Molecular Composition Of Dissolved Organic Matter Research Articles

Influences of molecular composition in dissolved organic matter on its reactivity with chlorine radicals (Cl• and Cl2•−)

Dissolved organic matter (DOM) is a major scavenger of chlorine radicals (e.g., Cl• and Cl2•−) in water. However, there is limited literature addressing the impact of DOM molecular composition on its reactivity towards chlorine radicals. This work focused on discovering the relationships between DOM molecular composition and its reactivity towards Cl• and Cl2•−. The molecular composition of 23 DOM isolates from different sources was characterized using high-resolution mass spectrometry, and their rate constants with Cl• (kDOM-Cl•) and Cl2•− (kDOM-Cl2•−) were determined using laser flash photolysis and competition kinetics. Orthogonal partial least squares (OPLS) analysis model was then used to identify the most correlated and effective predictors of kDOM-Cl• and kDOM-Cl2•−. The kDOM-Cl• positively correlated to higher unsaturation and aromaticity while negatively correlated to the proportion of several N- and S-containing formulas. The kDOM-Cl2•− values showed positive correlation with unsaturation and aromaticity while showing negative correlation with the proportion of CHOPwa formulas. These observations suggest that while unsaturation and aromaticity serve as useful indicators of reactivity with chlorine radicals, non-oxygen heteroatom-containing formulas within the DOM isolates play a pivotal role in governing their interactions with chlorine radicals.

Characterization and differentiation of dissolved organic matter in leachate derived from an old Japanese landfill site through Orbitrap mass spectrometry

AbstractElucidating the characteristics of dissolved organic matter (DOM) is crucial to assessing its impact on the bioavailability and mobility of pollutants in landfill leachate. This study reports a comprehensive 5–month investigation into the characteristics of DOM in leachate from an old Japanese landfill, collected at six different sampling points. The molecular composition, chemical properties, and structural characteristics of DOM were assessed using Orbitrap mass spectrometry and spectral analysis. The leachate DOM mainly consisted of CHO-containing molecules (58.5–88.9%), low-oxygen unsaturated phenolic compounds (40.5–54.0%), and aliphatic compounds (19.4–47.3%), with slight variation among sampling points. A significant portion of the nominal oxidation state of carbon was in the reduced zone (76.2–95.4%). The results underscore the distinct molecular composition of DOM in mature Japanese landfill leachate compared to young and mature leachates from other countries. Two of six sampling points, with notable differences in molecular characteristics, were compared and elucidated. The composition of landfill waste, rather than landfill age, was the main factor affecting the characteristics and differentiation of leachate DOM.

Storm-driven hydrological, seasonal, and land use/land cover impact on dissolved organic matter dynamics in a mid-Atlantic, USA coastal plain river system characterized by 21 T FT-ICR mass spectrometry

Introduction: Dissolved organic matter (DOM) as primary and secondary energy sources can be transported via rivers to estuaries and impact coastal biogeochemical cycles. Storm-induced high discharge events can alter the dominant river flow paths and enhance leaching of shallow organic-rich soil layers, leading to elevated terrestrial DOM export. Land use/land cover (LULC) and associated anthropogenic interventions (including artificial reservoirs and agricultural irrigation) can control sources and transformation processes of exported DOM along with hydrologic factors. The relative significance of LULC, hydrological factors, and temperature variations with seasons will differ depending on geographical locations and complicate their incorporation in biogeochemical models of DOM dynamics. This study investigates the role of LULC, seasonality, and storm events on DOM concentrations and molecular composition in the Murderkill River system.Method: Surface water samples were collected seasonally and before/after storm events from 6 sites representing forested, agricultural, and developed LULC units. The DOM was characterized via parallel factor analysis of excitation-emission matrix data and electrospray ionization 21 T Fourier-transform ion cyclotron resonance mass spectrometry to determine potential DOM sources and enable the development of a conceptual model for DOM dynamics in rivers impacted by anthropogenic reservoirs.Result and Discussion: Our results suggest that storm-induced shallow and overland flow paths can increase surface-vegetation/plant-litter derived DOM based on atomic ratios associated with specific biogenic precursors (i.e., lignin, tannins, and/or oxygenated aromatic DOM), particularly in winter when autochthonous production was suppressed due to reduced temperatures. We further demonstrate that the damming effects of artificial reservoirs enhance the role of seasonal patterns of autochthonous production, disrupting storm-shunt process and stimulating significantly more bio-produced DOM export during spring and summer (i.e., tryptophan/tyrosine-like. N- and S- containing, phytoplankton-derived compounds). Collectively, these results demonstrate how artificial reservoirs alter the characteristics of DOM exported from rivers with implications for understanding carbon export and fate at river-estuary interfaces.

Changes in coal waste DOM chemodiversity and Fe/Al oxides during weathering drive the fraction conversion of heavy metals

The long-term accumulation of coal waste on the surface during natural weathering leads to the inevitable migration of heavy metals contained in the coal waste, which increases the likelihood of environmental contamination and health risks. Dissolved organic matter (DOM) and Fe/Al oxides play crucial roles in the transformation and bioavailability of heavy metals. Thus, we analyzed the Fe/Al oxide content and DOM molecular composition in coal waste with different degrees of weathering and explored the influence of DOM chemical diversity and Fe/Al oxides on the potential mobility of heavy metals. Results showed that weathering-driven decrease in Fe oxides (Fed, FeO, and Fep decreased from 82.4, 37.5, and 3.6 mg∙L−1 to 41.3, 24.7, and 2.3 mg∙L−1, respectively) led to decreases in the reducible fractions of V and Cr. The potential environmental risks of more toxic metals of Cd and As, also increased as a result of the residual fractions decreased to 32.6 % and 41.3 %, respectively. Weathering caused an increase in oxygen-to‑carbon ratio, double-bond equivalent, modified aromaticity index, nominal oxidation state of carbon, and molecular diversity and a decrease in (m/z)w and (H/C)w, suggesting that the DOM of highly weathered coal waste possessed high unsaturation, aromatic structures, hydrophilicity, and strong oxidative characteristics. Additionally, although VMF and CrMF showed significant negative correlations with O/C ratio, polyphenolic, carbohydrates, and condensed aromatics, pH remained a key environmental factor determining the potential environmental risks of V and Cr by changing the residual fractions. The mobilities of Cd and As were significantly negatively correlated with those of Fe/Al oxides, particularly Fed, FeO, Fep, and Alp. Our findings contribute to the understanding of the impact of weathering on the geochemical cycling of different coal waste components, providing priority options for environmental risk prevention and control in coal mining areas.

Strong associations between dissolved organic matter and microbial communities in the sediments of Qinghai-Tibetan Plateau lakes depend on salinity

In aquatic ecosystems, dissolved organic matter (DOM) plays a vital role in microbial communities and the biogeochemical cycling of elements. However, little is known about the associations between DOM and microbial communities in lake sediments. This study investigated the composition of water-extractable organic matter and microbial communities in surface sediments of lakes with different salinities on the Qinghai-Tibet Plateau. Ultrahigh-resolution mass spectrometry and high-throughput microbial sequencing techniques were employed to assess the associations between molecular diversity and microbial diversity and the effects of salinity in 19 lakes spanning a salinity range from 0.22 ‰ to 341.87 ‰. Our results show that increasing salinity of lake water led to higher molecular diversity of DOM in surface sediments. High-salinity lakes exhibited distinct DOM characteristics, such as lower aromaticity, smaller molecular weight, and higher oxidation degree, compared to freshwater lakes. The complexity of the microbial network composition of sediments first increased and then decreased with the increase of salinity. Moreover, as salinity increases, the dominant species transitioned from Gammaproteobacteria to Bacteroidia, and this transition was accompanied by a decrease in microbial diversity and an increase in molecular diversity. Microbial factors accounted for 34.68 % of the variation in the molecular composition of DOM. Overall, this study emphasizes the significant effects of salinity on both molecular and microbial diversity in lake sediments. Furthermore, our findings underscore the importance of microbes in controlling the range of organic compounds present in lakes and deepen our knowledge of the biogeochemical cycling of DOM.

Enrichment of Geogenic Organoiodine Compounds in Alluvial-Lacustrine Aquifers: Molecular Constraints by Organic Matter.

Organoiodine compounds (OICs) are the dominant iodine species in groundwater systems. However, molecular mechanisms underlying the geochemical formation of geogenic OICs-contaminated groundwater remain unclear. Based upon multitarget field monitoring in combination with ultrahigh-resolution molecular characterization of organic components for alluvial-lacustrine aquifers, we identified a total of 939 OICs in groundwater under reducing and circumneutral pH conditions. In comparison to those in water-soluble organic matter (WSOM) in sediments, the OICs in dissolved organic matter (DOM) in groundwater typically contain fewer polycyclic aromatics and polyphenol compounds but more highly unsaturated compounds. Consequently, there were two major sources of geogenic OICs in groundwater: the migration of the OICs from aquifer sediments and abiotic reduction of iodate coupled with DOM iodination under reducing conditions. DOM iodination occurs primarily through the incorporation of reactive iodine that is generated by iodate reduction into highly unsaturated compounds, preferably containing hydrophilic functional groups as binding sites. It leads to elevation of the concentration of the OICs up to 183 μg/L in groundwater. This research provides new insights into the constraints of DOM molecular composition on the mobilization and enrichment of OICs in alluvial-lacustrine aquifers and thus improves our understanding of the genesis of geogenic iodine-contaminated groundwater systems.

The specific molecular signature of dissolved organic matter extracted from different arctic plant species persists after biodegradation

Dissolved organic matter (DOM) is a small but very reactive pool of organic matter (OM) in the environment. Its role is related to its composition, which depends on its source. In soils, vegetation is the main source of DOM, and biodegradation is the main regulating mechanism. This study aims to characterise DOM produced by contrasted arctic vegetation species and their biodegradation products.The water-extractable organic matter (WEOM) was produced from C. stellaris (lichen), E. vaginatum (sedge), A. polifolia (dwarf evergreen shrub) and B. nana (deciduous dwarf shrub). The WEOM were inoculated with a common aerobic heterotrophic soil bacteria (P. aureofaciens) and incubated for 7 days. During the experiment, WEOM was characterised through a wide range of analytical methods (TOC, UV–Vis absorbance, high-performance ion chromatography and HRMS Orbitrap).The results showed bacteria consumed a significantly greater proportion of WEOM produced by C. stellaris than by A. polifolia and B. nana at the end of the experiment (p < 0.05). Furthermore, the number of features in WEOM decreased for C. stellaris and E. vaginatum, whereas it increased for B. nana. These findings shed light on the species-specific biodegradation processes that rely on the initial composition of DOM, specifically influenced by the vegetation's capacity to produce recalcitrant compounds. Furthermore, our results emphasised that even though bacterial activity greatly impacted molecular characteristics, the WEOM produced by different vegetation species maintained their distinct molecular signatures. As a result, it can be inferred that the DOM found in natural environments directly reflects the relevant vegetation cover despite the strong influence of biogeochemical processes on DOM molecular composition. This should be considered when developing models to assess the influence of climate change on vegetation cover composition and its subsequent effects on DOM dynamics in soil and surface waters.

Decreasing Photoreactivity and Concurrent Change in Dissolved Organic Matter Composition With Increasing Inland Water Residence Time

AbstractPhotochemical degradation of dissolved organic matter (DOM) has been the subject of numerous studies; however, its regulation along the inland water continuum is still unclear. We aimed to unravel the DOM photoreactivity and concurrent DOM compositional changes across 30 boreal aquatic ecosystems including peat waters, streams, rivers, and lakes distributed along a water residence time (WRT) gradient. Samples were subjected to a standardized exposure of simulated sunlight. We measured the apparent quantum yield (AQY), which corresponds to DOM photomineralization per photon absorbed, and the compositional change in DOM at bulk and individual compound levels in the original samples and after irradiation. AQY increased with the abundance of terrestrially derived DOM and decreased at higher WRT. Additionally, the photochemical changes in both DOM optical properties and molecular composition resembled changes along the natural boreal WRT gradient at low WRT (&lt;3 years). Accordingly, mass spectrometry revealed that the abundance of photolabile and photoproduced molecules decreased with WRT along the boreal aquatic continuum. Our study highlights the tight link between DOM composition and DOM photodegradation. We suggest that photodegradation is an important driver of DOM composition change in waters with low WRT, where DOM is highly photoreactive.

Spatial gradients and molecular transformations of DOM, DON and DOS in human-impacted estuarine sediments

Dissolved organic matter (DOM) constitutes the most active fraction in global carbon pools, with estuarine sediments serving as significant repositories, where DOM is susceptible to dynamic transformations. Anthropogenic nitrogen (N) and sulfur (S) inputs further complicate DOM by creating N-bearing DOM (DON) and S-bearing DOM (DOS). This study delves into the spatial gradients and transformation mechanisms of DOM, DON, and DOS in Pearl River Estuary (PRE) sediments, China, using combined techniques of UV–visible spectroscopy, Excitation–emission matrix (EEM) fluorescence spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), and microbial high-throughput sequencing. Results uncovered a distinct spatial gradient in DOM concentration, aromaticity (SUVA254), hydrophobicity (SUVA260), the content of substituent groups including carboxyl, carbonyl, hydroxyl and ester groups (A253/A203) of chromophoric DOM (CDOM), and the abundances of tyrosine/tryptophan-like protein and humic-like substances in fluorophoric DOM (FDOM). These all decreased from upper to lower PRE, accompanied by a decrease in O3S and O5S components, indicating seaward reduction in the contribution of terrestrial OM, especially anthropogenic inputs. Additionally, sediments exhibited a reduction in molecular diversity (number of formulas) of DOM, DON, and DOS from upper to lower PRE, with molecules tending towards a lower nominal oxidation state of carbon (NOSC) and higher bio-reactivity (MLBL), molecular weight (m/z) and saturation (H/C). While molecular composition of DOM remained similar in PRE sediments, the relative abundance of lignin-like substances decreased, with a concurrent increase in protein-like and lipid-like substances in DON and DOS from upper to lower PRE. Mechanistic analysis identified the joint influence of terrestrial OM, anthropogenic N/S inputs, and microbial processes in shaping the spatial gradients of DOM, DON, and DOS in PRE estuarine sediments. This study contributes valuable insights into the intricate spatial gradients and transformations of DOM, DON, and DOS within human-impacted estuarine sediments.

The chemical succession in anoxic lake waters as source of molecular diversity of organic matter

The aquatic networks that connect soils with oceans receive each year 5.1 Pg of terrestrial carbon to transport, bury and process. Stagnant sections of aquatic networks often become anoxic. Mineral surfaces attract specific components of organic carbon, which are released under anoxic conditions to the pool of dissolved organic matter (DOM). The impact of the anoxic release on DOM molecular composition and reactivity in inland waters is unknown. Here, we report concurrent release of iron and DOM in anoxic bottom waters of northern lakes, removing DOM from the protection of iron oxides and remobilizing previously buried carbon to the water column. The deprotected DOM appears to be highly reactive, terrestrially derived and molecularly distinct, generating an ambient DOM pool that relieves energetic constraints that are often assumed to limit carbon turnover in anoxic waters. The Fe-to-C stoichiometry during anoxic mobilization differs from that after oxic precipitation, suggesting that up to 21% of buried OM escapes a lake-internal release-precipitation cycle, and can instead be exported downstream. Although anoxic habitats are transient and comprise relatively small volumes of water on the landscape scale, our results show that they may play a major role in structuring the reactivity and molecular composition of DOM transiting through aquatic networks and reaching the oceans.

Probing the optical and molecular properties of sedimentary dissolved organic matter in the laminated diatom mats from the southern Mariana Trench

Laminated diatom mats (LDMs) deposition, formed by the aggregation of giant diatoms (e.g., Ethmodiscus rex), are recognized as a crucial driver of the global carbon and silicon cycles due to their substantial contribution to the flux of organic carbon and biogenic silica. The biogenic silica-rich sediment is one of the typical sediment types in the deep-sea setting of the tropical Pacific Ocean. Here, we analyzed the concentrations of pore-water dissolved organic carbon (DOC) and phosphate (PO43−), the optical properties, and molecular compositions of dissolved organic matter (DOM) in the two LDMs cores and one non-LDMs core retrieved from the southern Mariana Trench. Our results showed that the LDMs sediments with higher total organic carbon (TOC) contents have lower concentrations of DOC and chromophoric dissolved organic matter (CDOM), compared to the non-LDMs core. Meanwhile, the LDMs samples exhibited lower relative intensity of fluorescent proteins-like, molecular lability boundary (MLBL%) and higher values for humification index (HIX) and aromaticity modification (AImod) compared to the non-LDM core, indicating a higher level of stability and recalcitrance of DOM likely resulting from microbial degradation of relatively labile DOM compounds. Furthermore, the LDMs samples were characterized by a high abundance of CHO-containing DOM components and a low abundance of nitrogen- and sulfur-containing components, potentially linked to microbial degradation of hydrocarbon compounds that were enriched in the LDMs sediments. Additionally, the unique formulas in the LDMs samples demonstrated higher degree of recalcitrance suggested by higher aromaticity and fraction of CRAM, which may be attributed to microbial transformation of DOM. These findings add to our limited knowledge of the optical properties and molecular composition of DOM in the deep-sea opal-rich sediments, and have implications for understanding DOM cycling in the deep oceans.

Depth-dependent variations of physicochemical properties of sedimentary dissolved organic matter and the influence on the elimination of typical pharmaceuticals

Sedimentary dissolved organic matter (DOM) could exert a significant influence on the transformation of trace organic contaminants. However, the variations of sedimentary DOM properties with depth and their impact on trace organic contaminants biodegradation remain unclear. In this study, the qualitative changes in DOM properties with depth were assessed using spectral techniques. Specifically, within the sediment range of 0–30 cm, humic acid and fulvic acid fractions exhibited higher degrees of humification and aromatization at 10–20 cm, while hydrophilic fractions showed higher degrees of humification and aromatization at 20–30 cm. Furthermore, electrochemical methods were employed to quantitatively assess the electron transfer capacity of sedimentary DOM at different depths, which displayed consistent variation trend with humification and aromatization degree. The high degree of humification and aromatization, along with strong electron-accepting capability of DOM, significantly enhanced the biodegradation rates of tetracycline and ritonavir. To gain deeper insights into the influence of molecular composition of DOM on its properties, two-dimensional gas chromatography-quadrupole mass spectrometry analysis revealed that quinones and phenolic hydroxyl compounds govern the redox reactivity of DOM. Simulated experiment of DOM-mediated biodegradation of typical pharmaceuticals confirmed the role of quinones and phenolic hydroxyl groups in the redox reactivity of DOM.

Micro-biological degradation and transformation of dissolved organic matter following continuous cropping of tobacco.

In recent years, the problems associated with continuous cropping (CC) that cause soil degradation have become increasingly serious. As a key soil quality property, dissolved organic matter (DOM) affects the circulation of carbon and nutrients and the composition of bacterial communities in soil. However, research on the changes in the molecular composition of DOM after CC is limited. In this study, the soil chemical properties, DOM chemical diversity, bacterial community structure, and their interactions are explored in the soil samples from different CC years (CC1Y, CC3Y, CC5Y, and CC7Y) of tobacco. With increasing CC year of tobacco, most of the soil chemical properties, such as total carbon, total nitrogen and organic matter, decreased significantly, while dissolved organic carbon first decreased and then increased. Likewise, the trends of DOM composition differed with changing duration of CC, such as the tannin compounds decreased from 18.13 to 13.95%, aliphatic/proteins increased from 2.73 to 8.85%. After 7 years of CC, the soil preferentially produced compounds with either high H/C ratios (H/C > 1.5), including carbohydrates, lipids, and aliphatic/proteins, or low O/C ratios (O/C < 0.1), such as unsaturated hydrocarbons. Furthermore, core microorganisms, including Nocardioides, wb1-P19, Aquabacterium, Methylobacter, and Thiobacillus, were identified. Network analysis further indicated that in response to CC, Methylobacter and Thiobacillus were correlated with the microbial degradation and transformation of DOM. These findings will improve our understanding of the interactions between microbial community and DOM in continuous cropping soil.

Emerging investigator series: impacts of land use on dissolved organic matter quality in agricultural watersheds: a molecular perspective.

In aquatic systems, dissolved organic matter (DOM) has important ecological and biogeochemical functions, where the molecular composition of DOM has larger-scale implications for climate change and global carbon cycles. However, there is limited information about the relationships between landscape characteristics and human disturbance that influence the molecular composition of DOM changes in watersheds. In this study, we collected water samples from 22 sites across a gradient of topographically characterized agricultural land coverage and community infrastructure development in the Kawartha region in Ontario, Canada. We employed a combination of Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and absorbance spectroscopy to investigate changes in the molecular composition of DOM with increasing agricultural and community development disturbance on the optical and molecular characteristics of DOM. We found that dissolved organic carbon (DOC) concentrations in disturbed (>75%) watersheds ranged from 3.67-32.8 mg L-1 and were significantly higher than in watersheds with more abundant forest coverage (3.78-9.13 mg L-1). In addition, watersheds with higher phosphorus concentrations had more negative nominal oxygenation state of carbon (NOSC) values, suggesting biologically processed DOM correlating with increased phosphorus levels in aquatic systems. To relate the molecular properties of DOM to landscape metrics, we used Spearman's correlation analysis to reveal that agriculturally impacted and community developments enhanced the molecular signature of unsaturated hydrocarbon. In addition, we identified 65 dissolved organic phosphorus (DOP) molecules that significantly increased in abundance with disturbance, likely due to microbial mineralization of existing DOM with the addition of phosphorus to form larger, biologically inaccessible molecules. The overall recalcitrance of the identified molecules can serve as molecular signatures when evaluating the level of disturbance of a watershed.

Chemodiversity of riverine dissolved organic matter: Effects of local environments and watershed characteristics

Riverine dissolved organic matter (DOM) is crucial to global carbon cycling and aquatic ecosystems. However, the geographical patterns and environmental drivers of DOM chemodiversity remain elusive especially in the waters and sediments of continental rivers. Here, we systematically analyzed DOM molecular diversity and composition in surface waters and sediments across 97 broadly distributed rivers using data from the Worldwide Hydrobiogeochemistry Observation Network for Dynamic River Systems (WHONDRS) consortium. We further examined the associations of molecular richness and composition with geographical, climatic, physicochemical variables, as well as the watershed characteristics. We found that molecular richness significantly decreased toward higher latitudes, but only in sediments (r = -0.24, p < 0.001). The environmental variables like precipitation and non-purgeable organic carbon showed strong associations with DOM molecular richness and composition. Interestingly, we identified that less-documented factors like watershed characteristics were also related to DOM molecular richness and composition. For instance, DOM molecular richness was positively correlated with the soil sand fraction for waters, while with the percentage of forest for sediments. Importantly, the effects of watershed characteristics on DOM molecular richness and composition were generally stronger in waters than sediments. This phenomenon was further supported by the fact that 11 out of 13 watershed characteristics (e.g., the percentages of impervious area and cropland) showed more positive than negative correlations with molecular abundance especially in waters. As the percentage of forest increased, there was a continuous accumulation of the compounds with higher molecular weight, aromaticity, and degree of unsaturation. In contrast, human activities accumulated the compounds with lower molecular weight and oxygenation, and higher bioavailability. Our findings imply that it may be possible to use a small set of broadly available data types to predict DOM molecular richness and composition across diverse river systems. Elucidation of mechanisms underlying these relationships will provide further enhancements to such predictions, especially when extrapolating to unsampled systems.

Exploring the diversity of dissolved organic matter (DOM) properties and sources in different functional areas of a typical macrophyte - derived lake combined with optical spectroscopy and FT-ICR MS analysis

Lake Baiyangdian is one of China's largest macrophyte - derived lakes, facing severe challenges related to water quality maintenance and eutrophication prevention. Dissolved organic matter (DOM) was a huge carbon pool and its abundance, property, and transformation played important roles in the biogeochemical cycle and energy flow in lake ecosystems. In this study, Lake Baiyangdian was divided into four distinct areas: Unartificial Area (UA), Village Area (VA), Tourism Area (TA), and Breeding Area (BA). We examined the diversity of DOM properties and sources across these functional areas. Our findings reveal that DOM in this lake is predominantly composed of protein - like substances, as determined by excitation - emission matrix and parallel factor analysis (EEM - PARAFAC). Notably, the exogenous tyrosine-like component C1 showed a stronger presence in VA and BA compared to UA and TA. Ultrahigh - resolution mass spectrometry (FT - ICR MS) unveiled a similar DOM molecular composition pattern across different functional areas due to the high relative abundances of lignan compounds, suggesting that macrophytes significantly influence the material structure of DOM. DOM properties exhibited specific associations with water quality indicators in various functional areas, as indicated by the Mantel test. The connections between DOM properties and NO3N and NH3N were more pronounced in VA and BA than in UA and TA. Our results underscore the viability of using DOM as an indicator for more precise and scientific water quality management.

Molecular formula assignment of dissolved organic matter by ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometry using two non-targeted data processing approaches: A case study from recirculating aquaculture systems

BackgroundThe accumulation of dissolved organic matter (DOM) poses an issue in the management of the water quality from recirculating aquaculture systems (RAS), but its characterization is often not detailed enough to understand the DOM transformations in RAS. In this study, we investigated the application of two distinct non-targeted data processing approaches using ultra-performance liquid chromatography (UPLC) with quadrupole time-of-flight mass spectrometry (QTOF-MS) and two software with different algorithmic designs: PetroOrg and Progenesis QI to accurately characterize the molecular composition of DOM in RAS by UPLC-QTOF-MS. ResultsThe UPLC-QTOF-MS resolution in combination with PetroOrg and Progenesis QI software successfully assigned 912 and 106 unique elemental compositions, respectively, including compounds containing carbon, hydrogen, and oxygen (CHO) and nitrogen-containing CHO compounds (CHON), in the DOM samples from RAS. The results of these two distinct data processing approaches were consistent with the list of DOM formulas from RAS identified by higher resolution mass spectrometry techniques confirming their reliability. PetroOrg approach revealed only compositional information in the DOM samples from RAS, while Progenesis QI in addition to identifying new elemental compositions, increased their chemical space by giving information about their polarity and their possible key structures. DOM samples from RAS were found to be rich in unsaturated CHO compounds, with tentatively key structures of terpenoids with medium polarity indicating natural origins in their composition. The analysis also revealed probable structures of sucrose fatty acid esters and polyethylene glycol, indicating anthropogenic sources. Significance and NoveltyThe combination of these two non-targeted data processing approaches significantly improves the characterization of the complex mixture of DOM from RAS by UPLC-QTOF-MS reporting for the first time accurate DOM results in terms of its composition, while proposing its key structures. The presented methods can also be used to analyze different DOM samples with other HRMS techniques and software.

Processes in the Surface Ocean Regulate Dissolved Organic Matter Distributions in the Deep

AbstractMarine dissolved organic matter (DOM) is a major global carbon pool, consisting of thousands of compounds with distinct lifetimes. While marine DOM persists for millennia, its molecular and isotopic composition imply that it is dynamic on shorter timescales. To determine the extent to which DOM deviates from conservative water mass mixing, we conducted a two‐endmember mixing analysis on dissolved organic carbon (DOC) concentration and DOM molecular composition in the Atlantic and Pacific. Endmembers were the deep water masses near their formation sites. For DOM composition, we considered 6118 molecular formulae (MF) identified via Fourier‐transform ion cyclotron resonance mass spectrometry in solid‐phase extracts (SPE) of 837 samples. Bulk DOC and SPE‐DOC concentrations behaved conservatively in both basins and ≥70% of the MF (14–20 μM SPE‐DOC) mixed conservatively. However, a small fraction (10%–20%) of the MF (&lt;3 μM SPE‐DOC) were added or removed during mixing. These MF were more reduced and oxidized, respectively, than the conservative fraction. There were also MF absent from the endmembers; these accounted for ≤1 μM of SPE‐DOC and positively correlated with DOM lability. Based on their distribution across the two basins, we conclude that the conserved MF are formed in the surface subtropical ocean and modified in overturning areas. In the deep ocean, however, these MF are solely controlled by mixing. This finding contrasts with the current paradigm of slow, continuous degradation of recalcitrant DOM in the deep ocean. Our analysis illustrates the importance of the surface ocean in controlling DOM cycling in the deep.

Bacterial community regulation of soil organic matter molecular structure in heavy metal-rich mangrove sediments

Heavy metals (HMs) profoundly impact soil carbon storage potential primarily through soil carbon structure. The association between HM content and soil carbon structure in mangrove sediments remains unclear, likely due to the involvement of microorganisms. In this study, surface sediments in the Futian National Mangrove Nature Reserve were sampled to investigate the chemical structure of soil organic carbon (SOC), the molecular composition of dissolved organic matter (DOM), and potential interactions with microorganisms. HMs, except for Ni, were positively correlated with soil carbon. HMs significantly reduced the alkyl C/O-alkyl C ratio, aromaticity index, and aromatic C values, but increased the labile carboxy/amide C and carbonyl C ratio in SOC. HMs also increased DOM stability, as reflected by the reduced abundance of labile DOM (lipids and proteins) and increased proportion of stable DOM (tannins and condensed aromatics). Bacteria increased the decomposition of labile DOM components (unsaturated hydrocarbons) and the accumulation of stable DOM components (lignins) under HM enrichment. In addition, the association between the bacterial groups and DOM molecules was more robust than that with fungal groups, indicating bacteria had a more significant impact on DOM molecular composition. These findings help in understanding the molecular mechanisms of soil carbon storage in HM-rich mangroves.

N-containing dissolved organic matter promotes dissolved inorganic carbon supersaturation in the Yangtze River, China

Dissolved inorganic carbon (DIC) represents a major global carbon pool and the flux from rivers to oceans has been observed to be increasing. The effect of weathering with respect to increasing DIC has been widely studied in recent decades; however, the influence of dissolved organic matter (DOM) on increasing DIC in large rivers remains unclear. This study employed stable carbon isotopes and Fourier transform ion cyclotron mass spectrometry (FT-ICR MS) to investigate the effect of the molecular composition of DOM on the DIC in the Yangtze River. The results showed that organic matter is an important source of DIC in the Yangtze River, accounting for 40.0 ± 12.1 % and 32.0 ± 7.2 % of DIC in wet and dry seasons, respectively, and increased along the river by approximately three times. Nitrogen (N)-containing DOM, an important composition in DOM with a percentage of ∼40 %, showed superior oxidation state than non N-containing DOM, suggesting that the presence of N could improve the degradable potential of DOM. Positive relationship between organic sourced DIC (DICOC) and N-containing DOM formulae indicated that N-containing DOM is crucial to facilitate the mineralization of DOM to DICOC. N-containg molecular formular with low H/C and O/C ratio were positively correlated with DICOC further verified these energy-rich and biolabile compounds are preferentially decomposed by bacteria to produce DIC. N-containing components significantly accelerated the degradation of DOM to DICOC, which is important for understanding the CO2 emission and carbon cycling in large rivers.