3% while increasing annual DOC fluxes of overland flow by 44.6%. Overall, considering both overland flow and interflow, crop straw amendment significantly increased hydrological DOC fluxes, whereas biochar had no significant effects on hydrological DOC fluxes throughout the three-year experiment. We conclude that crop straw incorporation strategies that aim to increase SOC stocks may enhance hydrological losses of DOC, thereby in turn offsetting its benefits in the subtropical montane agricultural landscapes.

Identifying the bioavailability and release-desorption mechanism of heavy metals (HMs) in soil is critical to understand the release risk of HMs. Simultaneously, the mechanistic investigation of affecting the bioavailability of HMs in soil is necessary, such as the grain-size distribution and soil mineralogy. Herein, the bioavailability of HMs (Cu, Cd, Ni, Pb, and Zn) in different area soils near a typical copper-smelter was evaluated by the sequential extraction technique (BCR), diffusive gradients in thin-films (DGT), and DGT-induced fluxes in sediments (DIFS) model. Results showed that the HMs proportion of the residual fraction in all soils was the highest. The average bioavailability concentration (CDGT) of Cu and Cd in industrial soil was the highest, with 45.12 μg· L⁻¹ and 9.06 μg· L⁻¹. The result of DIFS model revealed that the decreased order of the mean value of desorption rate constant (K₋₁) was Cd > Zn > Ni > Cu > Pb, 5.91 × 10⁻⁵, 4.96 × 10⁻⁵, 2.89 × 10⁻⁵, 9.64 × 10⁻⁶, and 8.69 × 10⁻⁶, respectively. According to the spatial distribution of release potential (R-value), the release potential of labile-Cu in agricultural soil was the highest, which was mainly attributed to fertilizer application in farmland. Simultaneously, the reduced hydroxyl was also related to the agricultural activities, resulting in the weakened adsorption capacity of HMs by soil. Redundancy analysis (RDA) results showed that the bioavailability of Cd, Ni, and Zn was mainly driven by soil pH, while the bioavailability of Cu and Pb was primarily driven by dissolved organic carbon (DOC). Meanwhile, carbonate minerals had a positive correlation with the bioavailability of Cd, Ni, and Zn, which could promote the release of HMs in mining soil as chemical weathering progresses. In conclusion, this study provides a structured method which can be used as a standard approach for similar scenarios to determine the geochemical fractionation, bioavailability, and release kinetics of heavy metals in soils.

Riverine carbon (C) composition and export are closely related to changes in the coastal environment and climate. Excessive C inputs from rivers to seas and their subsequent decomposition could result in harmful algal blooms and ecosystem degradation in the coastal sea. In this study, we explored the C transportation and composition in the 24 major rivers of the Bohai Sea (BS) Rim based on the investigation of dissolved organic carbon (DOC), carbon stable isotopes (δ¹³CDOC) and chromophoric dissolved organic matter (CDOM). The results showed that the riverine DOC concentrations were high (10.6 ± 6.04 mg/L) in the BS Rim compared with the DOC levels in the main rivers in Eastern China (4.98 ± 2.45 mg/L). The δ¹³CDOC ranged from −28.29‰ to −25.32‰ in the rivers of the BS Rim, suggesting that the DOC mainly originated from riverine plankton, soil organic matter mainly induced by C3 plants, and sewage. The excitation-emission matrix fluorescence spectroscopy of the CDOM indicated that a soluble, microbial by product-like material accounted for the largest proportion (approximately 40%) of CDOM in these rivers and that CDOM mainly originated from autochthonous riverine sources with high protein-like components. The rivers in the BS Rim transported approximately 0.55 Tg C of DOC to the BS each year, with more than 70% of reactive C based on the CDOM composition. The DOC yields in terms of unit drainage area transported from the small rivers to the BS were higher compared to those of the larger rivers in the world, which indicated that the small rivers in the Bohai Rim could be an important source of the C in the BS. This study would enrich our understanding of environmental evolution in coastal areas with numerous small rivers.