Interactions Of Dissolved Organic Matter Research Articles

Multiple effects of iron oxides on the adsorption and oxidation of dissolved organic matter by manganese oxides

Adsorptive fractionation and oxidation of dissolved organic matter (DOM) on manganese (Mn) oxide surfaces alter the molecular composition and stability of DOM, but the impact of iron (Fe) oxides on the coupled adsorption-oxidation processes of DOM by Mn oxides is largely unknown. In this study, the underlying mechanisms of molecular transformation of DOM on birnessite (Bir) in the presence of ferrihydrite (Fh), with varying Fh/Bir mass ratios, were investigated at both molecular levels and microscopic scales with a suite of characterization techniques, including Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and spherical aberration corrected scanning transmission electron microscopy (Cs-STEM). We found that higher Fh/Bir mass ratio impeded the adsorption of DOM by birnessite and the reductive dissolution of birnessite to release dissolved Mn, and the impediment on the reductive dissolution of birnessite was proportional to Fh/Bir mass ratio. Overall, during the interactions of DOM with ferrihydrite and birnessite, phenolic compounds were preferentially adsorbed by Fe and Mn minerals, and compounds with higher oxygen contents and polymeric substances were formed. FT-ICR-MS analysis further suggested that higher Fh/Bir mass ratio inhibited the occurrence of aromatic ring-opening and carboxylation of substituted groups on aromatic rings, but promoted polymerization of phenolic compounds. Cs-STEM analysis revealed that DOM distributions on ferrihydrite, birnessite, and their mixtures were regulated by their microscopic structures and reactivity. Compared with aromatic carbon (C), carboxylic and phenolic C were more likely to associate with birnessite. Our results highlighted the significance of organo-mineral associations with the mixed minerals in regulating the distribution and reactivity of organic C. This study has provided molecular evidences for molecular transformation of DOM mediated by both Mn and Fe oxides, which contributed to advancing our understanding on coupled reactions of organic C at the mineral–water interfaces in the environment.

Participation of strong charge-assisted hydrogen bonds in interactions of dissolved organic matter represented by Suwannee River Humic Acid

Terrestrial dissolved organic matter (DOM) plays critical roles in many biotic and abiotic environmental reactions as well as in water treatment. Its structure is therefore of great interest. We examined dissolved Suwannee River Humic Acid (HA) to probe the potential participation of exceptionally strong, negative charge-assisted hydrogen bonds, (−)CAHB, in DOM cohesion and interaction with small weak acids using high performance size exclusion chromatography (HPSEC), transmission electron microscopy, zeta-pH curves, and pH drift experiments. The results support a previously proposed two-tier state of aggregation, in which tightly-knit primary particles (≤ ∼10 kDa) form larger secondary aggregates (up to micrometer in size). Evidence for (−)CAHB is gained through zeta potential changes and pH drift experiments. The primary particles interact with (−)CAHB-capable solutes (simple carboxylic acids and phosphate) but not (−)CAHB-incapable solutes. We identified disruption of intra-segmental and inter-molecular (−)CAHB leading to swelling and disaggregation, as well as formation of nouveau (−)CAHB with free groups on HA. The effects were solute-concentration dependent and greater at pH 5 than pH 6, consistent with CAHB theory. Phosphate induced the greatest shifts in the HPSEC molecular size distribution curves. The shifts were unaffected by prior stripping of innate polyvalent metals. We conclude that the (−)CAHB contributes to the cohesion of DOM, affecting its size and charge, and provides a means by which weak acid pollutants, nutrients, and natural compounds can interact with DOM. Such interactions have implications for the behavior of DOM in the environment, the fate and transport of anthropogenic pollutants, and the roles DOM play in water treatment technologies.

Metagenomic and FT-ICR MS insights into the mechanism for the arsenic biogeochemical cycling in groundwater

Arsenic (As) is a groundwater contaminant of global concern. The degradation of dissolved organic matter (DOM) can provide a reducing environment for As release. However, the interaction of DOM with local microbial communities and how different sources and types of DOM influence the biotransformation of As in aquifers is uncertain. This study used optical spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), metagenomics, and structural equation modeling (SEM) to demonstrate the how the biotransformation of As in aquifers is promoted. The results indicated that the DOM in high-As groundwater is dominated by highly unsaturated low-oxygen(O) compounds that are quite humic and stable. Metagenomics analysis indicated Acinetobacter, Pseudoxanthomonas, and Pseudomonas predominate in high-As environments; these genera all contain As detoxification genes and are members of the same phylum (Proteobacteria). SEM analyses indicated the presence of Proteobacteria is positively related to highly unsaturated low-O compounds in the groundwater and conditions that promote arsenite release. The results illustrate how the biogeochemical transformation of As in groundwater systems is affected by DOM from different sources and with different characteristics.

Spectroscopic studies of the role of dissolved organic matter in acenaphthene photodegradation in liquid water and ice

The effect of concentration and origin of dissolved organic matter (DOM) on acenaphthene (Ace) photodegradation in liquid water and ice was investigated, and the components in DOM which were involved in Ace photodegradation were identified. The DOM samples included Suwannee River fulvic acid (SRFA), Elliott soil humic acid (ESHA), and an effluent organic matter (EfOM) sample. Due to the production of hydroxyl radical (•OH) and triplet excited-state DOM (3DOM*) which react with Ace, DOM had promotion effects on Ace photodegradation. However, the promotion effects of DOM were prevailed over by their suppressing effect of DOM including screening light effect, intermediates reducing effect and RS quenching effect, and thus, the photodegradation rates of Ace decreased in the presence of the three DOM with concentrations of 0.5–7.5 mg C/L in liquid water and ice. ESHA had higher light absorption and thus had higher screening light effect on Ace photodegradation in liquid water than SRFA and EfOM. At each DOM concentration, ESHA exhibited higher promotion effect on Ace photodegradation than SRFA and EfOM, in liquid water and ice. The binding of Ace with DOM was indicated by decreases in fluorescence intensity of Ace when coexisted with DOM. However, the binding of Ace to DOM played an unimportant role in suppressing Ace photodegradation. The photodegradation behavior of fluorophores in Ace with DOM present in ice was not similar to that in liquid water. C–O, C═O, carboxyl groups O–H and aliphatic C–H functional groups in DOM were involved in the interaction of DOM with Ace. The presence of Ace seemed to have no influence on the photodegradation behavior of functional groups in DOM.

Influence of Divalent Cation Inhibition and Dissolved Organic Matter Enhancement on Phenol Oxidation Kinetics by Manganese Oxides.

Manganese oxides can oxidize organic compounds, such as phenols, and may potentially be used in passive water treatment applications. However, the impact of common water constituents, including cations and dissolved organic matter (DOM), on this reaction is poorly understood. For example, the presence of DOM can increase or decrease phenol oxidation rates with manganese oxides. Furthermore, the interactions of DOM and cations and their impact on the phenol oxidation rates have not been examined. Therefore, we investigated the oxidation kinetics of six phenolic contaminants with acid birnessite in ten whole water samples. The oxidation rate constants of 4-chlorophenol, 4-tert-octylphenol, 4-bromophenol, and phenol consistently decreased in all waters relative to buffered ultrapure water, whereas the oxidation rate of bisphenol A and triclosan increased by up to 260% in some waters. Linear regression analyses and targeted experiments demonstrated that the inhibition of phenol oxidation is largely determined by cations. Furthermore, quencher experiments indicated that radical-mediated interactions from oxidized DOM contributed to enhanced oxidation of bisphenol A. The variable changes between compounds and water samples demonstrate the challenge of accurately predicting contaminant transformation rates in environmentally relevant systems based on experiments conducted in the absence of natural water constituents.

Stabilization of hydrophobic organic compounds in sediment using alkali-activated rice husk biochar: Enhancement of sorption by dissolved organic matter

Polycyclic aromatic hydrocarbons and phthalate esters are hydrophobic organic compounds (HOCs) that pose strong risks to aquatic and sediment ecosystems. The aim of this study was to develop a material for stabilizing (sorbing) HOCs in contaminated sediment. Activated biochar with a high surface area (called RH–NaOH) was successfully synthesized by activating rice husk biochar with an alkali (NaOH). The kinetics of HOC sorption to the RH–NaOH were described well by a three-stage intraparticle diffusion model. The sorption isotherms were adequately described by the Sips sorption model. The presence of dissolved organic matter (DOM) at environmentally relevant concentrations enhanced HOC sorption to the RH–NaOH by as much as a factor of 10, and this was mainly caused by the fulvic-acid- and humic-acid-like fractions of the DOM. The degree of sorption enhancement was predicted by the integrated volume of the fulvic-acid- and humic-acid-like fraction regions of the excitation–emission matrix that was used to characterize the DOM. The polycyclic aromatic hydrocarbon and phthalate ester stabilization efficiencies when 150 d was allowed for equilibration between the sediment and RH–NaOH to be reached were 96.5% and 94.6%, respectively. The stabilization tests indicated that HOC sorption proceeded via multiple stages with different kinetics. These stages were attributed to complex processes involving HOC and DOM sorption and desorption, HOC–DOM interactions, and HOC and HOC–DOM mixture diffusion into pores. The RH–NaOH has great potential for use as a sorbent for stabilizing HOCs in contaminated sediment.

Linking Redox Characteristics to Dissolved Organic Matter Derived from Different Biowaste Composts: A Theoretical Modeling Approach Based on FT-ICR MS Analysis.

Compost dissolved organic matter (DOM) is a complex mixture of redox-active organic molecules that impact various biogeochemical processes in soil environments. However, the impact of chemical complexity (heterogeneity and chemodiversity) on the electron accepting capacity (EAC) and electron donating capacity (EDC) of DOM molecules remains unclear, which hinders our ability to predict their environmental behavior and redox properties. In this study, the applicability of Vienna Soil Organic Matter Modeler 2 (VSOMM2) to the composting system based on the FT-ICR MS data has been validated. A molecular modeling approach using VSOMM2 and Schrödinger software was developed to quantitatively assess the redox sites and molecular interactions of compost DOM. Compost DOM molecules are categorized into three distinct groups based on their heterogeneous origins. In addition, we have developed 18 molecular models of compost DOM based on the links of molecules to EAC/EDC. Finally, Ar-OH, quinone, Ar-SH, and Ar-NH2 were identified as the redox sites; noncovalent contacts, H bonds, salt bridges, and aromatic-H bonds might be significant electronic transmission channels of compost DOM. Our findings contribute to the development of precise regulatory methods for functional molecules within compost DOM, providing the fine standards for composts matching specific ecosystem service requirements.

Interactions between particulate organic matter and dissolved organic matter in a weak dynamic bay revealed by stable isotopes and optical properties

Few studies have incorporated the tools of stable isotopes and optical properties to study the biogeochemical process of organic matter (OM), including particulate organic matter (POM) and dissolved organic matter (DOM), which prevents our comprehension of the interactions between POM and DOM in the marine environment. In this study, the origin, distribution, and fate of POM and DOM in Tieshangang Bay, a weak dynamic bay were investigated by measuring δ13C and δ15N of POM, dissolved organic carbon (DOC), and absorption and fluorescence of DOM (CDOM and FDOM). In the upper bay, POM source was mainly originated from terrestrial discharge, whereas the high fluorescence index (FI) indicated that external aquatic organism activity dominated DOM sources. In contrast, in the outer bay, the slightly increased δ13C and enriched δ15N of POM and enhanced fluorescence intensities of protein-like DOM components indicated the considerable contributions of the in situ biological activities to OM. A net addition of DOC and optical components of DOM occurred in both the upper and outer bays. The decomposition of terrestrial POM was responsible for the addition of DOM due to the weak dynamics in the upper bay, whereas the enhanced primary production and the strong decomposition of freshly produced POM jointly contributed to the addition of DOM in the outer bay. Our study suggests that hydrodynamics regulate the biogeochemistry and interactions of POM and DOM in the weak dynamic bay.

Dissolved Organic Matter and Lignin Modulate Aquatic Toxicity and Oxidative Stress Response Activated by Layered Double Hydroxides Nanomaterials.

Advanced nanomaterials can be released into the environment and can coexist with natural organic matter (NOM). However, evidence on the impacts of NOM on the environmental behavior and toxicity of advanced nanomaterials is still scarce. Here, we investigated the behavior and toxic effects of two layered double hydroxides (LDHs) nanomaterials with different metallic constituents (Mg-Al-LDH and Zn-Al-LDH) at relatively low exposure concentrations on a freshwater green alga (Chlorella pyrenoidosa) in the absence and presence of two types of NOM, namely dissolved organic matter (DOM) and dealkaline lignin (DL). The DOM or DL interaction with the LDHs at different mixture levels was shown to be an antagonistic effect on the growth inhibition toxicity to C. pyrenoidosa mainly. The estimation of the index of Integrated Biological Responses version 2 indicated that the joint interaction of the LDHs with DOM or DL occurred in the following order of frequency synergism > antagonism > additivity. Furthermore, the physicochemical characteristics of LDHs were crucial for illuminating the mechanism by which the DOM or DL modified the LDH-induced oxidative stress response. These findings highlighted the important role of NOM in the behavior and effect of LDHs as a representative of a new class of multifunctional nanomaterials in the freshwater environment.

Which sediment fraction mainly drives microplastics aging process: Dissolved organic matter or colloids?

Riparian sediment is the last barrier preventing contaminants from polluting aquatic ecosystems. Recently, microplastics (MPs) have frequently been found in sediments. However, the MP aging process and its impact on sediments remain unknown. This study aimed to identify the key driving factors and mechanisms of riparian sediment on MPs aging behavior. The results showed that MPs surface suffered heavy breakage and the oxygen-to-carbon ratio of MPs increased by 268% after accumulation in sediment for 214 d. The carbonyl index revealed that the degree of MP aging driven by dissolved organic matter (DOM) was 6.7-83.6% greater than that of colloids, indicating that DOM was the key sediment fraction driving MP aging. Sunlight was an important environmental factor that enhanced MPs aging by sediment fractions, because photo-irradiated DOM produced hydroxyl and superoxide radicals to damage the MPs structure. Benzoic acid, dibenzoylmethane, and 4-heptyl-4,6-diphenyl-tetrahydro-pytan-2-one were the main products during the MP aging process under the interaction of sunlight and DOM, which showed acute toxicity to aquatic organisms and caused more severe toxicity during the chronic period. These results clearly clarify the behavior and environmental risk of MPs after accumulation in sediment, providing guide information to control MP pollution in the riparian zone.

Environmental predictors of electroactive bacterioplankton in small boreal lakes.

Extracellular electron transfer (EET) by electroactive bacteria in anoxic soils and sediments is an intensively researched subject, but EET's function in planktonic ecology has been less considered. Following the discovery of an unexpectedly high prevalence of EET genes in a bog lake's bacterioplankton, we hypothesized that the redox capacities of dissolved organic matter (DOM) enrich for electroactive bacteria by mediating redox chemistry. We developed the bioinformatics pipeline FEET (Find EET) to identify and summarize predicted EET protein-encoding genes from metagenomics data. We then applied FEET to 36 bog and thermokarst lakes and correlated gene occurrence with environmental data to test our predictions. Our results provide indirect evidence that DOM may participate in bacterioplankton EET. We found a similarly high prevalence of genes encoding putative EET proteins in most of these lakes, where oxidative EET strongly correlated with DOM. Numerous novel clusters of multiheme cytochromes that may enable EET were identified. Taxa previously not considered EET-capable were found to carry EET genes. We propose that EET and DOM interactions are of ecologically important to bacterioplankton in small boreal lakes, and that EET, particularly by methylotrophs and anoxygenic phototrophs, should be further studied and incorporated into methane emission models of melting permafrost.

Promotion of the biodegradation of phenanthrene adsorbed on microplastics by the functional bacterial consortium QY1 in the presence of humic acid: Bioavailability and toxicity evaluation

The adsorption of hydrophobic organic compounds (HOCs) by microplastics (MPs) has attracted great attention in recent years. However, the ultimate environmental fate of the HOCs sorbed on MPs (HOCs-MPs) is poorly understood. In this work, we investigated the potential influence of the biotransformation process on the environmental fate of phenanthrene (PHE, a model HOC) sorbed on MPs (PHE-MPs) under the existence of humic acid (HA, the main ingredient of dissolved organic matter (DOM)) in the aquatic environment. The results indicated that the adsorption behavior of PHE on MPs decreased its bioavailability and thus inhibited its biotransformation efficiency. However, HA significantly promoted the biodegradation rate and percentage of PHE-MPs. This was probably because HA improved the desorption of PHE from MPs, which promoted the acquisition of PHE by bacteria from the aqueous phase. Further, HA dramatically increased the bacterial community diversity and richness and altered the community composition. The richness of some PHE-degrading bacteria, such as Methylobacillus and Sphingomonas, significantly increased, which may also be an important factor for promoting PHE biodegradation. Molecular ecological network analysis implied that HA enhanced the modularity and complexity of bacterial interaction networks, which was beneficial to maintaining the functional stability of the consortium QY1. Besides, HA decreased the cytotoxicity of functional microbes induced by HOCs-MPs. This work broadens our knowledge of the environmental fate of HOCs-MPs and interactions of MPs, HOCs, DOMs and functional microbial consortiums in aqueous environments.

Interactions of dissolved organic matter with short-range ordered aluminosilicates by adsorption and co-precipitation

Retention of dissolved organic matter (DOM) by short-range ordered aluminosilicates (SROAS) by adsorption and co-precipitation contributes to carbon accrual in soils and sediments. In this study, we investigated effects of SROAS composition on DOM adsorption, partitioning of carbon moieties by adsorption and co-precipitation, and the mineral structure of co-precipitates. We used four types of sorptive solutions, representing DOM collected in situ from topsoil and subsoil horizons of a Dystric Cambisol, and water-extracted DOM from beech and fir litter. We studied adsorption of soil DOM on three SROAS that structurally resemble proto-imogolites and Si-rich allophanes as a function of contact time (1–168 h) at initial pH 5. Co-precipitation of soil and litter-extracted DOM was quantified as a function of the molar Al:C ratio (0.3–1.4) and at two levels of Si concentration (molar Al:Si = 1 and 2). To resolve the impact of DOM on mineral structure, we first examined time-dependent structural evolution of SROAS within 1 to 72 h and subsequently investigated the effects of DOM interference in crystallization processes. Mineral structure of SROAS and co-precipitates was resolved by infrared, solid-state 27Al- and 29Si-NMR spectroscopy. Chemical composition of DOM prior to reaction with SROAS and in co-precipitates was analysed by solid-state 13C-NMR spectroscopy. Maximal C contents of adsorption complexes were 7.1 mg C g−1 for Al-rich and 20.4 mg C g−1 for Si-rich SROAS. We found selective adsorption of aromatic C and preferential exclusion of polysaccharide and alkyl C for both topsoil and subsoil DOM. Adsorption was larger for a Si-rich SROAS, since it exhibited a greater accessibility of aluminol groups. As a function of aromatic C content in initial DOM, 39.9 to 81% of C was retained by co-precipitation. Composition of co-precipitated organic matter was determined by C speciation in DOM supply, involving marked uptake of polysaccharides. In the absence of DOM, up to 50% of Si was present in imogolite-like configuration after 72 h, evidencing rapid development of short-range order. Complexation of Al by DOM during formation of SROAS caused partial exclusion of Si and slowed structural evolution, consequently enhancing abundance of ill-defied Si species in co-precipitates. Interactions of DOM with SROAS may cause selective accumulation of organic compounds and promote Si mobility in Andosols and Podzols.

New Insights into Microbial Interactions with Dissolved Organic Matter in Acid Mine Drainage with the Integration of Microbial Community and Chemical Composition Analysis

Acid mine drainage (AMD) environments are one of the most extreme ecosystems on earth, and their biogeochemical cycling has been widely studied. However, the carbon cycling underlying microbial interactions with dissolved organic matter (DOM) is poorly understood in these environments. Here, we evaluated the relationships between microbial populations and DOM pools in an AMD lake by combining high-throughput microbial and chemical compositional analyses. The results demonstrated that microalgae were the predominant primary producers in the system and significantly contributed to the total DOM concentration in the water column, whereas DOM chemodiversity was correlated with bacterial community diversity. Network analyses further revealed that DOM associated with microalgae had low diversity but high relative abundance, suggesting microalgal selective organic matter contribution to the DOM pool. Conversely, diverse DOM molecules with generally low abundance were associated with heterotrophic acidophiles, including members of Alphaproteobacteria, Actinobacteria, Firmicutes, and Acidobacteria. Moreover, microalgae and bacteria exhibited predominantly positive co-occurrences with potential metabolic interactions via DOM exchange. Taken together, this study provides new insights into the microbe–DOM interactions in extreme AMD ecosystems and has significant implications for understanding the carbon cycle and microbial metabolism in extreme environments.

Progress in the interaction of dissolved organic matter and microbes (1991-2020): a bibliometric review.

Dissolved organic matter (DOM) and microbes are key in the planetary carbon cycle, and research on them can lead to a better understanding of the global carbon cycle and an improved ability to cope with environmental challenges. Several papers have reviewed one or several aspects of the interaction of DOM and microbes, but no overall review has been performed. Here, we bibliometrically analyzed all publications from the Web of Science on DOM and microbes (1991-2020). The results showed that studies on DOM and microbes grew exponentially during this period; the USA contributed the most to the total publications, and China has had the fastest increasing rate since 2010. Moreover, we used the Latent Dirichlet Allocation model to identify topics and determine their (cold or hot) trends by analyzing the abstracts of 9851 publications related to DOM and microbes. A total of 96 topics were extracted, and these topics that are related to the source, composition, and removal path of DOM and the temporal-spatial patterns of DOM and microbes consistently rose from 1991 to 2020. Most studies have used accurate and rapid methods combined with microbiological genetic approaches to study the interaction of DOM and microbes in terrestrial and aquatic ecosystems. The results also showed that the impacts of climate change and land use on the interaction of DOM and microbes, and topics related to human health have received considerable attention. In the future, the interaction mechanism of DOM and microbes and its response to environmental change should be further elucidated.

Ultraviolet-visible and fluorescence spectra indicate the binding and transformation properties of hexavalent chromium in DOM solution

Dissolved organic matter (DOM) with complex functional groups affects the trace of binding and transformation of hexavalent chromium (Cr(VI)) in the environment. However, the mechanisms and quantitative indicators are still ambiguous. In this study, the perspectives of spectroscopy with synchronous and excitation-emission matrix (EEM) fluorescence, and ultraviolet-visible (UV–vis) were employed to probe the interaction of DOM and Cr(VI). The spectroscopic parameters with Dslope240–280 (the slope of the log-transformed absorbance in the range of 240–280 nm), DSlope325–375 (the slope of the log-transformed absorbance in the range of 325–375 nm), SR (the ratio of the slope of the log-transformed absorption coefficient with 275–295 nm to 350–400 nm), SFI (specific fluorescence intensities), AvgFI/AvgUVA (the ratio of average fluorescence to average UV), and SS (Stokes shift) of UV–vis and fluorescence were extracted to characterize the DOM properties. The UV–vis results showed carboxylic-like and total phenolic/carboxylic-like groups were contributed to the complexation of Cr, which resulted in forming macromolecular aggregates, however, the degree of participation of different functional groups was uneven and the binding sequence depended on the types of fractions especially the ratio of protein. Meanwhile, the EEM results proved interaction between DOM and Cr also affected the hydrophobicity and quantum yield of solutions. In addition, according to the change orders of substances and functional groups by Two-dimensional correlation spectroscopy (2DCOS) analysis, aromatic amino acids substances were much more sensitive binding onto Cr than fulvic-like fractions and humic-like fractions, and the mechanisms for Cr(VI) retention were developed. Statistical analysis results showed that SR and SFI were significantly correlated with the concentration of Cr(VI), and multiple linear regression models were developed to predict concentrations of Cr(VI). Moreover, it was found the goodness of fit of SFI was better than that of SR at low Cr concentrations, but opposite at high concentrations.

Iron (hydr)oxides mediated immobilization and interaction of dissolved organic matter and inorganic phosphate: A review

铁(氢)氧化物介导的溶解性有机质(DOM)和无机磷(DIP)的固定在水生态系统中普遍存在，对碳、磷元素的生物地球化学循环有重要的影响. 铁(氢)氧化物主要通过吸附和共沉淀两种过程固定DOM和DIP，且铁(氢)氧化物、DOM和DIP三者存在复杂的相互作用. 本文主要从铁(氢)氧化物对DOM和DIP的固定，铁(氢)氧化物、DOM和DIP之间的相互影响等方面综述了相关研究进展，梳理了铁(氢)氧化物、DOM和DIP在吸附和共沉淀过程中的相互作用机制与影响因素. DOM的存在会通过占据铁(氢)氧化物表面吸附点位、络合、抑制铁水解沉淀等途径影响铁(氢)氧化物对DIP的固定; 且不同机制与DOM的不同性质如分子大小、芳香组分、羧基官能团含量等有关. 而DIP的存在会改变铁(氢)氧化物对DOM的固定分馏过程，改变溶液中DOM的组分和性质. 在明晰三者相互作用基础上，探讨了铁(氢)氧化物介导的DOM和DIP的固定过程对湖泊内源磷释放和碳埋藏的可能影响，并对未来的研究方向进行了展望.;Iron(hydr)oxides mediated immobilization of dissolved organic matter (DOM) and inorganic phosphate (DIP) is ubiquitous in aquatic ecosystems, which plays an important role in the biogeochemical cycle of carbon and phosphorus. The immobilization of DOM and DIP based on iron(hydr)oxides is mainly via adsorption and coprecipitation, and there is a complex interaction among iron(hydr)oxide, DOM and DIP. This paper reviewed the relevant studies on the immobilization of DOM and DIP by iron(hydr)oxides and their interactions. We discussed the interaction mechanism and influencing factors on the interaction among iron (hydr)oxides, DOM and DIP during the processes of adsorption and coprecipitation. The presence of DOM affects the fixation of DIP by occupying the adsorption sites on the surface of iron(hydr)oxides, complexing and inhibiting iron hydrolysis and precipitation. The properties of DOM, such as molecular size, aromatic components, carboxyl functional group content are the main decisive factors. The presence of DIP changes the immobilization and fractionation of DOM by iron(hydr)oxides, and thus the composition and properties of DOM in solution. After clarifying the interaction of iron(hydr)oxides, DOM and DIP, the potential effects of these interactions on internal phosphate release and carbon burial in lakes were discussed. The potential future research issues were proposed.

FT-IR and synchronous fluorescence two-dimensional correlation spectroscopic analysis on the binding properties of mercury onto humic acids as influenced by pH modification and sulfide addition

Mercuric Hg2+ ion forms strong complexes with dissolved organic matter (DOM) in natural waters. The complexation of Hg2+ by sulfhydryl groups of DOM was regarded as the main mechanism for Hg2+-DOM interactions, particularly in anoxic sulfur and DOM-rich environments. In the present study, the influences of pH and sulfide addition on the molecular structure of Hg2+-DOM complexes and the characteristics of Hg2+ binding to DOM were investigated using FT-IR and synchronous fluorescence two-dimensional correlation spectroscopic analysis. Results showed that, during the Hg2+ binding process, the aromatic hydrogen CH in humic acids (HA) gave the fastest responses to pH perturbation and the S-reacted HA (S-HA) exhibited different reaction patterns from the unreacted HA. In S-HA, the esters/alcohols CO and carboxyl CO gave the fastest responses to Hg2+ binding. In the process of S-HA binding to Hg2+, the protein-like fractions including proteins, amino acids or monoaromatics played the leading role. Sulfide addition of HA enhanced the reactivity of small molecular weight compounds with low aromaticity and improved the binding ability of protein-like fractions to Hg2+. These findings provide a better understanding of the interaction mechanisms between Hg2+ and DOM at a molecular level and have important environmental implications in Hg2+ biogeochemical transformation, transport and cycling.

Distributions and interactions of dissolved organic matter and heavy metals in shallow groundwater in Guanzhong basin of China

Groundwater as the primary source of fresh water particularly in semi-arid regions is heavily threatened by various pollutants such as dissolved organic matter (DOM) and heavy metals due to anthropogenic activities. In this study, 113 shallow groundwater samples were collected from Guanzhong basin of China to explore spatial distributions and interactions of DOM and heavy metals (Fe, Mn and Cu). Fluorescence excitation-emission spectrophotometry with parallel factor analysis showed that DOM in groundwater mainly contained three humic-like and two protein-like substances with an average dissolved organic carbon (DOC) concentration of 12.85 mg L−1. Average Mn and Cu concentrations in groundwater were 19.92 μg L−1 and 7.05 μg L−1 with an increasing trend from west to east, whereas Fe concentration in central regions was much higher (34.23 μg L−1). Structural equation modeling analysis indicated that DOM in groundwater could be significantly affected by surface water, and heavy metals were influenced by urbanization. Moreover, DOM could strongly influence the bioavailability, migration, and transformation of Mn in groundwater. These findings would be beneficial for the effective utilization and protection of groundwater resources.

Technical note: Effects of iron(II) on fluorescence properties of dissolved organic matter at circumneutral pH

Abstract. Modern fluorescence spectroscopy methods, including excitation–emission matrix (EEM) spectra parsed using parallel factor analysis (PARAFAC) statistical approaches, are widely used to characterize dissolved organic matter (DOM) pools. The effect of soluble reduced iron, Fe(II), on EEM spectra can be significant but is difficult to quantitatively assign. In this study, we examine the effects of Fe(II) on the EEM spectra of groundwater samples from an anaerobic deltaic aquifer containing up to 300 mg L−1 Fe(II), located a few kilometres from the ocean and adjacent to the Fraser River in Richmond, British Columbia, Canada. We added varying quantities of Fe(II) into groundwater samples to evaluate Fe(II)–DOM interactions. Both the overall fluorescence intensity and the intensity of the primary peak, a humic-like substance at excitation and emission wavelengths of 239 and 441–450 nm (peak A), respectively, decreased by approximately 60 % as Fe(II) concentration increased from 1 to 306 mg L−1. Furthermore, the quenching effect was nonlinear and proportionally stronger at Fe(II) concentrations below 100 mg L−1. This nonlinear relationship suggests a static quenching mechanism. In addition, DOM fluorescence indices are substantially influenced by the Fe(II) concentration. With increasing Fe(II), the fluorescence index (FI) shifts to higher values, the humidification index (HIX) shifts to lower values, and the freshness index (FrI) shifts to higher values. Nevertheless, the 13-component PARAFAC model showed that the component distribution was relatively insensitive to Fe(II) concentration; thus, PARAFAC may be a reliable method for obtaining information about the DOM composition and its redox status in Fe(II)-rich waters. By characterizing the impacts of up to 300 mg L−1 Fe(II) on EEMs using groundwater from an aquifer which contains similar Fe(II) concentrations, we advance previous work which characterized impacts of lower Fe(II) concentrations (less than 2 mg L−1) on EEMs.