Transformation Of Dissolved Organic Matter Research Articles

Microbial transformation mechanisms of particulate organic carbon to mineral-associated organic carbon at the chemical molecular level: Highlighting the effects of ambient temperature and soil moisture

Soil dissolved organic matter (DOM), an important component of active soil organic carbon (C), plays a crucial role in controlling C transformation. However, the role of DOM in mediating the conversion of particulate organic C (POC) into mineral-associated organic C (MAOC) at the molecular level remains unclear. In this study, the microbial conversion of POC to MAOC at the molecular level was investigated at different ambient temperatures and soil moisture levels. An increase in ambient temperature led to the conversion of POC to labile C, whereas MAOC increased with soil moisture. CHO, CHNO, and CHOS increased with soil moisture and temperature. The highest temperature (35 °C) promoted conversion of lignin/cram (carboxyl-rich alicyclic molecules)-like molecules into aromatic components with the highest intragroup transformation of DOM (74%). The highest soil moisture (60%) favoured the conversion of refractory substances into aliphatic/peptide and lipid components with the highest intergroup transformation (28%). Compared to fungi, bacteria were the main driving force for DOM transformation. Therefore, changes in ambient temperature and soil moisture control the microbial formation and transformation of different C fractions (i.e. POC and MAOC) via DOM differently at the molecular level.

Unraveling the Coupled Dynamics between DOM Transformation and Arsenic Mobilization in Aquifer Systems during Microbial Sulfate Reduction: Evidence from Sediment Incubation Experiment

Geogenic arsenic (As)-rich groundwater poses a significant environmental challenge worldwide, yet our understanding of the interplay between dissolved organic matter (DOM) transformation and arsenic mobilization during microbial sulfate reduction remains limited. This study involved microcosm experiments using As-rich aquifer sediments from the Singe Tsangpo River basin (STR) and Jianghan Plain (JHP), respectively. The findings revealed that microbial sulfate reduction remarkably increased arsenic mobilization in both STR and JHP sediments compared to that in unamended sediments. Moreover, the mobilization of As during microbial sulfate reduction coincided with increases in the fluorescence intensity of two humic-like substances, C2 and C3 (R = 0.87/0.87 and R = 0.73/0.66 in the STR and JHP sediments, respectively; p < 0.05), suggesting competitive desorption between DOM and As during incubation. Moreover, the transformations in the DOM molecular characteristics showed significant increases in CHOS molecular and low-O/C-value molecular intensities corresponding to the enhancement of microbial sulfate reduction and the possible occurrence of methanogenesis processes, which suggests a substantial bioproduction contribution to DOM components that is conducive to As mobilization during the microbial sulfate reduction. The present results thus provide new insights into the co-evolution between As mobilization and DOM transformations in alluvial aquifer systems under strong microbial sulfate reduction conditions.

Leachate derived humic-like substances drive the variation in microbial communities in landfill-affected groundwater

Landfills are commonly used for waste disposal in many countries, and pose a significant threat of groundwater contamination. Dissolved organic matter (DOM) plays a crucial role as a carbon and energy source, supporting the growth and activity of microorganisms. However, the changes in the DOM signature and microbial community composition in landfill-affected groundwater and their bidirectional relationships remain inadequately explored. Herein, we showed that DOM originating from more recent landfills mainly comprises microbially produced substances resembling tryptophan and tyrosine. Conversely, DOM originating from older landfills predominantly comprises fulvic-like and humic-like compounds. Leachate leakage increases microbial diversity and richness and facilitates the transfer of foreign bacteria from landfills to groundwater, thereby increasing the vulnerability of the microbial ecosystem in groundwater. Deterministic processes dominated the assembly of the groundwater microbial community, while stochastic processes accounted for an increased proportion of the microbial community in the old landfills. The dominant phyla observed in groundwater were Proteobacteria, Bacteroidota, and Actinobacteriota, and humic-like substances play a crucial role in driving the variation in microbial communities in landfill-affected groundwater. Predictions using PICRUSt2 suggested significant associations between various metabolic pathways and microbial communities, with the Kyoto Encyclopedia of Genes and Genomes pathway “Metabolism” being the most predominant. The findings contribute to advancing our understanding of the transformation of DOM and its interplay with microbial communities and can serve as a scientific reference for decision-making regarding groundwater pollution monitoring and remediation.

Rivers and tidal flats as sources of dissolved organic matter and trace metals in the German Bight (North Sea)

The German Bight in the southern North Sea receives nutrients, dissolved organic matter (DOM), and trace metals from rivers, porewater reflux, and porewater outwelling. We studied the marine, riverine, and porewater sources analyzing molecular transformations of solid-phase extracted (SPE) DOM in the German Bight. We applied a combination of ultrahigh-resolution mass spectrometry (FT-ICR-MS) with quantitative data of dissolved organic sulfur (DOS), dissolved black carbon (DBC), dissolved trace metals (Ba, Co, Gd, Mo, Mn, W), and nutrients (nitrite, nitrate, phosphate, silicate). While aromatic DOM and DBC mainly originated from the rivers, nitrogen-containing, more saturated DOM was enriched offshore suggesting greater contributions of marine (algal) sources. Except for dissolved Mo, rivers were the primary source of trace metals and nutrients. However, tidal flats contributed to dissolved nutrient (e.g., dissolved phosphate), trace metal and DOS inventories of the southern North Sea. The input of DOS from intertidal flats was identified by the molecular index derived from sulfidic porewaters (ISuP), non-conservative behavior of elemental sulfur-to-carbon ratio and sulfur content of molecular formulae (from FT-ICR-MS). Dissolved Mn and Si were removed in the German Bight, likely due to precipitation as Mn(hydr)oxides and biological uptake, respectively. Preliminary estimates suggest that DOS from porewater outwelling is approximately four times higher than DOS discharged by the three main rivers in the region. Our study therefore highlights the need to consider porewater discharge in addition to riverine sources to comprehensively assess elemental budgets within the complex interplay and transformations of DOM, nutrients, and trace metals in coastal ecosystems.

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.

Bacteria Affect the Distribution of Soil-Dissolved Organic Matter on the Slope: A Long-Term Experiment in Black Soil Erosion

Soil erosion results in dissolved organic matter (DOM) loss and is one of the main paths of soil carbon loss. Bacteria affect the generation and transformation of DOM. However, the effect of bacteria on the composition and slope distribution of DOM has rarely been investigated under field conditions. Based on a long-term experiment of three gradients (3°, 5°, 8°) in a black soil erosion area of Northeast China, the content, composition, and source of DOM were studied. The results showed that the DOM of the 3° and 5° slope was enriched midslope, and the DOM of the 8° slope was enriched downslope. Parallel factor (PARAFAC) analysis indicated that the main substances in DOM were fulvic-like acid, humic-like acid, tryptophan-like protein, and soluble microbial metabolites. The upslope and downslope soils of 3° and 5° slopes showed high DOM bioavailability, while the downslope soil of the 8° slope showed high DOM bioavailability. The content of new DOM in downslope soil increased with the gradient. Bacteria played an important role in the synthesis and transformation of DOM and affected its composition and slope distribution. Verrucomicrobiota, Firmicutes, Planctomycetota, and Gemmatimonadota were the main factors affecting soil DOM. The results could be helpful in understanding the loss mechanism of DOM in eroded black soil and provide support for soil carbon sequestration.

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.

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.

Exogenous factors impact on bacterial-microalgal growth and chromophoric dissolved organic matter: a case study of Chrysotila dentata and Marinobacter hydrocarbonoclasticus

The relationship between Chrysolia dentata and bacteria that play an important role in the carbon cycle is complex yet closely intertwined. However, there is still limited knowledge about how phytoplankton interacts with heterotrophic bacteria under external influences. The transformation and processing of dissolved organic matter (DOM) by epiphytic bacteria for phytoplankton especially, under vitamin B12 (VB12) and abscisic acid (ABA) introducing have rarely been investigated. In this experiment, Marinobacter hydrocarbonoclasticus (CA6) was cultured with Chrysotila dentata to investigate growth and DOM release and transformation under the influence of VB12 and ABA. Three-dimensional (3D)-EEM, combined with fluorescence regional integration and the peak selecting method, was used to obtain fluorescent peaks (B, T, A, and C) and four indexes for DOM analysis. Our findings indicate that the incubation of CA6 significantly enhances the release of protein-like components (peak T) and humic-like components (peak C) during the incubation period. However, 100 μg/L VB12 or abscisic acid does not promote axenic microalgae growth or release of C. dentata-derived DOM. However, they have different effects on C. dentata-CA6 growth and the derived DOM. Abscisic acid can facilitate steady growth of both C. dentata and CA6 cells while enhancing the amounts of humic-like components. Conversely, VB12 inhibits the growth of CA6 and results in a rapid decrease in protein-like signal, but it does not significantly enhance C. dentata growth or the transformation of DOM. This indicates that ABA can support stable co-grown of microalgal and bacteria in a water environment, while VB12 may hinder CA6 bacterial growth, resulting in a less stable co-cultured environment. This study uncovers and verifies the impact of exogenous factors and heterotrophic bacteria in the growth of microalgae, underlining their role in transforming and generating algae-derived dissolved organic matter (DOM) within laboratory settings.

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.

Microbial metabolism influences microplastic perturbation of dissolved organic matter in agricultural soils.

An estimated 258 million tons of plastic enter the soil annually. Joining persistent types of microplastic (MP), there will be an increasing demand for biodegradable plastics. There are still many unknowns about plastic pollution by either type, and one large gap is the fate and composition of dissolved organic matter (DOM) released from MPs as well as how they interact with soil microbiomes in agricultural systems. In this study, polyethylene MPs, photoaged to different degrees, and virgin polylactic acid MPs were added to agricultural soil at different levels and incubated for 100days to address this knowledge gap. We find that, upon MP addition, labile components of low aromaticity were degraded and transformed, resulting in increased aromaticity and oxidation degree, reduced molecular diversity, and changed nitrogen and sulfur contents of soil DOM. Terephthalate, acetate, oxalate, and L-lactate in DOM released by polylactic acid MPs and 4-nitrophenol, propanoate, and nitrate in DOM released by polyethylene MPs were the major molecules available to the soil microbiomes. The bacteria involved in the metabolism of DOM released by MPs are mainly concentrated in Proteobacteria, Actinobacteriota, and Bacteroidota, and fungi are mainly in Ascomycota and Basidiomycota. Our study provides an in-depth understanding of the microbial transformation of DOM released by MPs and its effects of DOM evolution in agricultural soils.

Stratification of dissolved organic matter in the upper 5000 m water column in the western Pacific Ocean

Marine dissolved organic matter (DOM) is a principal reservoir involved in biogeochemical cycles and exerts a pivotal influence on global carbon flux dynamics. In this study, excitation-emission matrix fluorescence spectroscopy combined with parallel factor analysis (EEM-PARAFAC) was conducted on 230 DOM samples collected from 21 sites between February and April 2022 in the Western Pacific Ocean (WPO). We identified five distinct fluorescence peaks (peaks B, T, A, C, and M), predominantly protein-like and humic-like components. These findings, marked by significant differences (p < 0.01) in fluorescence intensities and spectral indices, characterized the transformation of DOM with ocean depth, illustrating a transition from active to recalcitrant forms. Additionally, random forest analysis (RFA) identified depth as a key factor influencing marine dissolved organic carbon (DOC), with a 32.59% importance value. Correlations between hydrological and fluorescent parameters underscored the complexity of DOM sources and influencing processes. Overall, this work broadens our understanding of DOM variability in the upper 5000 m of the WPO, enhancing our knowledge of the marine environment's role in the global carbon cycle.

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.

One-electron oxidant-induced transformation of dissolved organic matter: Optical and antioxidation properties and molecules

Dissolved organic matter (DOM) is a major sink of radicals in advanced oxidation processes (AOPs) and the radical-induced DOM transformation influences the subsequent water treatment processes or receiving waters. In this study, we quantified and compared DOM transformation by tracking the changes of dissolved organic carbon (DOC), UVA254, and electron donating capacity (EDC) as functions of four one-electron oxidants (SO4•−, Cl2•−, Br2•−, and CO3•−) exposures as well as the changes of functional groups and molecule distribution. SO4•− had the highest DOC reduction while Cl2•− had the highest EDC reduction, which could be due to their preferential reaction pathways of decarboxylation and converting phenols to quinones, respectively. Br2•− and CO3•− induced less changes in DOC, UVA254, and EDC than SO4•− and Cl2•−. Additionally, DOM enriched with high aromatic contents tended to have higher DOC, UVA254, and EDC reductions. Decreases in hydroxyl and carboxyl groups and increases in carbonyl groups were observed in these four types of radicals treated DOM using Fourier transform infrared spectroscopy. High resolution mass spectrometry using FTICR-MS showed that one-electron oxidants preferred to attack unsaturated carbon skeletons and transformed into molecules featuring high saturation and low aromaticity. Moreover, SO4•− was inclined to decrease oxidation state of carbon and O/C of DOM due to its strong decarboxylation capacity. This study highlights the distinct DOM transformation by four one-electron oxidants and provides comprehensive insights into the reactions of one-electron oxidants with DOM.

Copper Safeguards Dissolved Organic Matter from Sunlight-Driven Photooxidation.

Sunlight plays a crucial role in the transformation of dissolved organic matter (DOM) and the associated carbon cycle in aquatic environments. This study demonstrates that the presence of nanomolar concentrations of copper (Cu) significantly decreases the rate of photobleaching and the rate of loss of electron-donating moieties of three selected types of DOM (including both terrestrial and microbially derived DOM) under simulated sunlight irradiation. Employing Fourier transform ion cyclotron resonance mass spectrometry, we further confirm that Cu selectively inhibits the photooxidation of lignin- and tannin-like phenolic moieties present within the DOM, in agreement with the reported inhibitory impact of Cu on the photooxidation of phenolic compounds. On the basis of the inhibitory impact of Cu on the DOM photobleaching rate, we calculate the contribution of phenolic moieties to DOM photobleaching to be at least 29-55% in the wavelength range of 220-460 nm. The inhibition of loss of electrons from DOM during irradiation in the presence of Cu is also explained quantitatively by developing a mathematical model describing hydrogen peroxide (a proxy measure of loss of electrons from DOM) formation on DOM irradiation in the absence and presence of Cu. Overall, this study advances our understanding of DOM transformation in natural sunlit waters.

Organic amendment application affects the release behaviour, bioavailability, and speciation of heavy metals in zinc smelting slag: Insight into dissolved organic matter

Organic amendments are commonly used in assisted phytostabilization of mine wastes by improving their physicochemical and biological properties. These amendments are susceptible to leaching and degradation, resulting in the generation of dissolved organic matter (DOM), which significantly influences the geochemical behaviour of heavy metals (HMs). However, the geochemical behaviour of HMs in metal smelting slag driven by organic amendment-derived DOM remains unclear. In this study, we investigated the impact of cow manure-derived DOM on the release behaviour, bioavailability, and speciation of HMs (Cu, Pb, Zn, and Cd) in zinc smelting slag using a multidisciplinary approach. The results showed that DOM enhanced the weathering of the slag, with a minimal impact on the slag’s mineral phases, except for causing gypsum dissolution. The DOM addition resulted in a slight increase in HM release from the slag during the initial inoculation period, followed by a reduction in HM release during the later period. Furthermore, the DOM addition increased the diversity and relative abundance of the bacterial community. This, in turn, led to a decrease in the dissolved organic carbon (DOC) content and enhanced the transformation of labile DOM compounds into recalcitrant compounds. The variation in HM release during various inoculation periods can be attributed to the bacterial decomposition and transformation of DOM, which further enhanced the transformation of HM fractions. Specifically, during the later period, DOM promoted the conversion of a portion of the reducible and oxidizable fractions of Cu, Pb, and Zn into the acid-soluble and residual fractions. Moreover, it partially transformed the reducible, oxidizable, and residual fractions of Cd into the acid-soluble fraction. Overall, this study provides new insights into the geochemical behaviour of HMs in slag governed by the coupling effect of DOM and the bacterial community. These findings have implications for the use of organic amendments in assisted phytostabilization of metal smelting slag. Environmental implicationMetal smelting slag is hazardous due to its high levels of HMs, and its improper disposal has serious consequences for the ecosystem. Organic amendments are employed in assisted phytostabilization of the slag site by improving its microecological properties. However, the impact of organic amendment-derived DOM on HM migration and transformation in slag remains unclear. This study indicated that the coupling effects of DOM and microbes governed the geochemical behaviour of HMs in slag. These findings provide new insights into how organic amendments impact the geochemical behaviour of HMs in slag, contributing to the development of phytostabilization technology.

Evolution of dissolved organic nitrogen chemistry during transportation to the marginal sea: Insights from nitrogen isotope and molecular composition analyses

Estuaries are hotspots where terrestrially originated dissolved organic matter (DOM) is modified in molecular composition before entering marine environments. However, very few research has considered nitrogen (N) modifications of DOM molecules in estuaries, limiting our understanding of dissolved organic nitrogen (DON) cycling and the associated carbon cycling in estuaries. This study integrated optical, stable isotopes (δ15N and δ13C) and molecular composition (FT-ICR MS) to characterize the transformation of DOM in the Yangtze River Estuary. Both concentration of dissolved organic carbon (DOC) and DON decreased with increasing salinity, while their δ13C and δ15N increased with the increasing salinity. A significant positive correlation was found between δ15N and δ13C during the transportation of DOM to marginal seas, indicating that the behavior of both DOC and DON are primarily controlled by the mixing of freshwater and the seawater in the YRE. During the mixing process, the DON addition was observed using the conservative mixing curves. In the view of molecular composition, DOM molecules became more aromatic as the number of N atoms increased. Spearman correlations reveal that DOM molecules with fewer N atoms exhibited a higher enrichment in protein-like components, while those with more N atoms were more enriched in humic-like components. In addition, the δ15N and δ13C tended to increase as the N content of DOM decreased. Therefore, DON molecules with fewer N atoms were likely to be transformed into those with more N atoms based on the isotopic fractionation theory. This study establishes a linkage between the molecular composition and the δ15N of DOM, and discovers the N transformation pattern within DOM molecules during the transportation to marginal seas.

Molecular-level insights into the transformation and degradation pathways of dissolved organic matter during full-scale swine wastewater treatment

The rapid development of swine farming has resulted in the generation of a large amount of swine wastewater (SW), and dissolved organic matter (DOM) has a crucial role in determining the efficiency and safety of SW treatment. In this study, the transformation and influential mechanisms of DOM on the quality of SW effluent during full-scale SW treatment in actual engineering were systematically investigated using multispectral analysis and the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) technique. The results showed that S-containing, reduced, saturated, and less aromatic molecules were preferentially removed in the C-AF, while C-S preferentially removed reduced, unsaturated, and aromatic molecules, as well as molecules with large molecular weights. And in the two-stage A/O, the degradation of organic matter and DOM transformation occurred mainly in the A/O-1, with the A/O-2 acting as a supplement to further enhance the humification of DOM. Furthermore, the AOP preferentially removed lignin-like and highly unsaturated compounds, replacing them with a new generation of substances such as proteins and tannins with low aromaticity and unsaturation. More deeply, oxygen addition reactions dominate in both A/O and AOP. Specifically, the most common types of reactions in the A/O were the corresponding potential precursor-product pairs based on methyl to carboxylic acid (-H2 + O2) and alcohol to carboxylic acid (-H2 + O), while tri-hydroxylation (+O3) and di-hydroxylation (+H2O2) reactions were predominant in the AOP. Finally, the study's findings might suggest improving the actual engineering by prioritizing the AOP before the A/O-2 and using the C-S for safeguard treatment of the A/O-2 effluent. It is reliable that this kind of adjustment guarantees safe drainage indications and raises each process unit's efficiency in purifying.

Fate of carbon influenced by the in-situ growth of phototrophic biofilms at the soil–water interface of paddy soil

Phototrophic biofilms (PBs) are commonly found in the sediment/soil–water interface of paddy soils and have a significant impact on carbon cycles. However, the specific carbon fate influenced by the in-situ growth of PBs in paddy soil remains unclear. In this study, we investigated the effect of in situ PBs growth on methane and carbon dioxide emissions, as well as dissolved organic matter (DOM) transformation. Our findings demonstrated a negative correlation between PBs growth and methane and carbon dioxide emissions, while showing a positive correlation with DOM composition. The in-situ growth of PBs reduced methane emissions by approximately 79 % and carbon dioxide emissions by approximately 33 % in the daytime, and also slowed down the degradation rate of dissolved organic matter from over 30.4 % to <16 %. Microsensor measurements revealed that these changes were attributed to the increased concentration and penetration depth of oxygen, as well as variations in pH caused by the growth of in situ PBs. Co-occurrence analysis indicated a robust correlation between DOM transformation and the significantly suppressed methanogenesis by methanogens such as Methanosaeta, Methanomassiliicoccus and Methanosarcina, and also the notably enhanced methane oxidation by methanotrophs including Methylobacterium, Methyloversatilis and Methylomonas, in response to the growth of PBs. These findings shed light on the impact of in situ PBs on methane and carbon dioxide emissions and DOM transformation, providing new insights for understanding carbon cycling in paddy soils.

Hypoxia diversifies molecular composition of dissolved organic matter and enhances preservation of terrestrial organic carbon in the Yangtze River Estuary

Dissolved organic matter (DOM) is an essential component of the global carbon cycle, and estuaries link the rivers and the oceans, thus playing important roles in land-ocean DOM transformation and transport. However, the effects of hypoxia on DOM transport and fate in estuaries and coastal oceans remains poorly understood. To address this gap, we characterized the molecular composition of DOM in bottom water (BW) and sediment porewater (PW) at hypoxic and non-hypoxic sites in the Yangtze River Estuary (YRE) using ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry. Our results showed significant differences in DOM molecular composition between hypoxic and non-hypoxic areas for both BW and PW. Specifically, DOM in hypoxic sites was more recalcitrant than that in non-hypoxic areas for both BW and PW, with lower H/C, and higher O/C, double bond equivalent, and modified aromaticity index. The presence of higher polyphenols, and black carbon in hypoxic areas suggested that hypoxic conditions could facilitate the preservation of terrestrial organic matter. Furthermore, we identified a much higher number of hypoxia-unique formulas than ocean-non-hypoxia-unique formulas, indicating that hypoxia could diversify the DOM pool. Within hypoxia-unique formulas for PW, both biologically labile (unsaturated aliphatic compounds and peptides) and recalcitrant formulas (carboxyl-rich alicyclic molecules) were found, suggesting that hypoxia could facilitate the preservation of labile formulas and the production of recalcitrant formulas. In addition, we formulated that the sulfurization is more important in PW than BW in hypoxic areas based on the higher dissolved organic sulfur (DOS) abundance and larger number of hypoxia-only formulas in hypoxic PW, and also the precursor analysis results. Overall, our study provides insights into the effect of hypoxia on the molecular characteristics and preservation of DOM in estuaries and coastal oceans, highlighting the importance of considering hypoxia in understanding the biogeochemical processes of these ecosystems.