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.

Forest and agricultural land use affects the concentration and composition of dissolved organic carbon (DOC) in streams and rivers. To elucidate the impacts of forest and agricultural land use on stream DOC during storm events, we investigated DOC concentration ([DOC]), optical properties of dissolved organic matter (DOM), and Δ¹⁴C-DOC in both forest- and agriculture-dominated headwater streams in South Korea in the summer of 2012. One forested and five agricultural streams were investigated. During storms, the peak [DOC] of forest stream increased to 5.8 mg L⁻¹, approximately two times larger than that of the most agricultural stream (3.2 mg L⁻¹), demonstrating the weaker storm responses of the [DOC] of agricultural streams to hydrological change. Five PARAFAC components were identified, including three terrestrial humic-like substances (C1, C2, C3), one microbial humic substance (C4), and one microbial protein-like substances (C5). The mean (C4+C5)/(C1+C2+C3) of all storm events at the most agricultural stream was 1.5 times larger than that of the most forested stream, suggesting that more protein-like DOM is exported from agricultural watersheds. Whereas a forest stream was primarily composed of terrestrially derived and ¹⁴C-enriched modern DOC, the ¹⁴C-age of the most agricultural stream was up to ∼1000 years old. The results suggest that agricultural practices could decrease the old organic carbon pools from soils. However, how quickly the aged DOC can be degraded to CO₂ in streams is unknown, warranting future investigation on lability of the aged DOC and their effects on CO₂ evasion from rivers and estuaries downstream.

The Yellow River is the second largest river in China. Carbon transport by the Yellow River has significant influence on riverine carbon cycles in Asia. During the wet season, the riverine carbon was mainly found in dissolved form, i.e., dissolved organic carbon (DOC), along the entire course of the river. The distinct spatial variations of DOC concentration were observed at different reaches of the mainstream (p < 0.01), while the highest mean DOC concentration was generally observed at midstream (4.13 ± 0.91 mg/L). Carbon stable isotope analysis δ¹³C and C: N ratio of DOC, evidenced the sources of DOC in headwater and upstream were primarily the terrestrial plants (94% and 61%), but it was changed to soil organic matter (SOM) in mid- and downstream (36% and 37%), and the contribution of sewage to DOC were also increased to 17% and 18%. In the whole mainstream of the Yellow River, water temperature (WT) had a significant impact on DOC concentration, and it could explain 67% of the DOC variance. However, in a large catchment, the driving mechanisms on the DOC variations in headwaters will not necessarily be those controlling DOC trends in downstream. The study firstly quantified, in headwater and upstream, the natural factors explained as much as 65% and 73% of the DOC variations, respectively. In mid- and downstream areas, DOC was significantly influenced by the amount of wastewater discharged by the industry and the use of chemical fertilizers (p < 0.05). These findings may facilitate a better assessment of global riverine carbon cycling and may help to reveal the importance of the balance between development and environmental sustainability with the changing DOC transport features in the Yellow River due to human disturbances.

Restoring woody vegetation to riparian zones helps to protect waterways from excessive sediment and nutrient inputs. However, the associated leaf litter can be a major source of dissolved organic matter (DOM) leached into surface waters. DOM can lead to the formation of disinfection by-products (DBPs) during drinking water treatment. This study investigated the DBPs formed during chlorination of DOM leached from leaf litter and assessed the potential toxicity of DBPs generated. We compared the leachate of two native Australian riparian trees, Casuarina cunninghamiana and Eucalyptus tereticornis, and a reservoir water source from a catchment dominated by Eucalyptus species. Leachates were diluted to dissolved organic carbon concentrations equivalent to the reservoir (~9 mg L⁻¹). E. tereticornis leachates produced more trihalomethanes (THMs), haloacetic acids (HAAs), and haloketones after chlorination, while C. cunninghamiana produced more chloral hydrate and haloacetonitriles. Leachate from both species produced less THMs and more HAAs per mole of carbon than reservoir water. This may be because reservoir water had more aromatic, humic characteristics while leaf leachates had relatively more protein-like components. Using in vitro bioassays to test the mixture effects of all chemicals, chlorinated E. tereticornis leachate induced oxidative stress in HepG2 liver cells and bacterial toxicity more frequently and at lower concentrations than C. cunninghamiana and reservoir water. Overall, this study has shown that the DOM leached from litter of these species has the potential to generate DBPs and each species has a unique DBP profile with differing bioassay responses. E. tereticornis may pose a relatively greater risk to drinking water than C. cunninghamiana as it showed greater toxicity in bioassays. This implies tree species should be considered when planning riparian zones to ensure the benefits of vegetation to waterways are not offset by unintended increased DBP production and associated toxicity following chlorination at downstream drinking water intakes.

Atmospheric nitrogen (N) deposition is believed to accelerate dissolved organic carbon (DOC) production and could lead to increased heavy metal mobility into water resources. We sampled intact soil cores from the Isle of Skye with low background N deposition history and having Serpentine rock known for its higher heavy metal concentrations including zinc (Zn), copper (Cu), nickel (Ni) and lead (Pb). The effects of 16 (16kgN) and 32 kg N ha⁻¹ year⁻¹ (32kgN), and liming with 32kgN (32kgN+Lime) on soil solution chemistry and heavy metal mobilization were investigated over the 15-month study. Nitrogen in deposition load was added at five ammonium (NH₄⁺) to nitrate (NO₃⁻) ratios of 9:1, 5:1, 1:1, 1:5 and 1:9 along NO₃⁻dominance. We found significant effects of load on Cu and NH₄⁺/NO₃⁻ ratio on pH, DOC and Zn in soil solution. However, under lime and ratio experimental factors, liming significantly influenced pH, DOC, Cu and Pb, and NH₄⁺/NO₃⁻ ratio pH, DOC, Ni and Zn whereas interactions between lime and ratio was significant for Ni and Cu. pH and DOC increased with N load, liming and NO₃⁻ dominance, and both correlated significantly positively. Liming under NH₄⁺ dominance enhanced DOC production due to supply of base cations in lime. Mobilization of Cu, Ni and Pb was driven by DOC concentrations and, therefore, increased with load, liming and NO₃⁻ dominance in deposition. However, in contrast, low pH and high NH₄⁺ dominance was associated with Zn mobilization in soil solution. On the contrary, despite of some patterns, heavy metals in soil HNO₃ extracts were devoid of any load, lime and NH₄⁺/NO₃⁻ ratio effects. Our study suggests that the effects of N load and forms in deposition on sites with high accumulated loads of metals need to be better quantified through soil solution partitioning models.

Nitrous oxide (N2O) is a devastating greenhouse gas mainly released from soils to the atmosphere. Pasture soils, particularly acidic in nature, are large contributors of atmospheric N2O through deposition of urine-N. Devising strategies for reducing N2O emissions in acidic soils are the utmost need of the time. Therefore, the present study was carried out to investigate the possible efficacy of dolomite application to reduce N2O emissions from urine treated acidic soil. Application of urine to soil enlarged the production of NH4+-N, NO3−-N, microbial biomass C (MBC) and dissolved organic C (DOC), resulting in higher N2O emissions as compared to the control (soil only). The highest N2O emission rate (1.35 μg N2O-N kg−1 h−1) and cumulative flux (408 μg N2O-N kg−1) occurred in urine only treated soil. Dolomite addition, especially higher application dose, greatly reduced N2O emissions through improved soil pH. The results suggest that increasing pH of acidic soils is a good applicable approach for reducing N2O emissions from urine-treated soils.