Labile dissolved organic matter (DOM) and nitrogen inputs modified greenhouse gas dynamics: A source-to-estuary study of the Yangtze River.

Although rivers are increasingly recognized as essential sources of greenhouse gases (GHG) to the atmosphere, few systematic efforts have been made to reveal the drivers of spatiotemporal variations of dissolved GHG (dGHG) in large rivers under increasing anthropogenic stress and intensified hydrological cycling. Here, through a source-to-estuary survey of the Yangtze River in March (spring) and October (autumn) of 2018, we revealed that labile dissolved organic matter (DOM) and nitrogen inputs remarkably modified the spatiotemporal distribution of dGHG. The average partial pressure of CO2 (pCO2), CH4 and N2O concentrations of all sampling sites in the Yangtze River were 1015 ± 225 µatm, and 87.5± 36.5 nmol L-1, and 20.3 ± 6.6 nmol L-1, respectively, significantly lower than the global average. In terms of longitudinal and seasonal variations, higher GHG concentrations were observed in the middle-lower reach in spring. The dominant drivers of spatiotemporal variations in dGHG were labile, protein-like DOM components and nitrogen level. Compared with the historical data of dGHG from published literature, we found a significant increase in N2O concentrations in the Yangtze River during 2004-2018, and the increasing trend was consistent with the rising riverine nitrogen concentrations. Our study emphasized the critical roles of labile DOM and nitrogen inputs in driving the spatial hotspots, seasonal variations and annual trends of dGHG. These findings can contribute to constraining the global GHG budget estimations and controls of GHG emission in large rivers in response to global change.

Roles of dissolved organic matter (DOM) in shaping the distribution pattern of heavy metal in the Yangtze River.

Dissolved organic matter (DOM) strongly influences the solid-liquid partitioning and migration characteristics of heavy metals, yet little is known about the metal distribution and risk with the participation of DOM in large riverine systems. This study investigated the spatiotemporal distribution of 14 heavy metals and DOM along the entire Yangtze River (over 6000 km), and highlighted the critical roles of DOM in regulating the environmental behaviors of heavy metals. Significant spatial variations of metal contents were observed, with the river source and lower reach remarkably different from the upper-middle reaches. Heavy metals in the Yangtze River were mainly from the natural sources with minor anthropogenic disturbance. We found DOM could promote the conversion of metals from solid to liquid phase and DOM with higher aromaticity showed higher metal affinities. Although low ecological risks were observed in the Yangtze River, potential risks of metal leaching warrant attention, especially for As, Cd and Sb in the middle-lower reaches with higher DOM content and aromaticity. This study established a source-to-sea investigative approach to evaluate the influences of DOM features on metal partitioning, which is crucial for the risk control and sustainable management of large rivers.

Occurrence, distribution and risk assessment of polycyclic aromatic hydrocarbons in soils around main water source areas of Beijing, China.

Polycyclic aromatic hydrocarbons (PAHs) in urban environments have been globally concerned due to their significant health impacts on residents. However, little is known about potential risks of PAHs from centralized water source areas. In the present study, 326 soils samples from the main water source areas of Beijing were collected and the occurrence, source appointment, and risks of PAHs were systematically investigated based on the monitoring results from high-performance liquid chromatography (HPLC). The total PAHs (∑16 PAHs) concentrations ranged from 5.70 to 1512 ng/g with median value of 44.2 ng/g, in which 4-ring and 5-ring groups were the major components. PAHs concentrations in the cultivated land were significantly higher than other areas, which could reflect significant impact of soil organic matter and total nitrogen contents on the spatial variations of PAHs. Further source identifications through positive matrix factorization model (PMF) revealed that biomass (22.5%), coal (21.4%), gasoline (17.6%) and diesel (16.4%) combustion were dominant sources of soil PAHs in the study area. Moreover, the risk assessment indicated that total ecological and health risk of PAHs were negligible, but individual PAH, including pyrene and benzo(b)fluoranthene, should be concerned due to their potential risks in several monitored stations located in the secondary protection area of four reservoirs. Our study provided new insights into environmental risks of soils in main water source areas from PAHs and could be helpful for organic micropollutant controlling and drinking water safety in rapidly urbanizing cities.

Distribution, source identification, and health risk of emerging organic contaminants in groundwater of Xiong'an New Area, Northern China.

Groundwater contamination in China has been greatly concerned due to dramatically increasing fresh water demand accompanied by economic development. However, little is known about aquifer vulnerability to hazardous matters especially in previously contaminated site of rapidly urbanizing cities. Here, we collected 90 groundwater samples from Xiong'an New Area during wet and dry seasons of 2019 and characterized the composition and distribution of emerging organic contaminants (EOCs) in this strategically developing city. A total of 89 EOCs, assigned to organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and volatile organic compounds (VOCs), were detected with the frequencies ranging from 1.11 %-85.6 %. Methyl tert-butyl ether (16.3 µg/L), Epoxid A (6.15 µg/L), and α-Lindane (5.15 µg/L) could be identified as major contributors to groundwater organic pollution. Significant aggregation of groundwater EOCs along Tang River were found due to historical residue and accumulation from wastewater storage there before 2017. Significant seasonal variations (p < 0.05) in the types and concentrations of EOCs could be attributed to discrepant pollution sources between varying seasons. Human health effects from exposure to groundwater EOCs were further evaluated with negligible risk (<10-4) in most samples (97.8 %) and notable risk (10-6-10-4) in several monitored wells (2.20 %) located along Tanghe Sewage Reservoir. This study provides new evidences for aquifer vulnerability to hazardous matters in historically contaminated sites and is of significant to groundwater pollution controlling and drinking water safety for rapidly urbanizing cities.

Deficiency and excess of groundwater iodine and their health associations.

More than two billion people worldwide have suffered thyroid disorders from either iodine deficiency or excess. By creating the national map of groundwater iodine throughout China, we reveal the spatial responses of diverse health risks to iodine in continental groundwater. Greater non-carcinogenic risks relevant to lower iodine more likely occur in the areas of higher altitude, while those associated with high groundwater iodine are concentrated in the areas suffered from transgressions enhanced by land over-use and intensive anthropogenic overexploitation. The potential roles of groundwater iodine species are also explored: iodide might be associated with subclinical hypothyroidism particularly in higher iodine regions, whereas iodate impacts on thyroid risks in presence of universal salt iodization exhibit high uncertainties in lower iodine regions. This implies that accurate iodine supply depending on spatial heterogeneity and dietary iodine structure optimization are highly needed to mitigate thyroid risks in iodine-deficient and -excess areas globally.

Electrochemical degradation of atrazine by BDD anode: Evidence from compound-specific stable isotope analysis and DFT simulations.

Direct charge transfer (DCT) and •OH attack played important roles in contaminant degradation by BDD electrochemical oxidation. Their separate contributions and potential bond-cleavage processes were required but lacking. Here, we carried out promising compound-specific isotope fractionation analysis (CSIA) to explore 13C and 2H isotope fractionation of atrazine (ATZ), followed by assessing the reaction pathway by BDD anode. The correlation of 2H and 13C fractionation allows to remarkably differentiate DCT process and •OH attack, with Λ values of 18.99 and 53.60, respectively. Radical quenching identified that •OH accounted for 79.0%-88.5% in the whole reaction. While CSIA methods provided biased results, which suggested that ATZ degradation exhibited two stages with •OH contributions of 24.6% and 84.3% respectively, confirming CSIA was more sensitive and provided more possibilities to estimate degradation processes. Combined with Fukui index and intermediate products identification, we deduced that dechlorination-hydroxylation mainly occurred in the first 30 min by DCT reaction. While lateral chain oxidation with C-N broken was the governing route once •OH was largely generated, with the production of DEA (m/z 188), DIA (m/z 174), DEIA (m/z 146) and DEIHA (m/z 128). Our results demonstrated that isotope fractionation can offer "isotopic footprints" for identifying the rate-limiting steps and bond breakage process, and opens new avenues for degradation pathways of contaminants.

Influences of isolated fractions of natural organic matter on adsorption of Cu(II) by titanate nanotubes.

With different functional groups and hydrophobic/hydrophilic properties, natural organic matters (NOMs) displayed different combining capacities with metal ions. By using XAD-4 and DAX-8 resins, NOMs in natural lake were isolated into three fractions, i.e., HoB (hydrophobic base), HoA (hydrophobic acid) and HiM (hydrophilic matter). Afterwards, influences on Cu(II) adsorption onto titanate nanotubes (TNTs) were compared with varying NOMs and initial pH. As results, HoB can significantly control Cu(II) adsorption at pH 5, with the adsorption capacity increased 15% for 0.5 mg L-1 of HoB (ca. 120 mg g-1), which could be attributed to the formation of HoB-Cu complexation and electrostatic bridge effect of HoB with optimal concentration. Due to the easier ionization and complexation with Cu(II) at lower pH, HoA showed more obvious impaction on Cu(II) adsorption at pH 2. While HiM can influence Cu(II) adsorption at all pH ranges due to its hydrophilic groups and weak affinity to both TNTs and Cu(II). Furthermore, HoB dramatically changed the Langmuir model, with sharp increase of adsorption capacity as equilibrium Cu(II) increased, suggesting its significant involvement in Cu(II) adsorption. X-ray photoelectron spectroscopy (XPS) analysis revealed the absorbed Cu(II) existed in the form of TNTs­OCu, TNTs­COOCu and Cu(OH)2, proving Cu(II) adsorption mechanism including both direct adsorption by TNTs and bridging connection with NOMs. Moreover, the CO and OCO groups content ranked as HiM > HoB > HoA, while TNTs­COOCu content ranked as HoA > HoB > HiM, suggesting HoB had the moderate connection with both TNTs and Cu(II), thus the impact on Cu(II) adsorption was remarkable.

[Characterization of Dissolved Organic Matter Fractions in the Ning-Meng Section of the Yellow River and Relationship with Metal Ions].

Dissolved organic matter(DOM)is an important element of natural aquatic systems. Due to differences in their hydrophobic/hydrophilic properties and various functional groups, chemical appearances of DOM fractions also vary. In this study, seven natural waters, extending from Xiaheyan to Toudaoguai along the Ning-Meng section of the Yellow river, were sampled in April 2015. Four DOM fractions were obtained by pumping through XAD-4 and XAD-8 resins, i.e., hydrophobic acid (HOA), hydrophobic base (HOB), weak hydrophobic acid (WHOA), and hydrophilic matter (HYI). Based on detection by three-dimensional excitation-emission matrix fluorescence (EEM) and correlation analysis, relationships with five metal ions (Pb, Zn, Cu, Cr, As) were analyzed. Results show that DOC gradually increased along an upstream to downstream continuum in the Ning-Meng section. HYI (small molecular proteins) was the main DOM fraction present, followed by HOA, suggesting enhanced microbial-sourced impact from industrial sewage discharges. The significant peaks of humic-like (A, C) and protein-like compounds (T1) in the EEM chart further highlight the effect of endogenous pollution caused by wastewater. Furthermore, SPSS fitting results indicate that DOM is correlated with all five metal ions, especially with Cu. In terms of the four DOM fractions, HYI showed the strongest correlation with Cu, illustrating the significant relationship between HYI and Cu during the migration and transformation process. Moreover, the fluorescence intensity of protein-like compounds decreased with increasing Cu concentration, possibly due to fluorescence quenching caused by complexation between Cu and proteins in HYI.

Simulated discharge of treated landfill leachates reveals a fueled development of antibiotic resistance in receiving tidal river.

Around 350 million tons of solid waste is disposed of in landfills every year globally, with millions of cubic meters of landfill leachates released into neighboring environment. However, to date, little is known about the variations of antimicrobial resistance (AMR) in on-site leachate treatment systems and its development in leachate-receiving water environment. Here, we quantified 7 subtypes of antibiotic resistance genes (ARGs), 3 types of culturable antibiotic resistant bacteria (ARB) and 6 subtypes of mobile genetic elements (MGEs) in the effluents from a combined leachate treatment process, including biological treatment (MBR), physical separation (UF), ultraviolet (UV) disinfection and advanced oxidation process (AOP). The contents of ARGs, ARB and MGEs were generally enriched by the MBR, but then decreased significantly along with the tertiary treatment process. However, in the effluent-receiving water samples, the abundance of dominant ARGs (i.e. ermB, sul1, blaTEM) increased by 1.5 orders of magnitude within 96 h, alongside a general increase of MGEs (~10.0 log10(copies/mL) and total ARB (~1100 CFU/mL). Structural correlation analyses reveal that target ARGs were closely associated with MGEs, particularly in effluent-receiving samples (Procrustes test; M2 = 0.49, R = 0.71, P = 0.001); and occurrences of ARB were majorly affected by ARG's distribution and environmental conditions (e.g. nitrogen speciation) in effluent and recipient groups, respectively. This study indicates that current treatment technologies and operation protocols are not feasible in countering the development of AMR in effluent-receiving water environment, particularly in tidal rivers that are capable of retaining contaminants for a long residence time.