Nominal Oxidation State Of Carbon Research Articles

Improved Characterization of Soil Organic Matter by Integrating FT-ICR MS, Liquid Chromatography Tandem Mass Spectrometry, and Molecular Networking: A Case Study of Root Litter Decay under Drought Conditions.

Understanding of how soil organic matter (SOM) chemistry is altered in a changing climate has advanced considerably; however, most SOM components remain unidentified, impeding the ability to characterize a major fraction of organic matter and predict what types of molecules, and from which sources, will persist in soil. We present a novel approach to better characterize SOM extracts by integrating information from three types of analyses, and we deploy this method to characterize decaying root-detritus soil microcosms subjected to either drought or normal conditions. To observe broad differences in composition, we employed direct infusion Fourier-transform ion cyclotron resonance mass spectrometry (DI-FT-ICR MS). We complemented this with liquid chromatography tandem mass spectrometry (LC-MS/MS) to identify components by library matching. Since libraries contain only a small fraction of SOM components, we also used fragment spectral cosine similarity scores to relate unknowns and library matches through molecular networks. This integrated approach allowed us to corroborate DI-FT-ICR MS molecular formulas using library matches, which included fungal metabolites and related polyphenolic compounds. We also inferred structures of unknowns from molecular networks and improved LC-MS/MS annotation rates from ∼5 to 35% by considering DI-FT-ICR MS molecular formula assignments. Under drought conditions, we found greater relative amounts of lignin-like vs condensed aromatic polyphenol formulas and lower average nominal oxidation state of carbon, suggesting reduced decomposition of SOM and/or microbes under stress. Our integrated approach provides a framework for enhanced annotation of SOM components that is more comprehensive than performing individual data analyses in parallel.

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

Elucidating 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.

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.

Dissolved organic nitrogen is a key to improving the biological treatment potential of landfill leachate

Biological treatment is one of the most promising efficient, low-carbon and affordable approaches for the treatment of recalcitrantly degradable wastewater, such as landfill leachate. However, even the macroscopic molecular level analysis of dissolved organic matter (DOM) is limiting to the enhancement of biological treatment efficacy, and there is an urgent need for deeper exploration of DOM to gain insights into the key constraining substances. In the present study targeting at piercing leachate organic at molecular level, nitrogen-containing dissolved organic matter (DOMN) was identified to be the bottleneck that govern the biotreatment potential. The conclusion was made based on two series of experiments that compared the same anoxic-aerobic membrane bioreactor process (A process) operated stably at different regions, and compared with C process that coupling A process with a circulation aeration membrane bioreactor to improve aeration efficiency. The results confirmed that the relative abundance of DOMN was absolutely dominant among the three categories of DOM in all biologically treated samples, contributing to 60.36 %–65.81 % in removed-DOM, 60.33 %–70.95 % in refractory-DOM and 63.14 %–71.36 % in derived-DOM. Specifically, the high latitude A process had much lower DOMN removal rate than the low latitude A process (p < 0.05) and much higher refractory and derivatization rates than the low latitude A process (p < 0.05). DOM had similar results. No statistically significant differences were observed in the proportion of the three categories of DOM (DOMN), the elements composition, and the subcategory composition of the C process compared to the A process, in which the DOM (DOMN) derivation rate of NEC1-C (31.92 % and 33.41 %) was much higher than that of NEC1-A (20.88 % and 22.19 %). However, the AIwa and AImodwa of the derived-DOM (DOMN) were significantly higher in the C process than in the A process, which implied that excessive aeration did not enhance the biological treatment potential of the A process, but instead led to the proliferation of microorganisms and the secretion of extracellular polymer substances, which resulted in the derivation of more complex compounds. The results of the correlation analysis indicated that there were some regional differences in the molecular information of DOMN driven by climate temperature. In addition, it was worth mentioning that the nominal oxidation state of carbon (NOSCwa) of derived-DOMN in different regions of A process was noticeably higher than the corresponding DOM (p < 0.0001), implying that the derived-DOMN were still highly biodegradable, in other words, there was still great room for improving the biological treatment potential of landfill leachate. The present study provided a deeper insight and analysis of landfill leachate at the molecular level (DOMN) through multiple practical engineering cases, with a view to providing a theoretical basis for efficient optimization of biological treatment.

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.

Interactive effects of microbial functional diversity and carbon availability on decomposition – A theoretical exploration

Microbial functional diversity in litter and soil has been hypothesized to affect the rate of decomposition of organic matter and other soil ecosystem functions. However, there are no clear theoretical expectations on how these effects might change with substrate availability, heterogeneity in the substrate chemistry, and different aspects of functional diversity itself (number of microbial groups vs. distribution of functional traits). To explore how these factors shape the decomposition-diversity relation, we carry out numerical experiments using a flexible reaction network comprising microbial processes and interactions with bioavailable carbon (extracellular degradation, uptake, respiration, growth, and mortality), and ecological processes (competition among the different groups). We also considered diverse carbon substrates, in terms of varying nominal oxidation state of carbon (NOSC). The reaction network was used to test the effects of (i) number of microbial groups, (ii) number of carbon pools, (iii) microbial functional diversity, and (iv) amount of bioavailable carbon. We found that the decomposition rate constant increases with increasing substrate concentration and heterogeneity, as well as with increasing microbial functional diversity or variance of microbial traits, albeit these biological factors are less important. The multivariate dependence of the decomposition rate constant (and other decomposition and microbial growth metrics) on substrate and microbial factors can be described using power laws with exponents lower than one, indicating that diversity effects on decomposition and microbial growth are reduced at high substrate concentration and heterogeneity, or at high microbial diversity.

Unraveling the persistence of deep podzolized carbon: Insights from organic matter characterization

Over a billion tons of terrestrial carbon (C) is stored in deep soils from the Southeastern Coastal Plain of the United States. While the size and extent of this pool, known as deep podzolized carbon (DPC), have been reported in recent studies, the stabilization mechanisms responsible for its persistence are unclear. The main hypothesis of DPC stabilization is that hydrology, specifically water table fluctuations in the phreatic zone, slow microbial degradation and promote C accumulation. This accounts for the characteristic properties and distribution of DPC and provides a mechanistic distinction between DPC and shallow podzolized C in the region's soils, however it has yet to be tested. We characterized the organic matter composition of the bulk and dissolved fractions of DPC using elemental analysis, solvent extraction, infrared spectroscopy, and high-resolution mass spectrometry. Consistent with past work, the majority of DPC organic matter was extractable by sodium pyrophosphate solution; the influence of metal association was also observable in the water extractable fraction of DPC with large species being preferentially removed and a low compound diversity compared to those from other horizons overlying DPC. Only water extractable species with low molecular mass (m/z < 375 Da) showed significant change in average nominal oxidation state of carbon (NOSC) values, indicative of oxygen-limitation influence on the processing of these species. Infrared spectroscopy revealed an increase in abundance of aliphatic (C-H:C-O) bonds relative to polysaccharide bonds with depth whereas aromatic (C=C:C-O) bonds decreased with depth in DPC relative to other subsurface horizons. Our work shows that DPC is significantly more refractory than overlying surface soil C, and yet slightly more labile than the subsoils above DPC. Together our results suggest that the maintenance of low redox conditions via persistent water saturation contributes to the stabilization and persistence of DPC.

Riverine organic matter functional diversity increases with catchment size

A large amount of dissolved organic matter (DOM) is transported to the ocean from terrestrial inputs each year (~0.95 Pg C per year) and undergoes a series of abiotic and biotic reactions, causing a significant release of CO2. Combined, these reactions result in variable DOM characteristics (e.g., nominal oxidation state of carbon, double-bond equivalents, chemodiversity) which have demonstrated impacts on biogeochemistry and ecosystem function. Despite this importance, however, comparatively few studies focus on the drivers for DOM chemodiversity along a riverine continuum. Here, we characterized DOM within samples collected from a stream network in the Yakima River Basin using ultrahigh-resolution mass spectrometry (i.e., FTICR-MS). To link DOM chemistry to potential function, we identified putative biochemical transformations within each sample. We also used various molecular characteristics (e.g., thermodynamic favorability, degradability) to calculate a series of functional diversity metrics. We observed that the diversity of biochemical transformations increased with increasing upstream catchment area and landcover. This increase was also connected to expanding functional diversity of the molecular formula. This pattern suggests that as molecular formulas become more diverse in thermodynamics or degradability, there is increased opportunity for biochemical transformations, potentially creating a self-reinforcing cycle where transformations in turn increase diversity and diversity increase transformations. We also observed that these patterns are, in part, connected to landcover whereby the occurrence of many landcover types (e.g., agriculture, urban, forest, shrub) could expand DOM functional diversity. For example, we observed that a novel functional diversity metric measuring similarity to common freshwater molecular formulas (i.e., carboxyl-rich alicyclic molecules) was significantly related to urban coverage. These results show that DOM diversity does not decrease along stream networks, as predicted by a common conceptual model known as the River Continuum Concept, but rather are influenced by the thermodynamic and degradation potential of molecular formula within the DOM, as well as landcover patterns.

The transformation of dissolved organic matter and formation of halogenated by-products during electrochemical advanced oxidation pretreatment for shale gas produced water

Electrochemical advanced oxidation processes (EAOPs) have shown great potential for the treatment of shale gas produced water (SGPW). In this study, we investigated the transformation of dissolved organic matter (DOM) during EAOPs of SGPW and the formation of toxic halogenated by-products at various current densities, using fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry. We found that the priority of DOM removal was terrestrial humic-like > microbial humic-like > protein-like substances. Non-Halogenated organic compounds (non-HOCs) and HOCs were predominantly CHO, and CHOCl/CHOBr compounds in EAOP-treated SGPW, respectively. As applied current density and treatment time increased, the production of oxyhalides increased, with chlorate > bromate > perchlorate. Meanwhile, most DOM was mineralized, resulting in residual products with higher modified aromaticity index (AImod) and nominal oxidation state of carbon (NOSC). The resistants had lower mass-to-charge ratio (m/z), AImod, NOSC, and double bond equivalent minus oxygen per carbon ((DBE−O)/C). The dominant reactions were the addition of tri-oxygen and deallyl. Bromine addition dominated the reactions of halogenating addition, while chlorine addition took second place. Furthermore, the acute toxicity of SGPW was positively correlated with inorganic halogenated by-products. This study contributes to the understanding and improvement of EAOPs for the treatment of SGPW.

One thousand soils for molecular understanding of belowground carbon cycling

While significant progress has been made in understanding global carbon (C) cycling, the mechanisms regulating belowground C fluxes and storage are still uncertain. New molecular technologies have the power to elucidate these processes, yet we have no widespread standardized implementation of molecular techniques. To address this gap, we introduce the Molecular Observation Network (MONet), a decadal vision from the Environmental Molecular Sciences Laboratory (EMSL), to develop a national network for understanding the molecular composition, physical structure, and hydraulic and biological properties of soil and water. These data are essential for advancing the next generation of multiscale Earth systems models. In this paper, we discuss the 1000 Soils Pilot for MONet, including a description of standardized sampling materials and protocols and a use case to highlight the utility of molecular-level and microstructural measurements for assessing the impacts of wildfire on soil. While the 1000 Soils Pilot generated a plethora of data, we focus on assessments of soil organic matter (SOM) chemistry via Fourier-transform ion cyclotron resonance-mass spectrometry and microstructural properties via X-ray computed tomography to highlight the effects of recent fire history in forested ecosystems on belowground C cycling. We observed decreases in soil respiration, microbial biomass, and potential enzyme activity in soils with high frequency burns. Additionally, the nominal oxidation state of carbon in SOM increased with burn frequency in surface soils. This results in a quantifiable shift in the molecular signature of SOM and shows that wildfire may result in oxidation of SOM and structural changes to soil pore networks that persist into deeper soils.

Degradation of phosphorus-containing natural organic matter facilitates enrichment of geogenic phosphorus in Quaternary aquifer systems: A molecular perspective

Although degradation of phosphorus-containing natural organic matter (NOM) is an important process associated with geogenic phosphorus (P) enrichment, the detailed mechanism underlying the association remains unclear. Herein, we used molecular characteristics of P-containing dissolved organic matter (DOM) coupled with hydrogeochemistry and carbon isotopes to unravel this controlling mechanism. Results indicate that P-containing DOM is indeed an important factor controlling groundwater P enrichment. Further, one-P-atom (1P) and two-P-atom (2P) compounds were widely detected. Compared to 1P compounds, 2P compounds have greater numbers of N/S-containing compounds; smaller proportions of highly unsaturated and aliphatic compounds; larger proportions of polyphenols and polycyclic aromatics; lower H/C and nominal oxidation state of carbon (NOSC) values; and higher m/z, O/C, P/C, N/C, double bond equivalents (DBE), and modified aromaticity index (AImod) values. At the molecular level, P-containing DOM degradation overall results in an increase in H/C and a decrease in O/C, and a processing gradient is observed from 2P to 1P compounds, during which dissolved inorganic phosphorus (DIP) was gradually accumulated and retained, eventually becoming the predominating P pool in groundwater. To our knowledge, this is the first study to reveal geogenic P enrichment from a molecular perspective in groundwater systems worldwide.

Paleo-Geomorphology Determines Spatial Variability of Geogenic Ammonium Concentration in Quaternary Aquifers.

Naturally occurring (i.e., geogenic) ammonium in groundwater has been widely detected globally, but the major controls on its regional distribution have been poorly characterized. Here, we identified the dominant role of paleo-geomorphology driven by paleo-climate in controlling the spatial variability of geogenic ammonium in groundwater using random forest algorithm and revealed the underlying mechanisms based on borehole sediment analysis of data obtained from the Dongting Lake Plain of the central Yangtze River basins in China. In the paleo-channel (PC) area, the aquifer depth-matched sediments were deposited during the last deglaciation when warm climate resulted in rapid filling into incised valleys, and terrestrial organic matter (OM) mainly as lignin experienced less degradation prior to sedimentation and had lower humification, higher N abundance, and nominal oxidation state of carbon (NOSC). In the paleo-interfluve (PI) area, the depth-matched sediments were deposited during the last glaciation, followed by intensive erosion in the surface during the last glacial maximum, and terrestrial OM mainly as lignin had been partly degraded into aliphatics prior to sedimentation and had higher humification, lower N abundance, and NOSC. As a result, under the present anaerobic conditions, less-humic and N-rich OM with more oxidized C tends to be more intensively mineralized into ammonium in the PC area than those in the PI area. These findings highlight the importance of paleo-geomorphology with paleo-climate in controlling the enrichment of geogenic ammonium in groundwater, which has a universal significance for understanding the genesis and distribution of high N loads in the aquatic environment worldwide.

Novel insight into arsenic enrichment in aquifer sediments under different paleotemperatures from a molecular-level characterization of sedimentary organic matter

The heterogeneous distribution of As in sediments is governed by the abundance and type of SOM, which is closely associated with the depositional environment. However, few studies have revealed the effect of depositional environment (e.g., paleotemperature) on As sequestration and transport in sediments from the perspective of the molecular characteristics of sedimentary organic matter (SOM). In this study, we characterized the optical and molecular characteristics of SOM coupled with organic geochemical signatures to illustrate in detail the mechanisms of sedimentary As burial under different paleotemperatures. We identified that alternating paleotemperature changes result in the fluctuation of H-rich and H-poor organic matter in sediments. Further, we found aliphatic and saturated compounds with higher nominal oxidation state of carbon (NOSC) values predominate under high-paleotemperature (HT) conditions, while polycyclic aromatics and polyphenols with lower NOSC values accumulate under low-paleotemperature (LT) conditions. Under LT conditions, thermodynamically favorable organic compounds (higher NOSC values) are preferentially degraded by microorganisms to provide sufficient energy to sustain sulfate reduction, favoring sedimentary As sequestration. Under HT conditions, the energy gained from the decomposition of low NOSC value organic compounds approaches the energy required to sustain dissimilatory Fe reduction, leading to sedimentary As release into groundwater. This study provides molecular-scale evidence of SOM that indicates LT depositional environments favor sedimentary As burial and accumulation.

Comprehensive understanding of DOM reactivity in anaerobic fermentation of persulfate-pretreated sewage sludge via FT-ICR mass spectrometry and reactomics analysis

Understanding the composition and reactivity of dissolved organic matter (DOM) at molecular level is vital for deciphering potential regulators or indicators relating to anaerobic process performance, though it was hardly achieved by traditional analyses. Here, the DOM composition, molecular reactivity and transformation in the enhanced sludge fermentation process were comprehensively elucidated using high-resolution mass spectrometry measurement, and data mining with machine learning and paired mass distance (PMD)-based reactomics. In the fermentation process for dewatered sludge, persulfate (PDS) pretreatment presented its highest performance in improving volatile fatty acids (VFAs) production with the increase from 2,711 mg/L to 3,869 mg/L, whereas its activation in the presence of Fe (as well as the hybrid of Fe and activated carbon) led to the decreased VFAs production performance. In addition to the conventional view of improved decomposition and solubilization of N-containing structures from sludge under the sole PDS pretreatment, the improved VFAs production was associated with the alternation of DOM molecular compositions such as humification generating molecules with high O/C, N/C, S/C and aromatic index (AImod). Machine learning was capable of predicting the DOM reactivity classes with 74–76 % accuracy and found that these molecular parameters in addition to nominal oxidation state of carbon (NOSC) were among the most important variables determining the generation or disappearance of bio-resistant molecules in the PDS pretreatment. The constructed PMD-based network suggested that highly connected molecular network with long path length and high diameter was in favor of VFAs production. Especially, -NH related transformation was found to be active under the enhanced fermentation process. Moreover, network topology analysis revealed that CHONS compounds (e.g., C13H27O8N1S1) can be the keystone molecules, suggesting that the presence of sulfur related molecules (e.g., cysteine-like compounds) should be paid more attention as potential regulators or indicators for controlling sludge fermentation performance. This study also proposed the non-targeted DOM molecular analysis and downstream data mining for extending our understanding of DOM transformation at molecular level.

Particulate Organic Matter Mobilization and Transformation Along a Himalayan River Revealed by ESI‐FT‐ICR‐MS

AbstractTracing pathways and transformations of particulate organic carbon from landscape sources to oceanic sinks is commonly done using the isotopic composition or biomarker content of particulate organic matter (POM). However, similarity of source characteristics and complex mixing in rivers often preclude a robust deconvolution of individual contributions. Moreover, these approaches are limited in detecting organic matter transformations. This impedes understanding of carbon cycling. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT‐ICR‐MS) can simultaneously identify many molecular formulas from mixtures of organic matter, and provide direct information on its compositional variability. Here, we investigate how FT‐ICR‐MS can give insight into POM dynamics on a landscape scale, focusing on the trans‐Himalayan Kali Gandaki River, Nepal. Using molecular information, we identify source tracers in the solvent extractable lipid fraction of riverine POM, finding up to 102 indicative molecular formulas for individual sources. Further, we assess molecular transformations of the lipid fraction of POM during its transfer from litter into topsoil, and onwards into the river. A large number of shared mass formulas and a well‐preserved isoprenoidal patterns suggest efficient incorporation of litter into topsoil. In contrast, we observe a selective loss of mass formulas and a preferential export of formulas with low double bond equivalents and a low nominal oxidation state of carbon after organic matter entrainment in the river. Our results demonstrate the potential of FT‐ICR‐MS for source‐to‐sink studies, allowing detailed organic matter source characterization and discrimination, and tracking of molecular transformations along organic matter pathways spanning different spatial and temporal scales.

Dynamic utilization of low-molecular-weight organic substrates across a microbial growth rate gradient.

Low-molecular-weight organic substances (LMWOSs) are at the nexus between micro-organisms, plant roots, detritus, and the soil mineral matrix. The nominal oxidation state of carbon (NOSC) has been suggested as a potential parameter for modelling microbial uptake rates of LMWOSs and the efficiency of carbon incorporation into new biomass. In this study, we assessed the role of compound class and oxidation state on uptake kinetics and substrate-specific carbon use efficiency (SUE) during the growth of three model soil micro-organisms, a fungal isolate (Penicillium spinulosum) and two bacterial isolates (Paraburkholderia solitsugae, and Ralstonia pickettii). Isolates were chosen that spanned a growth rate gradient (0.046-0.316 h-1 ) in media containing 34 common LMWOSs at realistically low initial concentrations (25 μM each). Clustered, co-utilization of LMWOSs occurred for all three organisms. Potential trends (p < 0.05) for early utilization of more oxidized substrates were present for the two bacterial isolates (P. solitsugae and R. pickettii), but high variability (R2 < 0.15) and a small effect of NOSC indicate these relationships are not useful for prediction. The SUEs of selected substrates ranged from 0.16 to 0.99 and there was no observed relationship between NOSC and SUE. Our results do not provide compelling population-level support for NOSC as a predictive tool for either uptake kinetics or the efficiency of use of LMWOS in soil solution. Metabolic strategies of organisms are likely more important than chemical identity in determining LMWOS cycling in soils. Previous community-level observations may be biased towards fast-responding bacterial community members.

Molecular-level characterization of natural organic matter in the reactive electrochemical ceramic membrane system for drinking water treatment using FT-ICR MS

Applications of electrochemical advanced oxidation processes are rising in drinking water treatment for effective mitigation of refractory organic compounds. This study explored the fate of natural organic matter (NOM) (lake water and standard NOM (SRNOM solution)) at molecular-level in the reactive electrochemical membrane (REM) system utilizing Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Fluorescence spectroscopy showed above 90 % removal of the humic-like component in both lake water and SRNOM solution in 10 min of REM operation compared to 70–80 % removal of the fulvic-like component after 30 min. REM-based treatment effectively eliminated (>70 %) the disinfection byproduct precursors. The lake water, sharing ~70 % of similar compounds with SRNOM, displayed a different propensity toward electrochemical oxidation, and its finished water was characterized with relatively lower double-bond equivalent (DBE), nominal oxidation state of carbon (NOSC), and aromaticity compared to that of SRNOM. The chloride ions in the water matrix of lake water impacted the electrochemical oxidation and generated significantly different transformation products than SRNOM solution. The heteroatoms (N and S) containing compounds (CHON and CHOS) were preferentially degraded in lake water; however, CHOS compounds were removed fewer in SRNOM. The electrosorption and electrochemical oxidation on the REM surface were the significant contributors for NOM removal. The newly formed compounds were mostly retained on the REM surface and fewer were released in finished water. This study is believed to help understand the fate of NOM in real source drinking water during electrochemical treatment.

Unraveling the impact of iron oxides-organic matter complexes on iodine mobilization in alluvial-lacustrine aquifers from central Yangtze River Basin

The biodegradation of organic matter triggers the reductive dissolution of iron oxides with the transformation among iodine species has been mostly accepted as the key iodine mobilization process in groundwater system. However, molecular characteristics of natural organic matter (NOM) and their interaction with iron oxides on geogenic iodine enrichment remain unclear. We used Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to characterize the molecular composition of both dissolved organic matter (DOM) in groundwater and water-soluble organic matter (WSOM) in aquifer sediments being depth-matched with groundwater from monitoring wells in typical iodine-affected aquifers within the central Yangtze River Basin. The results show that WSOM in high-iodine sediments contains more high molecular weight (HMW) organic compounds with higher aromaticity and nominal oxidation state of carbon (NOSC), including polycyclic aromatics, polyphenols and highly unsaturated compounds. These compounds are mostly positively associated with amorphous iron oxides (Feox1) in aquifer sediments. The association between iodine and WSOM is highly consistent with that between amorphous Feox1 and WSOM, but is contrary to that between crystalline iron oxides (Feox2) and WSOM. DOM in groundwater with higher iodine concentration contains more aliphatic compounds and less polyphenols. The complexation of HMW organic compounds of WSOM to iodine-bearing amorphous Feox1 plays an important role in iodine mobilization, which could inhibit the amorphous Feox1 transformation to crystalline Feox2. These observations indicate the biodegradation of HMW organic matter (polycyclic aromatics, polyphenols and highly unsaturated compounds) in WSOM fueling the reductive dissolution of amorphous Feox1 predominantly promotes the release of iodine from aquifer sediments into groundwater. This research provides new insights into the mobilization mechanisms of iodine in alluvial-lacustrine groundwater system controlled by the Fe-OM complexation at the molecular level.

Coupling plant litter quantity to a novel metric for litter quality explains C storage changes in a thawing permafrost peatland.

Permafrost thaw is a major potential feedback source to climate change as it can drive the increased release of greenhouse gases carbon dioxide (CO2) and methane (CH4). This carbon release from the decomposition of thawing soil organic material can be mitigated by increased net primary productivity (NPP) caused by warming, increasing atmospheric CO2, and plant community transition. However, the net effect on C storage also depends on how these plant community changes alter plant litter quantity, quality, and decomposition rates. Predicting decomposition rates based on litter quality remains challenging, but a promising new way forward is to incorporate measures of the energetic favorability to soil microbes of plant biomass decomposition. We asked how the variation in one such measure, the nominal oxidation state of carbon (NOSC), interacts with changing quantities of plant material inputs to influence the net C balance of a thawing permafrost peatland. We found: (1) Plant productivity (NPP) increased post‐thaw, but instead of contributing to increased standing biomass, it increased plant biomass turnover via increased litter inputs to soil; (2) Plant litter thermodynamic favorability (NOSC) and decomposition rate both increased post‐thaw, despite limited changes in bulk C:N ratios; (3) these increases caused the higher NPP to cycle more rapidly through both plants and soil, contributing to higher CO2 and CH4 fluxes from decomposition. Thus, the increased C‐storage expected from higher productivity was limited and the high global warming potential of CH4 contributed a net positive warming effect. Although post‐thaw peatlands are currently C sinks due to high NPP offsetting high CO2 release, this status is very sensitive to the plant community's litter input rate and quality. Integration of novel bioavailability metrics based on litter chemistry, including NOSC, into studies of ecosystem dynamics, is needed to improve the understanding of controls on arctic C stocks under continued ecosystem transition.

Chemodiversity of Dissolved Organic Matter and Its Molecular Changes Driven by Rhizosphere Activities in Fe Ore Tailings Undergoing Eco-Engineered Pedogenesis.

Dissolved organic matter (DOM) plays an important role in soil structure and biogeochemical function development, which are fundamental for the eco-engineering of tailings-soil formation to underpin sustainable tailings rehabilitation. In the present study, we have characterized the DOM composition and its molecular changes in an alkaline Fe ore tailing primed with organic matter (OM) amendment and plant colonization. The results demonstrated that microbial OM decomposition dramatically increased DOM richness and average molecular weight, as well as its degree of unsaturation, aromaticity, and oxidation in the tailings. Plant colonization drove molecular shifts of DOM by depleting the unsaturated compounds with a high value of nominal oxidation state of carbon (NOSC), such as tannin-like and carboxyl-rich polycyclic-like compounds. This may be partially related to their sequestration by secondary Fe-Si minerals formed from rhizosphere-driven mineral weathering. Furthermore, the molecular shifts of DOM may have also resulted from plant-regulated microbial community changes, which further influenced DOM molecules through microbial-DOM interactions. These findings contribute to the understanding of DOM biogeochemistry and ecofunctionality in the tailings during early pedogenesis driven by OM input and pioneer plant/microbial colonization, providing an important basis for the development of strategies and technologies toward the eco-engineering of tailings-soil formation.