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.

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.

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.

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.

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.

With the upgrade of wastewater treatment plants (WWTPs) to meet more stringent discharge limits for nutrients, dissolved organic nitrogen (DON) is present at an increasing percentage (up to 85%) in the effluent. Discharged DON is of great environmental concern due to its potentials in stimulating algal growth and forming toxic nitrogenous disinfection by-products (N-DBPs). This article systematically reviewed the characteristics, transformation and ecological impacts of wastewater DON. Proteins, amino acids and humic substances are the abundant DON compounds, but a large fraction (nearly 50%) of DON remains uncharacterized. Biological treatment processes play a dominant role in DON transformation (65–90%), where DON serves as both nutrient and energy sources. Despite of the above progress, critical knowledge gaps remain in DON functional duality, relationship with dissolved inorganic nitrogen (DIN) species, and coupling/decoupling with the dissolved organic carbon (DOC) pool. Development of more rapid and accurate quantification methods, modeling transformation processes, and assessing DON-associated eutrophication and N-DBP formation risks should be given priority in further investigations.

Dissolved organic matter (DOM) is recognized as a good indicator of water quality as its concentration is influenced by land use, rainwater, windborne material and anthropogenic activities. Recent technological advances make it possible to characterize fluorescent dissolved organic matter (FDOM), the fraction of DOM that fluoresces. Among these advances, portable fluorometers and benchtop fluorescence excitation and emission spectroscopy coupled with a parallel factor analysis (EEM-PARAFAC) have shown to be reliable. Despite their rising popularity, there is still a need to evaluate the extent to which these techniques can assess DOM dynamics at the watershed scale. We compare the performance of in-situ measurements of FDOM with laboratory measurements of fluorescence spectroscopy within the context of two distinct glacierized watersheds in Peru. Glacierized watersheds represent unique testing environments with contrasting DOM conditions, flowing from pristine, vegetation-free headwaters through locations with obvious anthropogenic influences. We used an in-situ fluorometer and a portable multimeter to take 38 measurements of FDOM, pH and turbidity throughout the two catchments. Additionally, samples were analyzed in the laboratory using the EEM-PARAFAC method. Results were compared to dissolved organic carbon (DOC) measurements using standard high-temperature catalytic oxidation. Our results show that the three techniques together were able to capture the DOM dynamics for both studied watersheds. Taken individually, all three methods allowed detection of the watershed DOM main points of sources but in a more limited way. Due to the narrow bandwidth of the portable fluorometer used in the study, FDOM measurements were almost non-detectable to protein-like substances. Indeed, the more demanding EEM-PARAFAC was able to both differentiate between potential sources of DOM and provide an estimate of relative concentrations of different organic components. Finally, similar to FDOM but to a lesser extent, the DOC measurements showed some limits where protein-like substances make up most of the DOM composition.

Aquatic macrophytes play a significant role in nutrients removal in constructed wetlands, yet nutrients could be re-released due to plant debris decomposition. In this study, Myriophyllum aquaticum was used as a model plant debris and three debris biomass levels of 3 g, 9 g dry biomass, and 20 g fresh biomass (D3, D9, and F20, respectively) were used to simulate 120-d plant debris decomposition in a sediment-water system. The biomass first-order decomposition rate constants of D3, D9, and F20 treatments were 0.0058, 0.0117, and 0.0201 d⁻¹, respectively with no significant difference of decomposition rate among three mass groups (p > 0.05). Plant debris decomposition decreased nitrate and total nitrogen concentrations but increased ammonium, organic nitrogen, and dissolved organic carbon (DOC) concentrations in overlying water. The parallel factor analysis confirms that three components of DOC in overlying water changed over decomposition time. Emission fluxes of methane and nitrous oxide in the plant debris treatments were several to thousands of times higher than the control group within the initial 0–45 d, which was mainly attributed to DOC released from the plant debris. Plant debris decomposition can affect the gas emission fluxes for relatively shorter time (30–60 d) than water quality (>120 d). The 16S rRNA, nirK, nirS and hazA gene abundance increased in the early stage for plant debris treatments, and then decreased to the end of 120-d incubation time while ammonia monooxygenase α-subunit A gene abundance of ammonia-oxidizing archaea and bacteria had no large variations during the entire decay time compared with no plant debris treatment. The results demonstrate that decomposition of M. aquaticum debris could affect greenhouse gas emission fluxes and microbial gene abundance in the sediment-water system besides overlying water quality.

Dissolved organic carbon (DOC) is not only a critical component of global and regional carbon budgets, but also an important precursor for carcinogenic disinfection byproducts (DBP) generated during drinking water disinfection process. The lack of process based watershed scale model for carbon cycling has been a limiting factor impeding effective watershed management to control DOC fluxes to source waters. Here, we integrated terrestrial and aquatic carbon processes into the widely tested Soil and Water Assessment Tool (SWAT) watershed model to enable watershed-scale DOC modeling (referred to as SWAT-DOC hereafter). The modifications to SWAT mainly fall into two groups: (1) DOC production in soils and its transport to aquatic environment by different hydrologic processes, and (2) riverine transformation of DOC and their interactions with particular organic carbon (POC), inorganic carbon and algae (floating and bottom). We tested the new SWAT-DOC model in the Cannonsville watershed, which is part of the New York City (NYC) water supply system, using long-term DOC load data (from 1998 to 2012) derived from 1399 DOC samplings. The calibration and verification results indicate that SWAT-DOC achieved satisfactory performance for both streamflow and DOC at daily and monthly temporal scales. The parameter sensitivity analysis indicates that DOC loads in the Cannonsville watershed are controlled by the DOC production in soils and its transport in both terrestrial and aquatic environments. Further model uncertainty analysis indicates high uncertainties associated with peak DOC loads, which are attributed to underestimation of high streamflows. Therefore, future efforts to enhance SWAT-DOC to better represent runoff generation processes hold promise to further improve DOC load simulation. Overall, the wide use of SWAT and the satisfactory performance of SWAT-DOC make it a useful tool for DOC modeling and mitigation at the watershed scale.

Dissolved organic carbon (DOC) has a major influence upon sorption/desorption and transport of hydrophobic organic contaminants (HOCs) in soil environments. However, the molecular mechanisms of DOC sorption and its effects on aged HOC desorption in contaminated soils still remain largely unclear. Here, effects of three different DOC (one from commercial peat and two from biochars produced at 300 °C and 500 °C pyrolysis temperatures, respectively) and oxalate (as a reference) on abiotic desorption behavior of aged phenanthrene from three agricultural soils were investigated. Results showed that desorption of aged phenanthrene from soils was predominantly dependent on soil organic carbon content. The presence of DOC and oxalate resulted in higher desorption of phenanthrene compared to water alone, and the effects were positively related to soil organic carbon content and DOC/oxalate concentration. The facilitating effects of DOC were further increased during the second consecutive desorption, whereas oxalate had no such effect. Ultra-high-resolution Fourier transform-ion cyclotron resonance-mass spectrometry confirmed the molecular fractionation of DOC at the soil-water interface during DOC sorption. Specifically, the DOC molecules with O-rich moieties were preferentially adsorbed, whereas the molecules with phenolic and aromatic structures were selectively retained in the soil solutions through competitive displacement and co-sorption reactions during sorption. The enriched phenyl structures in the retained DOC facilitated its association with phenanthrene in the solutions and thus the release of phenanthrene from the soils. In contrast, oxalate replaced some organic carbon from the soils and thus released the associated phenanthrene into the solutions. Our findings highlight the importance of the molecular composition and structure of DOC for the desorption of phenanthrene in soil-water environments, which may help improve our understanding of the release and transport of organic compounds in the environments.