Characterization Of Dissolved Organic Matter Research Articles

Online LC-Orbitrap MS method for the rapid molecular characterization of dissolved organic matter.

High-resolution mass spectrometry (HRMS) combined with electrospray ionization (ESI) has been the most useful technique for molecular characterization of dissolved organic matter (DOM) derived from diverse sources. However, the comprehensive detection of DOM composition was hindered by ionization suppression observed in ESI sources. HRMS coupled with liquid chromatography (LC) is a potential tool for comprehensive molecular characterization of DOM. The Suwannee River fulvic acids (SRFAs) and two DOM samples from seawater and refinery wastewater extracted by solid phase extraction (SPE) were analyzed by LC-Orbitrap MS coupled with ESI. The mobile phases, solvent composition, and gradient in the LC-Orbitrap MS analysis were optimized. The number of detected molecular formulae of SRFAs by online LC-Orbitrap MS was significantly increased by approximately 40% compared to direct injection. These additional detected compounds are mainly protein and lignin-like compounds, with a low O/C ratio and high H/C ratio. For the SRFAs, the relative standard deviations (%) of reproducibility are 5.51, 2.33, 7.97, and 1.80 for average O/C, H/C, double bond equivalent, and modified aromaticity index, respectively. This study proposed a simple and rapid method based on LC-Orbitrap MS for an in-depth analysis of the molecular composition of DOM, achieving a remarkable analysis time of only 5 min per sample. The rapid method provides a dependable and efficient approach for the molecular characterization of DOM, thereby advancing our comprehension and investigation of DOM across diverse ecosystems.

Distinction of facilitating effects between dissolved organic matter derived from corn straw and fulvic acid on transport of titanium dioxide nanoparticles in saturated sand: Dependent on the solution chemistry

The application of organic materials into agricultural soil introduces dissolved organic matter (DOM) into environment. The DOM derived from organic materials would significantly affect the environmental behaviors of nanoparticles. In this study, DOM extracted from corn straw (CSDOM) was characterized and its effects on the transport of titanium dioxides nanoparticles (TiO2 NPs) in porous media were evaluated and compared with those of fulvic acid (FA). The characterization of DOMs indicated marked differences in molecular properties between CSDOM and FA. Weight-average molecular weight (Mw) of CSDOM was 3139 g/mol, higher than 1185 g/mol of FA, whereas CSDOM had a lower aromaticity than FA. Three distinct scenarios of nanoparticle mobility affected by CSDOM and FA were found. Under unfavorable conditions for nanoparticles mobility (pH 4.0 with/without electrolytes, pH 7.0 with electrolytes, and pH 10.0 with CaCl2), both DOMs facilitated TiO2 NPs mobility, and FA with higher aromaticity exerted stronger enhancing effects than CSDOM. However, the promoting effects of DOM on TiO2 NPs mobility were negligible under favorable conditions (pH 10.0 without electrolytes). Under the remaining conditions (pH 7.0 without electrolytes, and pH 10.0 with NaCl), DOM could facilitate the mobility of TiO2 NPs, while there was no difference in the facilitating effects between CSDOM and FA. It could be concluded that distinction of enhancing effects between CSDOM and FA on TiO2 NPs mobility was environmental chemistry-dependent. Furthermore, aromaticity rather than Mw would be a reasonable property determining the enhancing effects of DOM derived from distinct sources on nanoparticle mobility under unfavorable conditions.

Revealing degradation pathways of soluble and dissolved organic matter in alluvial-lacustrine aquifer systems impacted by high levels of geogenic ammonium

The excessive presence of geogenic ammonium (NH4+) in groundwater poses a global environmental concern, commonly linked to the degradation of nitrogen-containing dissolved organic matter (DOM). However, there is a gap in systematic studies on the combination of soluble organic matter (SOM) in sediments and DOM in groundwater, with few indoor incubation experiments to validate their degradation pathways. This study utilized ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry to analyze the molecular characteristics of DOM and SOM in aquifer systems affected by geogenic NH4+. Subsequently, indoor incubation experiments spanning up to 140 d were conducted to verify the degradation pathways. The experimental results revealed a two-phase degradation process for both the DOM and SOM. The initial stage was characterized by the degradation of aliphatic compounds (ALC) with the production of polyphenols (PPE) and highly unsaturated compounds (HUC). The second stage was dominated by the degradation of PPE and HUC, accompanied by the re-consumption of some ALC, while more recalcitrant HUC persisted. Notably, the first stage of SOM degradation exceeded that of DOM degradation, indicating that SOM exhibited greater resistance to aging. This phenomenon may be attributed to a wider range of active enzymes in sediments, the rapid replenishment of SOM by organic matter in sediments, or the accelerated degradation of DOM. The experimental results aligned with the molecular characterization of DOM and SOM in actual aquifer systems. It is hypothesized that NH4+ produced through the direct mineralization of SOM may contribute more to the enrichment of NH4+ in groundwater than that produced through the mineralization of DOM. This study is the first to analyze DOM and SOM together in aquifer systems and validate their degradation pathways through incubation experiments, thereby providing novel insights into the enrichment of geogenic NH4+ in groundwater.

Transformation of sedimentary dissolved organic matter in electrokinetic remediation catalogued by FT-ICR mass spectrometry

In electrokinetic remediation (EKR), the sedimentary dissolved organic matter (DOM) could impede remediation by scavenging reactive species and generating unintended byproducts. Yet its transformation and mechanisms remained largely unknown. This study conducted molecular-level characterization of the water-extractable DOM (WEOM) in EKR using negative-ion electrospray ionization coupled to 21 tesla Fourier transform ion cyclotron resonance mass spectrometry (21 T FT-ICR MS). The results suggested that ∼55 % of the ∼7,000 WEOM compounds identified were reactive, and EKR lowered their diversity, molecular weight distribution, and double-bond equivalent (DBE) through a combination of electrochemical and microbial redox reactions. Heteroatom-containing WEOM (CHON and CHOS) were abundant (∼ 35% of the total WEOM), with CHOS generally being more reactive than CHON. Low electric potential (1 V/cm) promoted the growth of dealkylation and desulfurization bacteria, and led to anodic CO2 mineralization, anodic cleavage of -SO and -SO3, and cathodic cleavage of -SH2; high electric potential (2 V/cm) only enriched desulfurization bacteria, and differently, led to anodic oxygenation and cathodic hydrogenation of unsaturated and phenolic compounds, in addition to cathodic cleavage of -SH2. The long-term impact of these changes on soil quality and nitrogen-sulfur-carbon flux may be need to studied to identify unknown risks and new applications of EKR.

Optical characterization of black carbon-derived DOM: Implication for the fluorescence detection of fuel combustion products in marine waters

Among pollutants released from shipping, black carbon (BC), also known as soot carbon, is of great interest due to its impacts on climate, air quality, human health and ecosystems. BC emitted from ships may enter marine waters and partially transfer to the seawater dissolved phase. In this study, we investigated the optical properties (absorbance and fluorescence) of dissolved organic matter (DOM) derived from BC particles (DOMBC) emitted by ships, which were compared to those of DOMBC of other origins (diesel-powered industrial machine, biomass burning, urban dust), and to terrestrial and marine DOM (DOMTER, DOMMAR). Ship and diesel DOMBC displayed higher ratios of fluorescence maximum intensity to dissolved organic carbon concentration (Fmax/DOC), higher specific UV absorbance at 254 nm (SUVA254), and lower fluorescence emission wavelengths than the other tested materials. The parallel factor analysis (PARAFAC)-derived fluorophores of the ship and diesel DOMBC exhibited significant correlations with the concentration of dissolved black carbon (DBC), determined using the benzenepolycarboxylic acid (BPCA) method. Based on these results, we propose the Combustion indeX (COX), to help detecting and tracking ship/fuel combustion pollutions in marine waters.

Enhancing Molecular Characterization of Dissolved Organic Matter by Integrative Direct Infusion and Liquid Chromatography Nontargeted Workflows.

Dissolved organic matter (DOM) in aquatic systems is a highly heterogeneous mixture of water-soluble organic compounds, acting as a major carbon reservoir driving biogeochemical cycles. Understanding DOM molecular composition is thus of vital interest for the health assessment of aquatic ecosystems, yet its characterization poses challenges due to its complex and dynamic chemical profile. Here, we performed a comprehensive chemical analysis of DOM from highly urbanized river and seawater sources and compared it to drinking water. Extensive analyses by nontargeted direct infusion (DI) and liquid chromatography (LC) high-resolution mass spectrometry (HRMS) through Orbitrap were integrated with novel computational workflows to allow molecular- and structural-level characterization of DOM. Across all water samples, over 7000 molecular formulas were calculated using both methods (∼4200 in DI and ∼3600 in LC). While the DI approach was limited to molecular formula calculation, the downstream data processing of MS2 spectral information combining library matching and in silico predictions enabled a comprehensive structural-level characterization of 16% of the molecular space detected by LC-HRMS across all water samples. Both analytical methods proved complementary, covering a broad chemical space that includes more highly polar compounds with DI and more less polar ones with LC. The innovative integration of diverse analytical techniques and computational workflow introduces a robust and largely available framework in the field, providing a widely applicable approach that significantly contributes to understanding the complex molecular composition of DOM.

Distribution characterization of MPs and DOM in ice-covered season in a saline-alkaline Lake in Daihai with an innovative analysis using 2DCOS and structural equation modelling

Due to the characteristics of low density, light weight, and strong hydrophobicity, microplastics (MPs) can adsorb dissolved organic matter (DOM) in lake water to jointly accomplish migration and transformation in the ice/water medium, which causes serious pollution to the lake during the ice period through accumulation. In this study, the distribution of Daihai Lake MPs and DOM was studied by fluorescence excited emission matrix (EEM) and micro-infrared spectroscopy, and the relationship between them was examined by two-dimensional correlation spectroscopy (2DCOS) and structural equation modelling (SEM) to obtain the influencing factors of pollution. The results indicate that the concentration of MPs in the surface ice layer is 1.35 times more than in the water and in the surface and bottom ice layers 1–2 times more than the middle layer. DOM in the ice cover is mainly protein-like (73.33%), and humus-like DOM (44.8%) is dominant in the water under the ice that is consistent with the distribution of MPs in the ice and water layer. As a result, MPs are more prospective to adsorb humus-like substances into the ice during migration. Through SEM analysis, it was concluded that human activities and the degree of economic development seriously affect the pollution level and the type of MPs and DOM in lakes. One of the most important factors in winter is the ice cover, and there is a strong correlation between the MPs and DOM in different ice layers. Combined with experimental data, it was concluded that the ice layer influences the distribution characteristics of the pollutants in lakes as well as the direction of migration. However, the adsorption mechanism of the ice is not clear, which will be a key direction for future research on microplastics in ice-covered lakes.

Spectral and molecular insights into the characteristics of dissolved organic matter in nitrate-contaminated groundwater

The characteristics of dissolved organic matter (DOM) serve as indicators of nitrate pollution in groundwater. However, the specific DOM components associated with nitrate in groundwater systems remain unclear. In this study, dual isotopes of nitrate, three-dimensional Excitation emission matrices (EEMs) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were utilized to uncover the sources of nitrate and their associations with DOM characteristics. The predominant nitrate in the targeted aquifer was derived from soil organic nitrogen (mean 46.0%) and manure &sewage (mean 34.3%). The DOM in nitrate-contaminated groundwater (nitrate-nitrogen >20 mg/L) exhibited evident exogenous characteristics, with a bioavailable content 2.58 times greater than that of uncontaminated groundwater. Regarding the molecular characteristics, DOM molecules characterized by CHO + 3N, featuring lower molecular weights and H/C ratios, indicated potential for mineralization, while CHONS formulas indicated the exogenous features, providing the potential for accurate traceability. These findings provided insights at the molecular level into the characterization of DOM in nitrate-contaminated groundwater and offer scientific guidance for decision-making regarding the remediation of groundwater nitrate pollution.

Assessing the spatiotemporal variability of dissolved organic matter fluorescence composition in the Lake George, NY watershed

Lake George (LG) is a temperate, oligotrophic, medium-sized lake (114 km2) located in northeastern New York State (U.S.). Lakes are highly understudied environments where extensive dissolved organic matter (DOM) processing occurs. With this study we establish the foundation for researching the organic biogeochemistry of the LG watershed, in particular, the numerous tributaries flowing into the lake. Collected were 213 samples from 64 tributaries and 12 lake locations. Some of the tributaries had unique wastewater, agricultural, or wetland influences. We employed fluorescence spectroscopy, a common biogeochemical technique, to characterize the fluorescent DOM (FDOM) component. We developed a parallel factor analysis (PARAFAC) model for the deconvolution of FDOM data allowing to depict six underlying FDOM constituents, which varied in source and biogeochemical reactivity on spatiotemporal scales. Tributary DOM, in comparison to lake DOM, was much more aromatic, of larger molecular weight, more humic, and contained less protein-like material. The distribution of humic and protein-like PARAFAC components was impacted by land-use and wastewater influences. Supporting characterization of the chromophoric DOM (CDOM) and total DOM (on dissolved organic carbon basis) allowed differentiating the influence of wetlands, which could not be depicted by spatiotemporally assessing the variability of PARAFAC components. Temporal assessment revealed minor variabilities in tributary DOM quantity and quality except in cases of point sources such as wastewater treatment facilities. Overall, this primer study establishes baseline understanding of the baseflow levels of DOM constituents in the LG watershed, and more broadly, presents a PARAFAC model for the deconvolution of fluorescence spectra of DOM from temperate and oligotrophic lake watersheds such as LG.

Fluorescence spectroscopy for tracking microbiological contamination in urban waterbodies

Dissolved organic matter (DOM) plays a crucial role in freshwater ecosystem function. Monitoring of DOM in aquatic environments can be achieved by using fluorescence spectroscopy. Particularly, DOM fluorescence can constitute a signature of microbiological contamination with a potential for high frequency monitoring. However, limited data are available regarding urban waterbodies. This study considers fluorescence data from field campaigns conducted in the Paris metropolitan region: two watercourses (La Villette basin and the river Marne), two stormwater network outlets (SO), and a wastewater treatment plant effluent (WWTP-O). The objectives of the study were to characterize the major fluorescence components in the studied sites, to investigate the impact of local rainfall in such components and to identify a potential fluorescence signature of local microbiological contamination. The components of a PARAFAC model (C1-C7), corresponding to a couple of excitation (ex) and emission (em) wavelengths, and the fluorescence indices HIX and BIX were used for DOM characterization. In parallel, fecal indicator bacteria (FIB) were measured in selected samples. The PARAFAC protein-like components, C6 (ex/em of 280/352 nm) and C7 (ex/em of 305/340 nm), were identified as markers of microbial contamination in the studied sites. In the La Villette basin, where samplings covered a period of more than 2 years, which also included similar numbers of wet and dry weather samples, the protein-like components were significantly higher in wet weather in comparison to dry weather. A positive relationship was obtained between C6 and FIB. In urban rivers, the high frequency monitoring of C6 levels would support the fecal contamination detection in rivers. In addition, it could help targeting specific field campaigns to collect comprehensive dataset of microbiological contamination episodes.

Toward a More Comprehensive Approach for Dissolved Organic Matter Chemical Characterization Using an Orbitrap Fusion Tribrid Mass Spectrometer Coupled with Ion and Liquid Chromatography Techniques.

Dissolved organic matter (DOM) represents one of the largest active organic carbon pools in the global carbon cycle. Although extensively studied, only <10% of DOM has been chemically characterized into individual dissolved compounds due to its molecular complexity. This study introduced a more comprehensive DOM characterization method by coupling both ion chromatography (IC) and liquid chromatography (LC) with high mass accuracy and resolution mass spectrometry. We presented a new on-the-fly mass calibration of the Orbitrap technique by utilizing the "lock mass" function in the Orbitrap Fusion Tribrid mass spectrometer (OT-FTMS), which assures high mass accuracy at every scan by a postcolumn introduction of internal labeled standards. With both IC and LC, tested unlabeled standards of amino acids, small peptides, and organic acids were consistently below 1.0 ppm mass error, giving the OT-FTMS the potential of reaching mass accuracy of the Fourier-transform ion cyclotron resonance mass spectrometer. In addition to mass accuracy, a pooled quality control sample (QC) was used to increase reproducibility by applying systematic error removal using random forest (SERRF). Using an untargeted mass spectrometry approach, estuarine DOM samples were analyzed by OT-FTMS coupled to IC in negative mode and LC in positive mode detection to cover a wide range of highly cationic to highly anionic molecules. As a proof of concept, we focused on elucidating the structures of three distinct DOM compound classes with varied acidities and basicities. In UPLC-OT-FTMS, a total of 915 compounds were detected. We putatively elucidated 44 small peptides and 33 deaminated peptides of these compounds. With IC-OT-FTMS, a total of 1432 compounds were detected. We putatively elucidated 20 peptides, 268 deaminated peptides, and 188 organic acids. Except for five compounds, all putatively elucidated compounds were uniquely detected in their corresponding chromatography technique. These results highlight the need for combining these two techniques to provide a more comprehensive method for DOM characterization. Application of the combined IC and LC techniques is not limited to DOM chemical characterization. It can analyze other complex compound mixtures, such as metabolites, and anthropogenic pollutants, such as pesticides and endocrine-disrupting chemicals, in environmental and biological samples.

Methods for molecular characterization of dissolved organic matter in the alpine water environment: an overview

The alpine area has become a sensitive indicator and amplifier of global climate change and human activities because of its unique geographical and climatic conditions. Being an essential part of biochemical cycling, dissolved organic matter (DOM) could effectively help understand the process, structure, and function of alpine aquatic ecosystems. Due to the low content and sampling difficulties, the analysis of DOM in alpine water demands high sensitivity with low sample volume, which has not been comprehensively reviewed. This review summarizes the DOM sampling, pretreatment, and analysis methods involving the characterization of concentration, spectroscopy, and molecular structure. Overall, conventional parameters are the basis of advanced characterization methods. Spectroscopic tests can reveal the optical properties of DOM in response to lights from ultraviolet to infrared wavelengths, to distinguish the chemical composition. Molecular structure characterizations can provide microscopic information such as functional groups, element ratios, and molecular weights. The combination of multiple methods can depict DOM composition from multiple perspectives. In sum, optimized sampling and pretreatment, high-sensitivity molecular characterization, and method integration are crucial for effectively analyzing DOM components in alpine waters. These perspectives help to standardize the DOM characterization process and to understand the correlation between DOM composition and its properties, as well as the migration and transformation of DOM.

Photochemical reactivity of water-soluble dissolved organic matter from microplastics and microfibers

Plastics in aquatic environments are a source of dissolved organic matter (DOM). However, its production pathways and environmental fate remain poorly understood. This study investigated the yields, characterization, and photochemical reactivities of water-soluble DOM from seven pristine microplastics (MPs) and three microfibers (MFs). We found yields of plastic-derived DOM per unit mass of MPs or MFs, including chromophoric DOM (CDOM) and dissolved organic carbon (DOC), were significantly influenced by polymer chemical structures. Notably, MFs exhibited consistently higher DOM yields compared to MPs. In addition, plastics containing aromatic rings, such as PETE and PS, were found to generate higher CDOM yields, although PVC also showed elevated CDOM yields. The plastic-derived DOM had a diverse molecular size-range, spanning from 60 nm (polyester-DOM) to 937 nm (LDPE-DOM), while Zeta potentials, which were predominantly negatively charged, varied from −42.5 mV (nylon-DOM) to +4.6 mV (LMW-PVC-DOM). Degradation rate constants for CDOM (0.001–0.022 h−1) were generally higher than DOC (0.0009–0.020 h−1), with a shorter half-life for PETE- and PS-derived DOM. The reactivity and degradation kinetics of plastic-derived DOM were notably manifested in changes of fluorescence spectra (excitation-emission matrixes) during photochemical weathering, showing the influence of polymeric composition/structures. This baseline study provides an improved understanding of the characterization and environmental fate of microfiber- and plastic-derived DOM in aquatic environments.

Expanding the Limits of Structural Characterization of Marine Dissolved Organic Matter Using Nonuniform Sampling Frequency-Reversed Edited HSQC NMR.

The multiplicity-edited heteronuclear single quantum correlation (ME-HSQC) NMR method is widely used for the structural characterization of marine dissolved organic matter (DOM), which is a complex molecular mixture comprising millions of individual compounds. However, the standard ME-HSQC suffers from significant signal cancellation and subsequent loss of crucial structural information due to the overlap between CH3/CH (positive) and CH2 (negative) cross-peaks in overcrowded regions. This study introduces nonuniform sampling in frequency-reversed ME-HSQC (NUS FR-ME-HSQC), highlighting its remarkable potential for the comprehensive structural characterization of marine DOM. By reversing the frequency of CH2 cross-peaks into an empty region, the FR-ME-HSQC method effectively simplifies the spectra and eliminates signal cancellation. We demonstrate that nonuniform sampling enables the acquisition of comparable spectra in half the time or significantly enhances the sensitivity in time-equivalent spectra. Comparative analysis also identifies vulnerable CH2 cross-peaks in the standard ME-HSQC that coincide with CH3 and CH cross-peaks, resulting in the loss of critical structural details. In contrast, the NUS FR-ME-HSQC retains these missing correlations, enabling in-depth characterization of marine DOM. These findings highlight the potential of NUS FR-ME-HSQC as an advanced NMR technique that effectively addresses challenges such as signal overcrowding and prolonged experimental times, enabling the thorough investigation of complex mixtures with implications in several fields, including chemistry, metabolomics, and environmental sciences. The advantages of NUS FR-ME-HSQC are experimentally demonstrated on two solid-phase-extracted DOM (SPE-DOM) samples from the surface and deep ocean. With this new technology, differences in the composition of DOM from various aquatic environments can be assigned to individual molecules.

Molecular characterization of DOM: A full-scale case study of an advanced DWTP from Jintan, China

Since the variation of dissolved organic matter (DOM) is complicated in the aquatic environment and water treatment processes, adverse effects on human and water quality may be triggered. Nowadays, more drinking water treatment plants (DWTPs) begin using pretreatment and advanced treatment processes for removing refractory DOM to pursue high-quality drinking water, including preozonation, and combined ozonation and biological activated carbon (BAC) treatment. The combination of Fourier transform ion cyclotron resonance mass spectrometer and fluorescence spectroscopy could comprehensively unveil the DOM composition and characteristics in water treatments. This study aims to provide information on the molecular and spectroscopic characteristics of DOM in a DWTP with pretreatments and advanced treatment processes and summarize the removal efficiency of different treatment processes on DOM. Results showed that the removal rate of low-molecular-weight acids (LMW-acids) by BAC was as high as 98 %, reflecting the synergistic effect of ozonation/BAC unit. Pre-ozonation enhanced coagulation process had a good removal effect on CHONS. The diversity of DOM increased and the relative abundance of DOM intensity was reduced in preozonation/coagulation/sedimentation and O3/BAC units. The preozonation-coagulation/sedimentation unit reduced the aromaticity or unsaturation of DOM while the advanced treatment process had a higher removal rate of fluorescent components.

Distinguishing between Sources of Natural Dissolved Organic Matter (DOM) Based on Its Characteristics

Increasing levels of dissolved organic matter (DOM) in watercourses in the northern hemisphere are mainly due to reduced acid rain, climate change, and changes in agricultural practices. However, their impacts vary in time and space. To predict how DOM responds to changes in environmental pressures, we need to differentiate between allochthonous and autochthonous sources as well as identify anthropogenic DOM. In this study we distinguish between allochthonous, autochthonous, and anthropogenic sources of DOM in a diverse watercourse network by assessing effects of land cover on water quality and using DOM characterization tools. The main sources of DOM at the studied site are forests discharging allochthonous humic DOM, autochthonous fulvic DOM, and runoff from urban sites and fish farms with high levels of anthropogenic DOM rich in protein-like material. Specific UV absorbency (sUVa) distinguishes allochthonous DOM from autochthonous and anthropogenic DOM. Anthropogenic DOM differs from autochthonous fulvic DOM by containing elevated levels of protein-like material. DOM from fishponds is distinguished from autochthonous and sewage DOM by having high sUVa. DOM characteristics are thus valuable tools for deconvoluting the various sources of DOM, enabling water resource managers to identify anthropogenic sources of DOM and predict future trends in DOM.

Effect of salinity on molecular characterization of dissolved organic matter using ESI FT-ICR MS

Solid-phase extraction (SPE) coupled with negative-ion Electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been widely used for molecular characterization of dissolved organic matter (DOM). However, little attention has paid to test whether the salinity of the sample and the presence of chloride ions in water samples affect the molecular composition of DOM extracted by SPE (SPE-DOM). In this study, one natural organic matter standard and several natural waters were selected to investigate how salinity affects the molecular composition of SPE-DOM and the selectivity of chloride ion adducts formation with respect to the molecular structure of SPE-DOM in negative ion ESI FT-ICR MS analysis. The results show that the molecular composition of SPE-DOM varied in a sample made by different salinity; and the variation pattern of DOM composition was different among different water samples under the treatment of consistent salinity gradients. The chloride ions can't be completely removed from cartridges in conventional SPE, thus leading organic compounds in SPE-DOM to form [M+Cl]‾ adducts when performing ESI FT-ICR MS analysis. In addition, the molecules with high H/C and low O/C ratios were likely to form [M+Cl]‾ ions. The relative abundance of [M+Cl]‾ ions could increase with the increase of salinity. These results are instructive to guide the pretreatment and molecular characterization of DOM in water samples with different salinity. Overall, we proposed a modification to the SPE to minimum reduce the formation of chloride ion adducts during the isolation of DOM.

Characterization of dissolved organic matter distribution in forestland and farmland of mollisol based on untargeted metabolomics

Mollisol soil is a major contributor to food production. Clarification of the molecular characteristics of dissolved organic matter (DOM) will contribute to the overall understanding and management of mollisol soil. However, the complexity of DOM poses a challenge to understanding its molecular characteristics. In this study, we investigated the molecular characteristics of DOM (< 1 000 Da) in mollisol soils with different soil use patterns (forestland and dryland) based on untargeted metabolomics. Here, we confirmed the feasibility of untargeted metabolomics for the molecular characterization of DOM in mollisol soils. DOM in forestland is mainly derived from plant metabolites, and DOM can perform more biological functions. However, DOM in dryland has complex composition and has powerful co-occurrence network interactions due to human activities. Water has better extraction efficiency for polar DOM, while organic reagents can efficiently extract lipid-like DOM, but the polarity of the extractant has less influence on the DOM than the soil physicochemical properties. Meanwhile, 14-dihydroxyzeatin screened based on metabolomics can be used as a potential indicator for corn land. Therefore, untargeted metabolomics can be an effective method to characterize the DOM molecules of mollisol soil, which provides new insights for management of mollisol soil and sustainable agricultural development.

Chlorpyrifos fate in the Arctic: Importance of analyte structure in interactions with Arctic dissolved organic matter

The insecticide and current use pesticide chlorpyrifos (CLP) is transported via global distillation to the Arctic where it may pose a threat to this ecosystem. CLP is readily detected in Arctic environmental compartments, but current research has not studied its partitioning between water and dissolved organic matter (DOM) nor the role of photochemistry in CLP's fate in aquatic systems. Here, the partition coefficients of CLP were quantified with various types of DOM isolated from the Arctic and an International Humic Substances Society (IHSS) reference material Suwannee River natural organic matter (SRNOM). While CLP readily partitions to DOM, CLP exhibits a significantly higher binding constant with Arctic lacustrine DOM relative to fluvial DOM or SRNOM. The experimental partitioning coefficients (KDOC) were compared to a calculated value estimated using poly parameter linear free energy relationship (pp-LFER) and was found to be in good agreement with SRNOM, but none of the Arctic DOMs. We found that Arctic KDOC values decrease with increasing SUVA254, but no correlations were observed for the other DOM compositional parameters. DOM also mediates the photodegradation of CLP, with stark differences in photo-kinetics using Arctic DOM isolated over time and space. This work highlights the chemo-diversity of Arctic DOM relative to IHSS reference materials and highlights the need for in-depth characterization of DOM that transcends the current paradigm based upon terrestrial and microbial precursors.

Complementary Elucidation of the Molecular Characteristics of Groundwater Dissolved Organic Matter Using Ultrahigh-Resolution Mass Spectrometry Coupled with Negative- and Positive-Ion Electrospray Ionization.

The formula assignment of the Fourier transform ion cyclotron resonance mass spectrometry coupled with positive-ion electrospray ionization [ESI(+)-FT-ICR MS] is challenging because of the extensive occurrence of adducts. However, there is a paucity of automated formula assignment methods for ESI(+)-FT-ICR MS spectra. The novel automated formula assignment algorithm for ESI(+)-FT-ICR MS spectra developed herein has been applied to elucidate the composition of dissolved organic matter (DOM) in groundwater during air-induced ferrous [Fe(II)] oxidation. The ESI(+)-FT-ICR MS spectra of groundwater DOM were profoundly impacted by [M + Na]+ adducts and, to a lesser extent, [M + K]+ adducts. Oxygen-poor and N-containing compounds were frequently detected when the FT-ICR MS was operated in the ESI(+) mode, while the components with higher carbon oxidation states were preferentially ionized in the negative-ion electrospray ionization [ESI(-)] mode. Values for the difference between double-bond equivalents and the number of oxygen atoms from -13 to 13 are proposed for the formula assignment of the ESI(+)-FT-ICR MS spectra of aquatic DOM. Furthermore, for the first time, the Fe(II)-mediated formation of highly toxic organic iodine species was reported in groundwater rich in Fe(II), iodide, and DOM. The results of this study not only shed light on the further algorithm development for comprehensive characterization of DOM by ESI(-)-FT-ICR MS and ESI(+)-FT-ICR MS but also highlight the importance of appropriate treatment of specific groundwater prior to use.