Mechanisms of photochemical release of dissolved organic matter and iron from resuspended sediments

Photochemical reactions can alter the transformation of sedimentary organic matter into dissolved organic matter (DOM) and affect its ultimate fate in water ecosystems. In the present study, the photorelease of DOM and Fe from resuspended lake sediments was investigated under different O₂ and NO₃^? concentration conditions to study the mechanisms of DOM and Fe photorelease. The amount of photoreleased Fe, which ranged from 0.22 to 0.70 μmol/L, was significantly linearly correlated with the amount of photoreleased DOM. O₂ and NO₃^? could promote the photochemical release of DOM and Fe, especially during the initial 4 h irradiation. In general, the order of the photorelease rates of DOM and Fe under different conditions was as follows: NO₃^?/aerobic > aerobic ≈ NO₃^?/anaerobic > anaerobic. The photorelease rates of DOM and Fe were higher for the initial 4 hr irradiation than these for the subsequent 8 hr irradiation. The photorelease of DOM and Fe is thought to proceed via direct photodissolution and indirect processes. The relative contributions of indirect processes (>60%) was much greater than that of direct photodissolution (<40%). The photoproduced H₂O₂ under aerobic and anaerobic conditions indicated that hydroxyl radicals (?OH) are involved in the photorelease of DOM. Using ?OH scavengers, it was found that 38.7%, 53.7%, and 77.6% of photoreleased DOM was attributed to ?OH under anaerobic, aerobic, and NO₃^?/aerobic conditions, respectively. Our findings provide insights for understanding the mechanisms and the important role of ?OH in the DOM and Fe photorelease from resuspended sediments.     

Influence of dissolved organic matter on methylmercury transformation during aerobic composting of municipal sewage sludge under different C/N ratios

Current knowledge about the transformation of total mercury and methylmercury (MeHg) in aerobic composting process is limited. In this study, the composition and transformation of mercury and dissovled organic matter (DOM) in aerobic composting process of municipal sewage sludge were were comprehensively characterized, and the differences among the three C/N ratio (20, 26 and 30) were investigated. The main form of mercury in C/N 20 and 26 was organo-chelated Hg (F3, 46%-60%); while the main form of mercury in C/N 30 was mercuric sulfide (F5, 64%-70%). The main component of DOM in C/N 20 and 26 were tyrosine-like substance (C1, 53%-76%) while the main fractions in C/N 30 were tyrosine-like substance (C1, 28%-37%) and fulvic-like substance (C2, 17%-39%). The mercury and DOM varied significantly during the 9 days composting process. Compared to C/N 20 and 26, C/N 30 produced the less MeHg after aerobic composting process, with values of 658% (C/N 20), 1400% (C/N 26) and 139% (C/N 30) of the initial, respectively. Meanwhile, C/N 30 produced the best compost showed greater degree of DOM molecular condensation and humification. Hg fraction had been altered by DOM, as indicated by a significant correlation between mercury species and DOM components. Notably, C/N 30 should be used as an appropriate C/N ratio to control the methylation processes of mercury and degration of DOM.     

Ultraviolet humic-like component contributes to riverine dissolved organic matter biodegradation

Biological degradation of dissolved organic matter(DOM) regulates its structure and fate in river ecosystems. Previous views suggested that labile components were dominantly consumed by microbial metabolism. Here we provide new observations that a part of recalcitrant compounds largely contribute to riverine DOM biodegradation. The excitationemission matrix fluorescent spectroscopy combined with peak picking and parallel factor analysis are used to explore component variability during DOM incuba...     

Linking the electron donation capacity to the molecular composition of soil dissolved organic matter from the Three Gorges Reservoir areas, China

Soil dissolved organic matter(DOM) plays an essential role in the Three Gorges Reservoir(TGR) as a linkage between terrestrial and aquatic systems.In particular,the reducing capacities of soil DOM influence the geochemistry of contaminants such as mercury(Hg).However,few studies have investigated the molecular information of soil DOM and its relationship with relevant geochemic al reactivities,including redox properties.We collected samples from eight sites in the TGR areas and studied the link between the molecular characteristics of DOM and their electron donation capacities(EDCs) toward Hg(II).The average kinetic rate and EDC of soil DOM in TGR areas were(0.004±0.001) hr~(-1) and(2.88±1.39) nmol e~-/mg DOM_(bulk),respectively.Results suggest that higher EDCs and relatively rapid kinetics were related to the greater electron donating components of ligninderived and perhaps pyrogenic DOM,which are the aromatic constituents that influenced the reducing capacities of DOM in the present study.Molecular details revealed that even the typical autochthonous markers are important for the EDCs of DOM as well,in contrast to what is generally assumed.More studies identifying specific DOM molecular components involved in the abiotic reduction of Hg(II) are required to further understand the relations between DOM sources and their redox roles in the environmental fate of contaminants.     

Assessing the utility of dissolved organic matter photoreactivity as a predictor of in situ methylmercury concentration

Methylmercury(MeHg) bioaccumulation is a growing concern in ecosystems worldwide. The absorption of solar radiation by dissolved organic matter(DOM) and other photoreactive ligands can convert MeHg into less toxic forms of mercury through photodemethylation. In this study, spectral changes and photoreactivity of DOM were measured to assess the potential to control photoreactions and predict in situ MeHg concentration. Water samples collected from a series of lakes in southwestern Nova Scotia in June, August, and September were exposed to controlled ultraviolet-A(UV-A) radiation for up to 24 hr. Dissolved organic matter photoreactivity, measured as the loss of absorbance at 350 nm at constant UV-A irradiation, was positively dependent on the initial DOM concentration in lake waters(r~2=0.94). This relationship was consistent over time with both DOM concentration and photoreactivity increasing from summer into fall across lakes. Lake in situ MeHg concentration was positively correlated with DOM concentration and likely catchment transport in June(r = 0.77) but not the other sampling months. Despite a consistent seasonal variation in both DOM and Fe, and their respective correlations with MeHg, no discernable seasonal trend in MeHg was observed. However, a 3-year dataset from the 6 study lakes revealed a positive correlation between DOM concentration and both Fe(r = 0.91) and MeHg concentrations(r = 0.51) suggesting a more dominant landscape mobility control on MeHg.The DOM-MeHg relationships observed in these lakes highlights the need to examine DOM photoreactivity controls on MeHg transport and availability in natural waters particularly given future climate perturbations.     

Diverse molecular compositions of dissolved organic matter derived from different composts using ESI FT-ICR MS

Dissolved organic matter (DOM) derived from various composts can promote significant changes of soil properties. However, little is known about the DOM compositions and their similarities and differences at the molecular level. In this study, the molecular compositions of DOM derived from kitchen waste compost (KWC), green waste compost (GWC), manure waste compost (MWC), and sewage sludge compost (SSC) were characterized by electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The molecular formulas were classified into four subcategories: CHO, CHON, CHOS, and CHONS. The KWC, MWC, and SSC DOM represented the highest fraction (35.8%-47.4%) of CHON subcategory, while the GWC DOM represented the highest fraction (68.4%) of CHO subcategory. The GWC DOM was recognized as the nitrogen- and sulfur-deficient compounds that were less saturated, more aromatic, and more oxidized compared with other samples. Further analysis of the oxygen, nitrogen-containing (N-containing), and sulfur-containing (S-containing) functional groups in the four subcategories revealed higher organic molecular complexity. Comparison of the similarities and differences of the four samples revealed 22.8% ubiquitous formulas and 17.4%, 11.1%, 10.7%, and 6.3% unique formulas of GWC, KWC, SSC, and MWC DOM, respectively, suggesting a large proportion of ubiquitous DOM as well as unique, source-specific molecular signatures. The findings presented herein provide new insight into the molecular characterization of DOM derived from various composts and demonstrated the potential role of these different compounds for agricultural utilization.     

Revealing the characteristics of dissolved organic matter in urban runoff at three typical regions via optical indices and molecular composition

Dissolved organic matter (DOM) plays a major role in ecological systems and influences the fate and transportation of many pollutants. Despite the significance of DOM, understanding of how environmental and anthropogenic factors influence its composition and characteristics is limited, especially in urban stormwater runoff. In this article, the chemical properties (pollutant loads, molecular weight, aromaticity, sources, and molecular composition) of DOM in stormwater extracted from three typical end-members (traffic, residential, and campus regions) were characterized by UV–visible (UV–vis) spectroscopy, excitation-emission matrix spectroscopy combined with parallel factor analysis (EEM-PARAFAC), and ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). There are three findings: (1) The basic properties of DOM in stormwater runoff varied obviously from three urban fields, and the effect of initial flush was also apparent. (2) The DOM in residential areas mainly came from autochthonous sources, while allochthonous sources primarily contributed to the DOM in traffic and campus areas. However, it was mainly composed of terrestrial humic-like components with CHO and CHON element composition and HULO and aliphatic formulas. (3) The parameters characterizing DOM were primarily related to terrestrial source and aromaticity, but their correlations varied. Through the combination of optical methods and UPLC-Q-TOF spectrometry, the optical and molecular characteristics of rainwater are effectively revealed, which may provide a solid foundation for the classification management of stormwater runoff in different urban regions.     

Effects of soil properties on production and bioaccumulation of methylmercury in rice paddies at a mercury mining area, China

Rice paddy soil is recognized as the hotspot of mercury(Hg) methylation, which is mainly a biotic process mediated by many abiotic factors. In this study, effects of key soil properties on the production and bioaccumulation of Hg and methylmercury(MeHg) in Hg-contaminated rice paddies were investigated. Rice and soil samples were collected from the active Hg smelting site and abandoned Hg mining sites(a total of 124 paddy fields) in the Wanshan Mercury Mine, China. Total Hg(THg) and MeHg in soils and rice grains, together with sulfur(S),selenium(Se), organic matter(OM), nitrogen(N), phosphorus(P), mineral compositions(e.g., SiO_2, Al_2O_3 and Fe_2O_3) and pH in soils were quantified. The results showed that long-term Hg mining activities had resulted in THg and MeHg contaminations in soil-rice system. The newly-deposited atmospheric Hg was more readily methylated relative to the native Hg already in soils, which could be responsible for the elevated MeHg levels in soils and rice grains around the active artificial Hg smelting site. The MeHg concentrations in soils and rice grains showed a significantly negative relationship with soil N/Hg, S/Hg and OM/Hg ratio possibly due to the formation of low-bioavailability Hg–S(N)–OM complexes in rhizosphere. The Hg–Se antagonism undoubtedly occurred in soil-rice system, while its role in bioaccumulation of MeHg in the MeHg-contaminated rice paddies was minor. However, other soil properties showed less influence on the production and bioaccumulation of MeHg in rice paddies located at the Wanshan Mercury Mine zone.     

Spatiotemporal optical properties of dissolved organic matter in a sluice-controlled coastal plain river with both salinity and trophic gradients

Due to the combined effect of sluices and sea tide, the sluice-controlled coastal plain river would be characterized by both trophic state and salinity gradients, affecting the spatiotemporal optical properties of dissolved organic matter (DOM). In this study, we investigated the spatiotemporal variation of water quality parameters and optical properties of DOM in the Haihe River, a representative sluice-controlled coastal plain river in Tianjin, China. A significant salinity gradient and four trophic states were observed in the water body of the Haihe River. Two humic- and one protein-like substances were identified from the DOM by the three-dimensional fluorescence spectra combined with the parallel factor (PARAFAC) analysis. Pearson's correlation analysis and redundancy analysis (RDA) showed that the salinity significantly affected the abundance of chromophoric DOM (CDOM) but did not cause significant changes in the fluorescence optical characteristics. In addition, the effect of Trophic state index (TSI) on the CDOM abundance was greater than that on the fluorescence intensity of fluorescent dissolved organic matter (FDOM). In the water body with both salinity and trophic state gradients, TSI posed a greater influence than salinity on the CDOM abundance. Our results fill the research gap in spatiotemporal DOM characteristics and water quality variation in water bodies with both salinity and trophic state gradients. These results are beneficial for clarifying the joint influence of saline intrusion and sluices on the DOM characteristics and water quality in sluice-controlled coastal plain rivers.     

Characterisation of dissolved organic matter in stormwater using high-performance size exclusion chromatography

Understanding the complexity of dissolved organic matter(DOM)in stormwater has drawn a lot of interest,since DOM from stormwater causes not only environmental impacts,but also worsens downstream aquatic quality associated with water supply and treatability.This study introduced and employed high-performance size exclusion chromatography(HPSEC)coupled with an ultraviolet–visible(UV–vis)diode array detector to assess changes in stormwater-associated DOM characteristics.Stormwater DOM was also analysed in relation to storm event characteristics,water quality and spectroscopic analysis.Statistical tools were used to determine the correlations within DOM and water quality measurements.Results showed that dissolved organic carbon(DOC)and UV absorbance at 254 nm(UV_(254))as conventional DOM parameters were found to be correlated well to the changes in stormwater quality during each of the three storm events studied.Both detector wavelengths(210and 254 nm)and their ratio(A_(210)/A_(254))were found to provide additional information on the physiochemical properties of stormwater-associated DOM.This study indicated that A_(210)/A_(254) is an important parameter which could be used to estimate the DOM proportions of functional groups and conjugated carbon species.This study provided also an understanding of stormwater quality constituents through assessing variability and sensitivity for various parameters,and the additional information of rainfall characteristics on runoff quality data for a better understanding of parameter correlations and influences.     

Sulfur-driven methylmercury production in paddies continues following soil oxidation

Methylmercury (MeHg) production in paddy soils and its accumulation in rice raise global concerns since rice consumption has been identified as an important pathway of human exposure to MeHg. Sulfur (S) amendment via fertilization has been reported to facilitate Hg methylation in paddy soils under anaerobic conditions, while the dynamic of S-amendment induced MeHg production in soils with increasing redox potential remains unclear. This critical gap hinders a comprehensive understanding of Hg biogeochemistry in rice paddy system which is characterized by the fluctuation of redox potential. Here, we conducted soil incubation experiments to explore MeHg production in slow-oxidizing paddy soils amended with different species of S and doses of sulfate. Results show that the elevated redox potential (1) increased MeHg concentrations by 10.9%−35.2%, which were mainly attributed to the re-oxidation of other S species to sulfate and thus the elevated abundance of sulfate-reducing bacteria, and (2) increased MeHg phytoavailability by up to 75% due to the reductions in acid volatile sulfide (AVS) that strongly binds MeHg in soils. Results obtained from this study call for attention to the increased MeHg production and phytoavailability in paddy soils under elevated redox potentials due to water management, which might aggravate the MeHg production induced by S fertilization and thus enhance MeHg accumulation in rice.     

Dissolved organic carbon, a critical factor to increase the bioavailability of phosphorus during biochar-amended aerobic composting

Considerable research efforts have been devoted to increase phosphorus（P） availability during aerobic composting.However,there is little discussion weather the dissolved organic carbon（DOC） controls the transformation among P-fractions.Thus,we investigated the changes in DOC compositions and P-fractions during biochar-amended composting（wet weight basis,5% and 10%）.TP content continuously increased since the ’concentration effect’ during aerobic composting.NaHCO₃-Pi,NaOH-Pi and HCl-Pi...     

Understanding the excretion rates of methylmercury and inorganic mercury from human body via hair and fingernails

Effective biomarkers are necessary to better understand the human mercury (Hg) exposure levels. However, mismatched biomarker sampling method causes extra uncertainty in assessing the risk of Hg exposure. To compare the differences between hair and fingernail, and further understand the excretion rates of methylmercury (MeHg) and inorganic mercury (IHg) via hair and fingernails, the total mercury (THg), MeHg, and IHg concentrations in paired hair and fingernail samples were investigated through paired samples collected from two typical mining areas, Wanshan mercury mine area (WMMA) and Hezhang zinc smelting area (HZSA). The positive correlation in THg, MeHg, and IHg concentrations (p <0.01) between hair and fingernail samples indicated that those two biomarkers can be corrected in application of assessing human Hg exposure. Compared to fingernails, the hair was suggested to be a more sensitive biomarker as the concentration of THg, MeHg and IHg were 2 ∼ 4 times higher than those in fingernails. Furthermore, the amounts of THg, MeHg, and IHg excreted via hair were 70 ∼ 226 times higher than that excreted via fingernails, and the hair plays a more important role than fingernails in the excretion of Hg from human bodies. Present study therefore provides some new insights to better understand the fate of human assimilated Hg.     

Formation of regulated and unregulated disinfection byproducts during chlorination and chloramination: Roles of dissolved organic matter type, bromide, and iodide

Algal blooms and wastewater effluents can introduce algal organic matter (AOM) and effluent organic matter (EfOM) into surface waters, respectively. In this study, the impact of bromide and iodide on the formation of halogenated disinfection byproducts (DBPs) during chlorination and chloramination from various types of dissolved organic matter (DOM, e.g., natural organic matter (NOM), AOM, and EfOM) were investigated based on the data collected from literature. In general, higher formation of trihalomethanes (THMs) and haloacetic acids (HAAs) was observed in NOM than AOM and EfOM, indicating high reactivities of phenolic moieties with both chlorine and monochloramine. The formation of haloacetaldehydes (HALs), haloacetonitriles (HANs) and haloacetamides (HAMs) was much lower than THMs and HAAs. Increasing initial bromide concentrations increased the formation of THMs, HAAs, HANs, and HAMs, but not HALs. Bromine substitution factor (BSF) values of DBPs formed in chlorination decreased as specific ultraviolet absorbance (SUVA) increased. AOM favored the formation of iodinated THMs (I-THMs) during chloramination using preformed chloramines and chlorination-chloramination processes. Increasing prechlorination time can reduce the I-THM concentrations because of the conversion of iodide to iodate, but this increased the formation of chlorinated and brominated DBPs. In an analogous way, iodine substitution factor (ISF) values of I-THMs formed in chloramination decreased as SUVA values of DOM increased. Compared to chlorination, the formation of noniodinated DBPs is low in chloramination.     

Effects of natural organic matter on cadmium mobility in paddy soil: A review

Cadmium (Cd) contamination in paddy soil has caused public concern. The uptake of Cd by rice plants depends on soil Cd mobility, which is in turn substantially influenced by organic matter (OM). In this review, we first summarize the fate of Cd in soil and the role of OM. We then focus on the effects of OM on Cd mobility in paddy soil and the factors influencing the remedial effectiveness of OM amendments. We further discuss the performance of straw incorporation in the remediation of Cd-contaminated paddy soils reported in laboratory and field studies. Considering the huge production of organic materials (such as straw) in agriculture, the use of natural OM for soil remediation has obvious appeal due to the environmental benefits and low cost. Although there have been successful application cases, the properties of OM amendments and soil can significantly affect the remedial performance of the OM amendments. Importantly, straw incorporation alone does not often decrease the mobility of Cd in soil or the Cd content in rice grains. Careful evaluation is required when considering natural OM amendments, and the factors and mechanisms that influence their remedial effectiveness need further investigation in paddy soil with realistic Cd concentrations.     

水环境中溶解性有机物溯源分析及分子结构表征概述

溶解性有机物(DOM)是地球上最大的碳基化合物反应性储层之一,涉及各种生物地化反应并且在污染物溶解度、毒性、生物利用度、流变性和分布中发挥重要作用。本文介绍了当前用于表征水环境中DOM的策略和工具,探讨了当前研究在技术限制(预处理过程复杂、仪器分辨率低、数据处理困)、结构复杂性、结构多变性等方面存在的诸多局限性。分析认为:已有研究主要侧重于溯源分析和分子结构特征解析,未来研究应该在不同的结构层面和角度开展,加强多学科融合、数据库创建、对照实验和协同工作。     

Degradation of dissolved organic matter in effluent of municipal wastewater plant by a combined tidal and subsurface flow constructed wetland

Dissolved organic matter (DOM) is an important constituent of wastewater treatment plant (WWTP) effluent. A novel combined tidal and subsurface flow constructed wetland (TF-SSF-CW) of 90 L was constructed for a ten-month trial of advanced treatment of the WWTP effluent. Excitation emission matrix (EEM) fluorescence spectroscopy, parallel factor (PARAFAC) analysis and a two end-member mixing model were employed to characterize the composition and removal process of the effluent DOM (EfOM) from the WWTP. The results showed that the TF-SSF-CW performed an efficient EfOM removal with dissolved organic carbon (DOC) removal rate of 88% and dissolved organic nitrogen (DON) removal rate of 91%. Further analysis demonstrated that the EfOM consisted mainly of two protein moieties and two humic-like groups; protein moieties (76%) constituted the main content of EfOM in raw water and humic-like groups (57%) became the dominating contributor after treatment. The EfOM from the WWTP was mainly of aquatic bacterial origin and evolved to a higher proportion of terrigenous origin with higher humification in the TF-SSF-CW effluent. A common controlling treatment-related factor for determining the concentrations of the same kind of substances (protein groups or humic-like groups) was revealed to exist, and the ratio of removal rates between the same substances in treatment was calculated. Our study demonstrates that the TF-SSF-CW can be a novel and effective treatment method for the EfOM from WWTPs, and is helpful for understanding of the character of EfOM in wetland treatment.     

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent

Molecular level characterization of dissolved organic sulfur(DOS) by electrospray ionizationFourier transform ion cyclotron resonance mass spectrometry(ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ioni...     

Ant colonization increased total mercury but reduced methylmercury contents in boreal mires, Northeast China

Soil macroinvertebrates as ecosystem engineers play significant, but largely ignored, roles in affecting mercury (Hg) cycle by altering soil physical-chemical properties. Ant is likely expanded into boreal mires with climate warming, however, its impacts on Hg cycle remained poorly understood. We compared total Hg (THg) and methylmercury (MeHg) contents in soils from antmounds (Lasius flavus) and the nearby ambient in a boreal mire in Northeast China. The present work seeks to unravel factors that controlling MeHg levels in case of ant appearance or absence. The average THg was 179 µg/kg in the ant mound and was 106.1 µg/kg in nearby soils, respectively. The average MeHg was 10.9 µg/kg in the ant mound and was 12.9 µg/kg in nearby soils, respectively. The ratios of MeHg to THg (%MeHg) were 7.61% in ant mounds and 16.75% in nearby soils, respectively. Ant colonization caused THg enrichment and MeHg depletion, and this change was obvious in the 10-20 cm depth soil layer where ants mainly inhabited. Spectrometry characteristics of soil dissolved organic matter (DOM) exert a stronger control than microorganisms on MeHg variation in soils. A structural equation model revealed that the molecular weight of DOM inhibited MeHg irrespective of ant presence or absence, while humification conducive to MeHg significantly in ant mound soils. Microorganisms mainly affected Hg methylation by altering the molecular weight and humification of DOM. We propose that the effects of ant colonization on MeHg rested on DOM feature variations caused by microorganisms in boreal mires.     

Characterization of dissolved organic matter and membrane fouling in coagulation-ultrafiltration process treating micro-polluted surface water

Coagulation–ultrafiltration(C–UF) is widely used for surface water treatment. With the removal of pollutants, the characteristics of organic matter change and affect the final treatment efficiency and the development of membrane fouling. In this study, we built a dynamic C–UF set-up to carry out the treatment of micro-polluted surface water, to investigate the characteristics of dissolved organic matter from different units. The influences of poly aluminum chloride and poly dimethyldiallylammonium chloride(PDMDAAC) on removal efficiency and membrane fouling were also investigated. Results showed that the dosage of PDMDAAC evidently increased the UV254 and dissolved organic carbon removal efficiencies,and thereby alleviated membrane fouling in the C–UF process. Most hydrophobic bases(HoB)and hydrophobic neutral fractions could be removed by coagulation. Similarly, UF was good at removing HoB compared to hydrophilic substances(HiS) and hydrophobic acid(HoA)fractions. HiS and HoA fractions with low molecule weight accumulated on the surface of the membrane, causing the increase of transmembrane pressure(TMP). Membrane fouling was mainly caused by a removable cake layer, and mechanical cleaning was an efficient way to decrease the TMP.