Humic-like Components Research Articles

Deciphering riverine dissolved organic matter biodegradation: Evidence from three-dimensional fluorescence

Biological degradation contributes significantly to aquatic dissolved organic matter (DOM) turnover. Yet to date, the specific biological pathways involved in DOM degradation are still obscure. Here, we show how DOM changes in response to 28-d incubation in a karst river, via the combined fluorescent excitation-emission matrix (EEM) with parallel factor analysis (PARAFAC) and peak picking. Tyrosine-, tryptophan- and UV humic-like components were identified as the primary DOM in original waters. Notable decreases of protein-like components were observed after 15 ℃ incubation, suggesting preferential consumption of biogenic DOM. Elevated temperature (30 ℃), however, caused significant decreases in visible humic-like and terrestrial fulvic-like components, but an increase in UV humic-like components in comparison to 15 ℃ incubation (p < 0.05). Humification index (HIX) decreased dramatically after 15 ℃ incubation, indicating that biological processes regulated river DOM properties. Our results highlight the significant biogenic signals in karst rivers, and evidence that fluorescence measurement can decipher riverine DOM biodegradation as a useful approach.

Evaluation of persulfate enhanced electrocoagulation (EC/PS) for bio-treated landfill leachate: Organics transformation pathways and carbon flow quantitative analysis

The sulfate radical-based advanced oxidation processes (SR-AOPs) have shown promise in treating bio-treated landfill leachate (BLL). However, little is known about the dissolved organic matter (DOM) transformation and reaction mechanisms at the molecular level after treating BLL using SR-AOPs. This study investigates the DOM degradation and transformation pathways during both electrocoagulation (EC) and persulfate enhanced electrocoagulation (EC/PS) of real BLL samples. The results indicate that the removal efficiency of chemical oxygen demand (COD) and total organic carbon (TOC) were enhanced to 46.34% and 36.39%, respectively, once persulfate is coupled with EC. Additionally, the removal of fluorescent contaminants in BLL significantly enhanced after treatment with EC/PS to 91.57%, 80.99%, and 39.10% for biogenic humic-like components C1, C2, and C3, respectively. A decrease in the proportion of macromolecular and aromatic matters was observed after the EC/PS process. The degree of oxidation of DOM was reduced, and the compounds with unstable structure and high biodegradability became the main compounds in the EC/PS effluent. The analysis of sediments generated by EC and EC/PS showed a similar composition of FeOOH and Fe3O4, although there was additional Fe2(SO4)3 in the EC/PS sludge. The degraded organics in the solution and sediment phase were quantified by material flow analysis, indicating that the precipitation was the main contributor to DOM removal during the EC/PS process. These findings aid in understanding the role of PS in the EC/PS process during real landfill leachate treatment and reevaluate the advantages and limitations of PS as an oxidant.

Impact of light-aged microplastic on microalgal production of dissolved organic matter

Microplastics (MPs) can affect phytoplankton and its photosynthetic performance in many but often in negative ways. Phytoplankton is an important source of dissolved organic matter (DOM) in aquatic ecosystems, but the impact of MPs on the algal production of DOM is poorly known. We investigated the impacts of polyvinyl chloride MPs on the growth and DOM production by Chlamydomonas reinhardtii microalgae in a 28-day-long experiment. During the exponential growth phase of C. reinhardtii, MPs slightly affected algal growth and DOM production. At the end of experiment, MPs decreased the biomass of C. reinhardtii by 43 % in the treatment with MPs exposed to simulated solar radiation prior the experiment (light-aged) and more than in the treatment with virgin MPs. The light-aged MPs decreased algal DOM production by 38 % and modified the chemical composition of DOM. According to spectroscopic analyses, the light-aged MPs increased aromaticity, average molecular weight and fluorescence of DOM produced by C. reinhardtii. The elevated fluorescence was associated with humic-like components identified by a 5-component parallel factor analysis (PARAFAC) from the excitation-emission matrices. We conclude that although MPs can leach DOM to aquatic ecosystems, they potentially modify the aquatic DOM more by interfering with the algal production of DOM and changing the composition of produced DOM.

The characteristics of CDOM structural composition and the effect on indirect photodegradation of sulfamerazine

Sulfamerazine (SM) is a commonly used antibiotic and have been widely used to control various bacterial infectious diseases. The structural composition of colored dissolved organic matter (CDOM) is known to be a major factor that influences the indirect photodegradation of SM, yet the influence mechanism remains unknown. In order to understand this mechanism, CDOM from different sources was fractionated using ultrafiltration and XAD resin, and characterized using UV–vis absorption and fluorescence spectroscopy. The indirect photodegradation of SM in these CDOM fractions was then investigated. Humic acid (JKHA) and Suwannee River natural organic matter (SRNOM) were used in this study. The results showed that CDOM could be divided into four components (three humic-like components and one protein-like component), and terrestrial humic-like components C1 and C2 were found to be the main components that promote SM indirect photodegradation due to their high aromaticity. The indirect photodegradation of SM was much faster in low molecular weight (MW) solutions, whose structures were dominated by greater aromaticity and terrestrial fluorophores in JKHA and higher terrestrial fluorophores in SRNOM. The HIA and HIB fractions of SRNOM contained large aromaticity and high fluorescence intensities of C1 and C2, resulting in a greater indirect photodegradation rate of SM. The HOA and HIB fractions of JKHA had abundant terrestrial humic-like components and contributed more to SM indirect photodegradation.

Organic matter degradation and arsenic enrichment in different floodplain aquifer systems along the middle reaches of Yangtze River: A thermodynamic analysis

Geogenic arsenic (As) contaminated groundwater has been widely accepted associating with dissolved organic matter (DOM) in aquifers, but the underlying enrichment mechanism at molecular-level from a thermodynamic perspective is poorly evidenced. To fill this gap, we contrasted the optical properties and molecular compositions of DOM coupled with hydrochemical and isotopic data in two floodplain aquifer systems with significant As variations along the middle reaches of Yangtze River. Optical properties of DOM indicate that groundwater As concentration is mainly associated with terrestrial humic-like components rather than protein-like components. Molecular signatures show that high As groundwater has lower H/C ratios, but greater DBE, AImod, and NOSC values. With the increase of groundwater As concentration, the relative abundance of CHON3 formulas gradually decreased while that of CHON2 and CHON1 increased, indicating the importance of N-containing organics in As mobility, which is also evidenced by nitrogen isotope and groundwater chemistry. Thermodynamic calculation demonstrated that organic matter with higher NOSC values preferentially favored the reductive dissolution of As-bearing Fe(III) (hydro)oxides minerals and thus promoted As mobility. These findings could provide new insights to decipher organic matter bioavailability in As mobilization from a thermodynamical perspective and are applicable to similar geogenic As-affected floodplain aquifer systems.

Evaluation of Efficiently Removing Secondary Effluent Organic Matters (EfOM) by Al-Based Coagulant for Wastewater Recycling: A Case Study with an Industrial-Scale Food-Processing Wastewater Treatment Plant.

The reuse of wastewater has been identified as an important initiative for the sustainable development of the environment; thus, the removal of secondary effluent organic matter (EfOM) to ensure the safety of reused wastewater is the key step and a subject of extensive research. In this study, Al2(SO4)3 and anionic polyacrylamide were selected as coagulant and flocculant, respectively, for the treatment of secondary effluent from a food-processing industry wastewater treatment plant to meet the standard regulatory specifications for water reuse. In this process, the removal efficiencies of chemical oxygen demand (COD), components with UV254, and specific ultraviolet absorbance (SUVA) were 44.61%, 25.13%, and 9.13%, respectively, with an associated reduction in chroma and turbidity. The fluorescence intensities (Fmax) of two humic-like components were reduced during coagulation, and microbial humic-like components of EfOM had a better removal efficiency because of a higher Log Km value of 4.12. Fourier transform infrared spectroscopy showed that Al2(SO4)3 could remove the protein fraction of the soluble microbial products (SMP) of EfOM by forming a loose SMP protein complex with enhanced hydrophobicity. Furthermore, flocculation reduced the aromaticity of secondary effluent. The cost of the proposed secondary effluent treatment was 0.034 CNY t-1 %COD-1. These results demonstrate that the process is efficient and economically viable for EfOM removal to realize food-processing wastewater reuse.

Molecular Responses of Dissolved Organic Matter to Anthropogenic Groundwater Recharge: Characteristics, Transformations, and Sensitive Molecules.

The groundwater quality impacts associated with anthropogenic groundwater recharge (AGR) are of great concern for water management. However, the impacts of AGR on the molecular properties of dissolved organic matter (DOM) in aquifers are poorly understood. Herein, Fourier transform ion cyclotron resonance mass spectrometry was used to unravel the molecular characteristics of DOM in groundwaters from recharge areas by reclaimed water (RWRA) and natural water from South-to-North Water Diversion Project (SNWRA). Compared with RWRA groundwater, significantly fewer nitrogenous compounds, more sulfur-containing compounds, higher concentrations of NO3-N, and lower pH were observed in SNWRA groundwater, indicating the occurrence of deamination, sulfurization, and nitrification. The occurrence of these processes was further supported by transformations of more molecules related to nitrogen and sulfur in SNWRA groundwater relative to RWRA groundwater. The intensities of most common molecules in all samples were significantly correlated with the water quality indicators (e.g., Cl- and NO3-N) and fluorescent indicators (e.g., humic-like components (C1%)), indicating that those common molecules may have the potential to track the environmental impact of AGR on groundwater, especially these specific molecules having great mobility and being significantly correlated with other inert tracers like C1% and Cl-. This study is helpful to understand the environmental risks and regional applicability of AGR.

How does anthropogenic activity influence the spatial distribution of dissolved organic matter in rivers of a typical basin located in the Loess Plateau, China

River ecosystems interact strongly with adjacent terrestrial environments and receive dissolved organic matter (DOM) from a variety of sources, all of which are vulnerable to human activities and natural processes. However, it is unclear how and to what extent human and natural factors drive DOM quantity and quality changes in river ecosystems. Here, three fluorescence components were identified via optical techniques, including two humic-like substances and one protein-like component. The protein-like DOM was mainly accumulated in anthropogenically impacted regions, while humic-like components exhibit the opposite trend. Furthermore, the driving mechanisms of both natural and anthropogenic factors on the variations in DOM composition were investigated using partial least squares structural equation modelling (PLS-SEM). Human activities, especially agriculture, positively influence the protein-like DOM directly by enhancing anthropogenic discharge with protein signals and also indirectly by affecting water quality. Water quality directly influences the DOM composition by stimulating in-situ production through a high nutrient load from anthropogenic discharge and inhibiting the microbial humification processes of DOM due to higher salinity levels. The microbial humification processes can also be restricted directly by a shorter water residence time during the DOM transport processes. Furthermore, protein-like DOM was more sensitive to direct anthropogenic discharge than indirect in-situ production (0.34 vs. 0.25), especially from non-point source input (39.1%), implying that agricultural industry optimization may be an efficient way to improve water quality and reduce protein-like DOM accumulation.

Seasonal and Spatial Variations in the Optical Characteristics of Dissolved Organic Matter in the Huma River Basin, China

Dissolved organic matter (DOM) plays a central role in the global carbon cycle. The Huma River Basin (HRB) in China is affected by humic substances in its forests with high background values. DOM in the HRB was studied using spectroscopic techniques combined with statistical analysis in order to better understand its characteristics in natural waters affected by humic substances in forests. UV-visible parameters showed that the DOM predominantly consisted of aromatic and high-molecular-weight natural organic matter. Fluorescence excitation-emission matrix (EEM) spectroscopy-parallel factor analysis (PARAFAC) recognized four characteristic components, representing humic-like substances (C1, C2, and C3) and protein-like substances (C4). Fluorescence parameters showed that the allochthonous terrestrially-derived DOM had a humic character. Fourier transform infrared (FT-IR) spectra characterized the structure of DOM, containing aromatic, aliphatic, carbohydrate, and protein compounds. Principal component analysis (PCA) revealed that humic-like components explained approximately 86.7% of the total variance, suggesting that terrestrial humic-like substances were dominant in the HRB. Correlation coefficient matrix analysis indicated that CODMn and DOC were mainly derived from humic-like substances. The results demonstrated that the background value in the HRB was mainly attributed to terrestrial humic-like substances. Such knowledge could assist in monitoring and managing rivers with high background values.

Removal of carbonaceous and nitrogenous disinfection by-product precursors in biological activated carbon process of drinking water: Is service life a pivotal factor?

Biological activated carbon (BAC) process is commonly used for drinking water treatment. Granular activated carbon (GAC) serving as the initial filter media can be converted to BAC with biofilm development during extending service life. Consequently, GAC/BAC effectiveness for disinfection by-product (DBP) precursors removal varies over service life. Effluents of full-scale ozonation and BACs operated for 1–3 months (1-month GAC), 4–6 months (4-month BAC), and about 7 years (7-year BAC) were analyzed. All BACs were efficient in fluorescence components removal, with decreasing efficiency in the order of 1-month GAC > 4-month BAC > 7-year BAC. Accordingly, reduction ratios of total DBPs concentration formed in post-chlorination dropped from 39% to 21% and 8% by BACs with different ages. Due to varied toxic potencies of DBPs, toxicities reduction was not completely related to DBPs concentration reduction. Haloacetonitriles (HANs) group accounted for small proportion of DBPs concentration but drove both of cytotoxicity and genotoxicity. Hence, the precursor removals of carbonaceous (C-) DBPs and nitrogenous (N-) DBPs were further compared in detail. 1-month GAC exhibited relatively higher effectiveness for protein-like components removal than humic-like component removal, for HANs formation reduction than trihalomethanes (THMs) formation reduction, and for HANs cytotoxicity reduction than THMs cytotoxicity reduction. A similar pattern was observed for 4-month BAC, while 7-year BAC exhibited the opposite pattern. Given the complexity of real water, this full-scale study provides valuable insights into the differences in precursor removals of C-DBPs and N-DBPs by BACs with different ages, which is critical for advancing our understanding of BAC process.

Coupled effects of sedimentary iron oxides and organic matter on geogenic phosphorus mobilization in alluvial-lacustrine aquifers

The organic matter (OM) biodegradation and reductive dissolution of iron oxides have been acknowledged as key factors in the release of geogenic phosphorus (P) to groundwater. However, the coupled effects of natural OM with iron oxides on the mobilization of geogenic P remain unclear. Groundwater with high and low P concentrations has been observed in two boreholes in the alluvial-lacustrine aquifer system of the Central Yangtze River Basin. Sediment samples from these boreholes were examined for their P and Fe species as well as their OM properties. The results show that sediments from borehole S1 with high P levels contain more bioavailable P, particularly iron oxide bound P (Fe-P) and organic P (OP) than those from borehole S2 with low P levels. Regarding borehole S2, Fe-P and OP show positive correlations with total organic carbon as well as amorphous iron oxides (FeOX1), which indicate the presence of Fe-OM-P ternary complexes, further evidenced by FTIR results. In a reducing environment, the protein-like component (C3) and terrestrial humic-like component (C2) will biodegrade. In the process of C3 biodegradation, FeOX1 will act as electron acceptors and then undergo reductive dissolution. In the process of C2 biodegradation, FeOX1 and crystalline iron oxides (FeOX2) will act as electron acceptors. FeOX2 will also act as conduits in the microbial utilization pathway. However, the formation of stable P-Fe-OM ternary complexes will inhibit the reductive dissolution of iron oxides and OM biodegradation, thus inhibiting the mobilization of P. This study provides new insights into the enrichment and mobilization of P in alluvial-lacustrine aquifer systems.

Water quality, basin characteristics, and discharge greatly affect CDOM in highly turbid rivers in the Yellow River Basin, China

Significant variations exist in water quality parameters and inherent optical properties (IOPs) in highly turbid rivers. For rivers in the Yellow River (YR) Basin, 83.33% of the collected samples exhibited high turbidity, and the absorption of non-algal particles (NAPs) was the main contributor to total water absorption. In this study, we investigated the compositions of chromophoric dissolved organic matter (CDOM) using the absorption index and fluorescence components, examined the quantitative effects of environmental factors on CDOM at the sub-basin scale and identified where and how carbon was produced in the area. The humic-like component (FR5) of CDOM was the main component in the tributaries and the main stream of the YR, especially for the Huangshui River, with FR5 accounting for 58.12%. Water quality parameters greatly affected CDOM in turbid rivers. Dissolved organic carbon and electrical conductivity were positively correlated with the CDOM concentration (p < 0.05), while dissolved oxygen, pH, chlorophyll-a and turbidity significantly affected CDOM composition (p < 0.01). Basin characteristics exerted significant influences on CDOM. The spectral slope (S275-295) increased as the altitude of the sub-basins increased. The percentage of built-up area exerted the most significant effects on CDOM composition, with high correlations with tryptophan-like protein (FR2) and FR5 (r > 0.59, p < 0.01). Forest percentage and grassland percentage showed positive correlations with CDOM concentration (r = 0.36, p < 0.05) and S275-295 (r = 0.30, p < 0.05), respectively. Moreover, the discharge from rivers in the YR Basin showed that the carbon flux of rivers in the YR Basin is more likely to be limited by dissolved organic matter (DOM) sources although negative but nonsignificant effects of discharges on CDOM parameters were shown. Consequently, additional research is necessary to clarify this correlation. This research is crucial and necessary for improving the accuracy of CDOM evaluation with remote sensing, revealing the influencing mechanisms and monitoring carbon cycling.

Comparisons in molecular weight distributions and size-dependent optical properties among model and reference natural dissolved organic matter.

Humic acid (HA) and reference natural organic matter (NOM) have been widely used in environmental assessment, biogeochemistry, and ecotoxicity studies. Nevertheless, similarities and differences among the commonly used model/reference NOMs and bulk dissolved organic matter (DOM) have rarely been systematically evaluated. In this study, HA, SNOM (Suwannee River NOM) and MNOM (Mississippi River NOM), both from International Humic Substances Society, and freshly collected unfractionated NOM (FNOM) were concurrently characterized to evaluate their heterogeneous nature and size-dependent chemical properties. We found that molecular weight distributions, PARAFAC-derived fluorescent components, and size-dependent optical properties are NOM-specific and highly variable with pH. The < 1kDa DOM abundance followed the order of HA < SNOM < MNOM < FNOM. In addition, FNOM was more hydrophilic and contained more protein-like and autochthonous components with a higher UV-absorbance ratio index (URI) and biological fluorescenceindex, whereas HA and SNOM contained more allochthonous, humic-like components with a higher aromaticity and lower URI. Significant differences in molecular composition and size spectra between FNOM and model/reference NOMs suggest that environmental role of NOMs should be evaluated at the levels of molecular weight and functionalities under the same experimental conditions and that HA and SNOM may not represent bulkNOM in the environment. This study provides new information about similarities and differences in DOM size-spectra and chemical properties between reference NOMs and in-situ NOM and highlights the need to better understand the heterogenous roles of NOMs in regulating the toxicity/bioavailability and environmental fate of pollutants in aquatic environments.

Water mass age and dissolved organic matter properties drive the diversity of pelagic prokaryotes in the Western Mediterranean Sea

The deep sea is among the largest, yet still poorly known, ecosystems on Earth. This knowledge gap is particularly evident for the bathypelagic layer (between 1000 and 4000 m) of the deep Mediterranean Sea (MS), characterized by peculiar environmental conditions at meso- and bathypelagic depths, such as the thermal signature of the deep waters, showing temperatures approximately 10 °C higher than any oceanic system at comparable depths. This sustains high rates of prokaryotic activities and fast dissolved organic matter (DOM) mineralization rates, and likely selects for unique microbial assemblages. We collected seawater samples in stations representative of different areas of the Western Mediterranean Sea (Algero-Provençal Basin, Alboran Sea and Gulf of Lion), from the surface to the bathypelagic layer (down to 2680 m) and in different water masses, and described the composition of pelagic prokaryotic communities, along with measurements of the main physical-chemical variables, concentration and optical properties (absorption and fluorescence) of DOM. Remarkable differences in DOM optical properties were observed among water masses, with highest dissolved organic carbon (DOC) values in surface waters and lowest in the oldest water masses represented by the Western Mediterranean Deep Water (WMDW) and the Levantine Intermediate Water (LIW), which were characterized by the highest concentration of recalcitrant DOM. The water mass had a significant partitioning effect on microbial community composition, which showed the highest richness in LIW. DOC, the marine humic-like component of DOM (C1mh) and oxygen were the main drivers of prokaryotic community structure. Changes in quality of DOM were reflected in shifts in community composition, supporting the existence of strong relationships between DOM quality and microbial community composition in the deep MS. Our data shed light on the community composition and diversity patterns of prokaryotic plankton in the deep western MS, helping to elucidate the major microbial players in the DOM cycling, and to progress towards a better comprehension of its future trends in light of changing conditions that are modifying the oceanography of the entire MS basin.

Mechanistic insights into dissolved organic matter-driven protistan and bacterial community dynamics influenced by vegetation restoration

Vegetation restoration projects can not only improve water quality by absorbing and transferring pollutants and nutrients from non-vegetation sources, but also protect biodiversity by providing habitat for biological growth. However, the mechanism of the protistan and bacterial assembly processes in the vegetation restoration project were rarely explored. To address this, based on 18 S rRNA and 16 S rRNA high-throughput sequencing, we investigated the mechanism of protistan and bacterial community assembly processes, environmental conditions, and microbial interactions in the rivers with (out) vegetation restoration. The results indicated that the deterministic process dominated the protistan and bacterial community assembly (94.29% and 92.38%), influenced by biotic and abiotic factors. For biotic factors, microbial network connectivity was higher in the vegetation zone (average degree = 20.34) than in the bare zone (average degree = 11.00). For abiotic factors, the concentration of dissolved organic carbon ([DOC]) was the most important environmental factor affecting the microbial community composition. [DOC] was lower significantly in vegetation zone (18.65 ± 6.34 mg/L) than in the bare zone (28.22 ± 4.82 mg/L). In overlying water, vegetation restoration upregulated the protein-like fluorescence components (C1 and C2) by 1.26 and 1.01-folds and downregulated the terrestrial humic-like fluorescence components (C3 and C4) by 0.54 and 0.55-folds, respectively. The different DOM components guided bacteria and protists to select different interactive relationships. The protein-like DOM components led to bacterial competition, whereas the humus-like DOM components resulted in protistan competition. Finally, the structural equation model was established to explain that DOM components can affect protistan and bacterial diversity by providing substrates, facilitating microbial interactions, and promoting nutrient input. In general, our study provides insights into the responses of vegetation restored ecosystems to the dynamics and interactives in the anthropogenically influenced river and evaluates the ecological restoration performance of vegetation restoration from a molecular biology perspective.

Characteristics, sources and driving factors of riverine CDOM in a severe erosion basin on the Loess Plateau, China

Chromophoric dissolved organic matter (CDOM) plays a crucial role in aquatic ecosystems and biogeochemical processes. The characteristics, sources and influencing factors of riverine CDOM were determined with 56 samples collected in the Wuding River (WDR) Basin in spring and summer. The CDOM optical characteristics varied greatly during different seasons. The mean S275-295 was higher in spring than in summer, while SUVA254 exhibited the opposite result. The mean biological source index (BIX) was lower in summer than in spring, while the mean humification index (HIX) was higher in summer than in spring (p < 0.01). C1 and C3 (humic-like components) and C2 (tryptophan-like component) were extracted by parallel factor analysis (PARAFAC). C1 and C3 were prominent in summer, while C2 was prominent in spring. The effects of environmental factors on CDOM showed great differences. Chlorophyll a (Chla), dissolved organic carbon (DOC), electrical conductivity (EC) and dissolved oxygen (DO) had significant effects on the CDOM concentration (p < 0.05) in spring, while only DOC exerted significant effects on the CDOM concentration in summer. However, water quality parameters played important roles in evaluating the CDOM fluorescence components in summer. Total suspended matter (TSM) and turbidity (Tur) exerted significant effects on the humic-like fluorescence peaks (p < 0.05), while pH, Chla, DO, and EC had significant influences on tryptophan-like substances during this period. Based on redundancy analysis, precipitation, water erosion area and human activity intensity greatly affected the CDOM concentration, C1 and C3, while human activity intensity significantly affected C2 in the sub-basins in summer. CDOM was not significantly influenced by the surrounding environmental factors in spring except for the human activity intensity, which greatly influenced C1 and C3.

Spatiotemporal response of dissolved organic matter diversity to natural and anthropogenic forces along the whole mainstream of the Yangtze River

The Yangtze River, the largest river in Asia, plays a crucial role in linking continental and oceanic ecosystems. However, the impact of natural and anthropogenic disturbances on composition and transformation of dissolved organic matter (DOM) during long-distance transport and seasonal cycle is not fully understood. By using a combination of elemental, isotopic and optical techniques, as well as Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), we investigated DOM abundance and composition along the whole mainstream at highly spatial resolution in the dry and early wet seasons. Our findings showed that the concentration and flux of dissolved organic carbon (DOC) in the Yangtze River was much lower compared with other worldwide larger rivers. The distribution of δ13CDOC and higher abundance of humic-like fluorescent component and highly unsaturated and phenolics (HUPs) compound reflected a prominent contribution of allochthonous DOM. Further optical and molecular analysis revealed humic-like fluorescent components were coupled with CHO molecules and HUPs compound with higher aromatic, unsaturated, molecular weight and stable characteristics between upstream and midstream reaches. With increasing agricultural and urban land downstream, there were more heteroatomic formulae and labile aliphatic and protein-like compounds which were derived from human activities and in situ primary production. Meanwhile, DOM gradually accumulates with slow water flow and additional autochthonous organics. Weaker solar radiation and water dilution during the dry/cold season favours highly aromatic, unsaturated and oxygenated DOM compositions. Conversely, higher discharge during the wet/warm season diluted the terrestrial DOM, but warm temperatures could promote phytoplankton growth that releases labile aliphatic and protein-like DOM. Besides, chemical sulfurization, hydrogenation and oxygenation were found during molecular cycling processes. Our research emphasizes the active response of riverine DOM to natural and anthropogenic controls, and provides a valuable preliminary background to better understand the biogeochemical cycling of DOM in a larger river.

Transformation of algal-dissolved organic matter via sunlight-induced photochemical and microbial processes: interactions between two processes.

Algal-dissolved organic matter (ADOM) is an important fraction of dissolved organic carbon (DOC) in eutrophic water. Although ADOM is known to be readily transformed by microbes, the role of sunlight-induced photochemical process and the interactions between two processes on ADOM transformation remains unclear. In this study, three types of treatments for ADOM, including photochemical process under natural solar light (L treatment), microbial process (M treatment), and the simultaneous photochemical plus microbial process (L&M), were performed for 18days. Our results showed that M treatment was more effective for the loss of DOC, chromophoric DOM (CDOM) at short wavelengths (a254 and a280), than L treatment, while L treatment was more effective for the transformation of a350 and the fluorescent components of the ubiquitous humic-like component and the tryptophan-like component. Comparison in the decay kinetics of DOC and CDOM in the three treatments showed that the simultaneous photochemical and biological processes exhibited an inhibitory effect on DOC decay rate but not the percentage of labile DOC fraction. Higher relative abundance of protein-like substances was found after L&M treatment, while the relative abundance of humic-like substance and aromaticity increased after M treatment, and the low molecular-weight compounds were produced after L treatment. Our results emphasized the importance of photochemistry in processing ADOM to mediate the chemodiversity in natural water.

An innovative approach for landfill leachate treatment based on selective adsorption of humic acids with carbon nitride

Selective adsorption of humic acids is innovative in landfill leachate treatment, since it can both address the UV quenching substance (UVQS) problems and recover humic acids as liquid fertilizers applied in agriculture and forestry. However, due to lacking available adsorbents, it remains a great challenge. Herein, we evaluated the application of graphitic carbon nitride (g-CN) for selective adsorption of humic acids from landfill leachate. First, 10 types of leachate were considered and characterized, and the leachate contained humic acids of different contents. The common method was used to prepare g-CN with similar properties to the previously reported counterparts. Then, kinetics, isotherms, and removal for adsorption of the leachate by g-CN were studied. It was found that the adsorption was fast and controlled by the surface and intraparticle diffusion. For all the leachate, the removal of UV absorbance at 254 nm (UV254) was 30 ∼ 70%, much greater than that for total organic carbon. In particular, the UV254 removal was mainly contributed by the selective adsorption of humic acids with a high selectivity coefficient (>3.06). The recovery rate and purity of the adsorbed humic-like components were 100% in some cases. Finally, the mechanisms for selective adsorption were elucidated. The results revealed that, in addition to the major π-π interactions, the adsorption was affected by electrostatic interactions and hydrogen bondings, along with the newly proven conformation-variation effect. The findings will expand a promising direction for disposal of landfill leachate.

Characterizing the effects of stormwater runoff on dissolved organic matter in an urban river (Jiujiang, Jiangxi province, China) using spectral analysis.

The effect of stormwater runoff on dissolved organic matter (DOM) in rivers is one of the central topics in water environment research. Jiujiang is one of the first cities established in the green development demonstration zone of the Yangtze River Economic Belt (Jiangxi Province, China). Three-dimensional excitation-emission matrix fluorescence with parallel factor analysis (3DEEM-PARAFAC) and ultraviolet-visible (UV-Vis) spectroscopy were used to explore the effects of runoff on organic matter in Shili River (Jiujiang, Jiangxi Province, China). The results show that the runoff led to an increase of some critical pollutants and DOM concentrations, especially in the middle reaches of the river. The concentration and relative molecular weight of DOM in water increased as a result of runoff. Three humic-like (C1-C3) and two protein-like (C4 and C5) components of DOM were identified using the PARAFAC model. The sources of the three humic-like components (C1, C2, C3) were consistent, unlike those of the protein-like component C4. Compared with the pre-rainfall period, the content of humus compounds flowing into the river through the early rainwater runoff was lower, which caused the relative content and proportion of humic substances little change and protein-like species increasing. The DOM mainly derived from autochthonous sources, and runoff had limited effect on its characteristics. Jiujiang is a key demonstration city for Yangtze River conservation. Rainwater runoff is one of the pollution sources of urban rivers, which leads to the deterioration of water quality and influences the distribution characteristics of DOM in water bodies. The PARAFAC components could adequately represent different indicators and sources of DOM in urban rivers, providing an important reference for urban river management.