Reactivity Of Dissolved Organic Matter Research Articles

Long-term straw return enhanced the chlorine reactivity of soil DOM: Highlighting the molecular-level activity and transformation trade-offs

Chemical properties and molecular diversity of dissolved organic matter (DOM) in agricultural soils are important for soil carbon dynamics and chlorine activity. Yet the chlorine reactivity of soil DOM at the molecular level under agricultural management practices remains unidentified. Here, we investigated the chlorine reactivity of soil DOM under long-term straw return and the molecular activities and transformations during chlorination. The 9-year straw return enhanced the chlorine reactivity of soil DOM, leading to increases in the production of traditional disinfection byproducts (DBPs) and decreases in the formation of emerging high molecular weight DBPs. C17HnOmCl1–2 and C22HnNmOzCl were the highest relative abundances of emerging DBPs. The emerging DBPs were primarily generated through chlorine substitution reactions, with their precursors exhibiting higher H/Cwa (1.47) and O/Cwa (0.41) ratios under straw return. The molecular transformation ability and inactive molecules of soil DOM under long-term straw return were reduced after chlorination, resulting in increased DOM instability. Chlorination led to a shift in the thermodynamic processes of soil DOM molecules from thermodynamically limited to thermodynamically favorable processes, and lignin-like compounds displayed higher potentials for transformation into protein/amino sugar-like compounds. C19H26O6 was identified as a sensitive formula for tracing chlorine reactivity under straw return, and a network illustrating the generation of DBPs from C19H26O6 was established. Overall, these results highlighted the strong chlorine reactivity of soil DOM under long-term straw return.

Molecular Weights of Dissolved Organic Matter Significantly Affect Photoaging of Microplastics.

The fate of ubiquitous microplastics (MPs) is largely influenced by dissolved organic matter (DOM) in aquatic environments, which has garnered significant attention. The reactivity of DOM is reported to be greatly regulated by molecular weights (MWs), yet little is known about the effects of different MW DOM on MP aging. Here, the aging behavior of polystyrene MPs (PSMPs) in the presence of different MW fulvic acids (FAs) and humic acids (HAs) was systematically investigated. Under ultraviolet (UV) illumination, O/C of PSMPs aged for 96 h surged from 0.008 to 0.146 in the lower MW FA (FA<1kDa) treatment, suggesting significant PSMP aging. However, FA exhibited a stronger effect on facilitating PSMP photoaging than HA, which can be attributed to the fact that FA<1kDa contains more quinone and phenolic moieties, demonstrating a higher redox capacity. Meanwhile, compared to other fractions, FA<1kDa was more actively involved in the increase of different reactive species yields by 50-290%, including •OH, which plays a key role in PSMP photoaging, and contributed to a 25% increase in electron-donating capacity (EDC). This study lays a theoretical foundation for a better understanding of the environmental fate of MPs.

Complexation with Metal Ions Affects Chlorination Reactivity of Dissolved Organic Matter: Structural Reactomics of Emerging Disinfection Byproducts.

Metal ions are liable to form metal-dissolved organic matter [dissolved organic matter (DOM)] complexes, changing the chemistry and chlorine reactivity of DOM. Herein, the impacts of iron and zinc ions (Fe3+ and Zn2+) on the formation of unknown chlorinated disinfection byproducts (Cl-DBPs) were investigated in a chlorination system. Fe3+ preferentially complexed with hydroxyl and carboxyl functional groups, while Zn2+ favored the amine functional groups in DOM. As a consequence, electron-rich reaction centers were created by the C-O-metal bonding bridge, which facilitated the electrophilic attack of α-C in metal-DOM complexes. Size-reactivity continuum networks were constructed in the chlorination system, revealing that highly aromatic small molecules were generated during the oxidation and decarbonization of metal-DOM complexes. Molecular transformation related to C-R (R represents complex sites) loss was promoted via metal complexation, including decarboxylation and deamination. Consequently, complexation with Fe3+ and Zn2+ promoted hydroxylation by the C-O-metal bonding bridge, thereby increasing the abundances of unknown polychlorinated Cl-DBPs by 9.6 and 14.2%, respectively. The study provides new insights into the regulation of DOM chemistry and chlorine reactivity by metal ions in chlorination systems, emphasizing that metals increase the potential health risks of drinking water and more scientific control standards for metals are needed.

Molecular-level insights into dissolved organic matter and its variations of the full-scale processes in a typical petrochemical wastewater treatment plant

Petrochemical wastewater (PCWW) treatment poses challenges due to its unique and complex dissolved organic matter (DOM) composition, originating from various industrial processes. Despite the addition of advanced treatment units in PCWW treatment plants to meet discharge standards, the mechanisms of molecular-level sights into DOM reactivity of the upgraded full-scale processes including multiple biological treatments and advanced treatment remain unclear. Herein, we employ water quality indexes, spectra, molecular weight (MW) distribution, and Fourier transform ion cyclotron resonance mass spectrometry to systematically characterize DOM in a typical PCWW treatment plant including influent, micro-oxygen hydrolysis acidification (MOHA), anaerobic/oxic (AO), and micro-flocculation sand filtration–catalytic ozonation (MFSF–CO). Influent DOM is dominated by tryptophan-like and soluble microbial products with MW fractions 〈 1 kDa and 〉 100 kDa, and CHO with lignin and aliphatic/protein structures. MOHA effectively degrades macromolecular CHO (10.86 %) and CHON (5.24 %) compounds via deamination and nitrogen reduction, while AO removes CHOS compounds with MW < 10 kDa by desulfurization, revealing distinct DOM conversion mechanisms. MFSF–CO transforms unsaturated components to less aromatic and more saturated DOM through oxygen addition reactions and shows high CHOS and CHONS reactivity via desulfurization and deamination reactions, respectively. Moreover, the correlation among multiple parameters suggests UV254 combined with AImod as a simple monitoring indicator of DOM to access the chemical composition. The study provides molecular-level insights into DOM for the contribution to the improvement and optimization of the upgraded processes in PCWW.

Treeline displacement may affect lake dissolved organic matter processing at high latitudes and altitudes

Climate change induced shifts in treeline position, both towards higher altitudes and latitudes induce changes in soil organic matter. Eventually, soil organic matter is transported to alpine and subarctic lakes with yet unknown consequences for dissolved organic matter (DOM) diversity and processing. Here, we experimentally investigate the consequences of treeline shifts by amending subarctic and temperate alpine lake water with soil-derived DOM from above and below the treeline. We use ultra-high resolution mass spectrometry (FT-ICR MS) to track molecular DOM diversity (i.e., chemodiversity), estimate DOM decay and measure bacterial growth efficiency. In both lakes, soil-derived DOM from below the treeline increases lake DOM chemodiversity mainly through the enrichment with polyphenolic and highly unsaturated compounds. These compositional changes are associated with reductions in bulk and compound-level DOM reactivity and reduced bacterial growth efficiency. Our results suggest that treeline advancement has the potential to enrich a large number of lake ecosystems with less biodegradable DOM, affecting bacterial community function and potentially altering the biogeochemical cycling of carbon in lakes at high latitudes and altitudes.

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.

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.

Universal microbial reworking of dissolved organic matter along environmental gradients.

Soils are losing increasing amounts of carbon annually to freshwaters as dissolved organic matter (DOM), which, if degraded, can offset their carbon sink capacity. However, the processes underlying DOM degradation across environments are poorly understood. Here we show DOM changes similarly along soil-aquatic gradients irrespective of environmental differences. Using ultrahigh-resolution mass spectrometry, we track DOM along soil depths and hillslope positions in forest catchments and relate its composition to soil microbiomes and physico-chemical conditions. Along depths and hillslopes, we find carbohydrate-like and unsaturated hydrocarbon-like compounds increase in abundance-weighted mass, and the expression of genes essential for degrading plant-derived carbohydrates explains >50% of the variation in abundance of these compounds. These results suggest that microbes transform plant-derived compounds, leaving DOM to become increasingly dominated by the same (i.e., universal), difficult-to-degrade compounds as degradation proceeds. By synthesising data from the land-to-ocean continuum, we suggest these processes generalise across ecosystems and spatiotemporal scales. Such general degradation patterns can help predict DOM composition and reactivity along environmental gradients to inform management of soil-to-stream carbon losses.

MIEX resin and enhanced coagulation treatment of high-bromide natural water: Chlorine reactivity and DBP precursors removal

Both organic and inorganic constituents play a major role in the formation and speciation of disinfection by-products (DBPs) under chlorination. In this study, the removal of organic and inorganic precursors to DBPs by ion exchange and coagulation was examined, and the relationships between characteristics of dissolved organic matter (DOM), chlorine reactivity, and the formation of DBPs in high-bromide natural water were investigated. Formation potential tests were conducted for trihalomethanes (THMs) and haloacetronitriles (HANs) before and after the different treatments (coagulation, magnetic ion exchange (MIEX) resin, and combined MIEX/coagulation). At a low resin dose, MIEX was more effective than coagulation for DOM removal. The advantages of the MIEX resin were more prominent at a high resin dose because substantial amounts of DOM and bromide were simultaneously removed. The maximum bromide uptake on the MIEX resin was 0.02 mg-Br/mL. A 4-component PARAFAC model was developed using a dataset of 148 fluorescence excitation-emission matrices (EEMs) generated from pre-chlorinated and post-chlorinated samples. The maximum fluorescence intensities of humic-like components were found to be strongly correlated to THMs formation (R2 = 0.79–0.89). The MIEX treatment substantially lowered the formation of THMs (19–51%) and HANs (70–95%) due to its ability to remove humic-like DOM and bromide. The fluorescence loss for humic-like DOM was found to increase over a chlorination time of 3 days, suggesting that these compounds had stronger reactivity to chlorine compared to protein-like DOM. The chlorine reactivity of protein-like DOM increased after treatments as the residual chlorine was able to react with the less reactive fractions of DOM after chlorine-reactive compounds were removed.

Linking the source, molecular composition, and reactivity of dissolved organic matter in major rivers across the pearl river delta

Dissolved organic matter (DOM) constitutes a substantial portion of the global carbon cycle and serves as the largest reservoir of reactive carbon on Earth. Studying DOM's sources, molecular compositions, and reactivity is central to understanding the fate and environmental effects of organic carbon, yet, links between DOM composition and reactivity remain to be established. In this study, stable carbon isotopic composition and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) were combined with degradation experiments to comprehensively study DOM's properties in the major rivers across the Pearl River Delta (PRD) in South China. The increasing δ13C-DOC along the Pearl River at the PRD suggests that terrestrial DOM from upstream was gradually diluted by local processes. Although affected by different interaction patterns of multiple sources, a major component of DOM, enriched in CHO and lignins, is molecularly indistinguishable in different rivers (molecular Bray-Curtis dissimilarity of 15%–31%). The photo-degradation removed 34% (PDOC%) of initial DOM within 14 days, twice that by biodegradation (BDOC%). In contrast to earlier research, the distinctive integration of molecular characterization with DOM degradation kinetics indicates that both regional (common shared molecules) and local (partial shared and unique molecules) derived DOM play a collective role in governing the bio-degradation kinetics of DOM, while the photo-degradation kinetics of DOM are barely correlated to molecular composition. The thorough investigation of DOM molecular composition and its correlation with bulk DOM properties in the PRD region, though requiring further investigation into its mechanisms, offers valuable insights into the role of riverine DOM in coastal hypoxia and the global carbon cycle.

Evaluation of the role of superoxide radical as chain carrier for the formation of hydroxyl radical during ozonation

Superoxide radicals (O2•−) have been suggested as an important chain carrier in the radical chain reaction that promotes ozone (O3) decomposition to hydroxyl radicals (•OH) during ozonation. However, due to the difficulty in measuring transient O2•− concentrations, this hypothesis has not been verified under realistic ozonation conditions during water treatment. In this study, a probe compound was used in combination with kinetic modeling to evaluate the role of O2•− for O3 decomposition during ozonation of synthetic solutions with model promotors and inhibitors (methanol and acetate or tert-butanol) and natural waters (one groundwater and two surface waters). By measurement of the abatement of spiked tetrachloromethane (as a O2•− probe), the O2•− exposure during ozonation was determined. Based on the measured O2•− exposures, the relative contribution of O2•− to O3 decomposition, in comparison to OH−, •OH, and dissolved organic matter (DOM), was quantitatively evaluated using kinetic modeling. The results show that water compositions (e.g., the concentration of promotors and inhibitors, and the O3 reactivity of DOM) have a considerable effect on the extent of the O2•−-promoted radical chain reaction during ozonation. In general, the reaction with O2•− accounted for ∼59‒70% and ∼45‒52% of the overall O3 decomposition during ozonation of the selected synthetic solutions and natural waters, respectively. This confirms that O2•− plays a critical role in promoting O3 decomposition to •OH. Overall, this study provides new insights on the controlling factors for ozone stability during ozonation processes.

A Temporal Graph Model to Predict Chemical Transformations in Complex Dissolved Organic Matter.

Dissolved organic matter (DOM) is a complex mixture of thousands of natural molecules that undergo constant transformation in the environment, such as sunlight induced photochemical reactions. Despite molecular level resolution from ultrahigh resolution mass spectrometry (UHRMS), trends of mass peak intensities are currently the only way to follow photochemically induced molecular changes in DOM. Many real-world relationships and temporal processes can be intuitively modeled using graph data structures (networks). Graphs enhance the potential and value of AI applications by adding context and interconnections allowing the uncovering of hidden or unknown relationships in data sets. We use a temporal graph model and link prediction to identify transformations of DOM molecules in a photo-oxidation experiment. Our link prediction algorithm simultaneously considers educt removal and product formation for molecules linked by predefined transformation units (oxidation, decarboxylation, etc.). The transformations are further weighted by the extent of intensity change and clustered on the graph structure to identify groups of similar reactivity. The temporal graph is capable of identifying relevant molecules subject to similar reactions and enabling to study their time course. Our approach overcomes previous data evaluation limitations for mechanistic studies of DOM and leverages the potential of temporal graphs to study DOM reactivity by UHRMS.

Manganese oxides mediated dissolve organic matter compositional changes in lake sediment and cadmium binding characteristics

In sediment environments, manganese (Mn) minerals have high dissolved organic matter (DOM) affinities, and could regulate the changes of DOM constituents and reactivity by fractionation. However, the effects of DOM fractionation by Mn minerals on the contaminant behaviors remain unclear. Herein, the transformations of mineral phases, DOM properties, and Cd(II) binding characteristics to sediment DOM before and after adsorption by four Mn oxides (δ-MnO2, β-MnO2, γ-MnOOH, and Mn3O4) were investigated using multi-spectroscopic tools. Results showed a subtle structural variation of Mn oxides in response to DOM reduction, and no phase transformations were observed. Two-dimensional correlation spectroscopy based on synchronous fluorescence spectra and Fourier transform infrared spectroscopy indicated that tryptophan-like substances and the amide (II) N–H groups could preferentially interact with Cd(II) for the original DOM. Nevertheless, preferential bonding of Cd(II) to tyrosine-like substances and phenolic OH groups was exhibited after fractionations by Mn oxides. Furthermore, the binding stability and capacity of each DOM fraction to Cd(II) were decreased after fractionation based on the modified Stern-Volmer equation. These differences may be attributed to DOM molecules with high aromaticity, hydrophobicity, molecular weight, and amounts of O/N-containing group were preferentially removed by Mn oxides. Overall, the environmental hazard of Cd will be more severe after DOM fractionation on Mn minerals. This study facilitates a better understanding of the Cd geochemical cycle in lake sediments under the DOM–mineral interactions, and recommends being careful with outbreaks of aquatic Cd pollution when sediments are rich in dissolved protein-like components and Mn minerals.

Sampling terrigenous diffuse sources in watercourse: Influence of land use and hydrological conditions on dissolved organic matter characteristics

Diffuse and point sources of dissolved organic matter (DOM) in streams influence its composition, interactions and fate in the aquatic ecosystem. These inputs can be very numerous at the scale of a watershed, and their identification remains a challenge, especially for diffuse sources related to land use. The complexity of the transfer mechanisms and the reactivity of DOM throughout the soil-water column continuum raise questions about the sampling of diffuse sources in watercourses. To answer this issue, we compared the characteristics of soil-extracted DOM influenced by a particular land use (homogenous sub-catchment of forest and vineyard) and DOM collected from the watercourse adjacent to the soil samples. A 28-day incubation experiment of soil extracts was designed to remove the labile fraction of DOM. During the first 3 days, between 40 and 70 % of the DOC mass was lost for both types of soils. A set of optical indicators (UV–Visible, EEM fluorescence and HPSEC/UV-fluorescence) showed that the labile fraction was mostly composed by low (<1 kDa) and high (>10 kDa) protein-like molecules. At the end of the incubation, soil-extracted DOM was mainly composed of medium molecules (1–10 kDa) associated to terrigenous humic-like compounds. Its optical and size molecular signature tended towards that in the adjacent watercourses and was specific to land use. However, the characteristics of DOM in watercourses was also influenced by the hydrological conditions, probably due to a transfer of top soil DOM during high water periods and both deep soil and autochthonous DOM during low water periods. These results were obtained by a set of indicators, including novel ones derived from HPSEC/UV-fluorescence. Finally, this study demonstrated that it is possible to sample the DOM representative of a land use directly in the river downstream of the homogeneous sub-basin by multiplying the samples during contrasting hydrological conditions.

Size exclusion chromatography and stable carbon isotopes reveal the limitations of solid phase extraction with PPL to capture autochthonous DOM production

The study of the elemental and carbon isotopic composition of dissolved organic matter (DOM) is of great interest in deciphering the origin and transformations of organic matter in estuarine and coastal environments. Styrene-divinylbenzene copolymer (PPL) sorbent is currently the most commonly used material for the isolation of DOM from environmental samples. It is notably used for the development of molecular formula-based indices used to study DOM reactivity. However, any extraction procedure (including with PPL) will fractionate the DOM. If this fractionation is not well constrained it can lead to biased interpretations of the biogeochemical processes affecting DOM. In this work we investigate the fractionation effects of the PPL sorbent on the size class distribution of DOM and the carbon isotopic composition of the PPL retentate. The use of size exclusion chromatography, that does not require a pre-concentration step, allows a precise study of the fractionation of DOM (including aromaticity) by the PPL resin. Extractions performed on two types of humic substances dissolved in artificial seawater, using the PPL resin, showed high extraction yield (> 85%) and the stable isotopic carbon composition (δ13C) of these compounds was successfully recovered. These results indicate that salinity is not a parameter affecting extraction yield on PPL sorbent. For a hydrophilic compound (atropine) the extraction efficiency was low (33%) and δ13C signature was underestimated. Size exclusion chromatography measurements, in samples collected along a salinity gradient, demonstrate that the PPL sorbent strongly fractionates DOM. Although the DOM size class distributions in freshwaters and marine waters were initially different, their retentates were marked by similar size class distributions. This work demonstrates that PPL resin captures DOM compounds with less nitrogenous content and it seems to have a lower affinity for aromatic compounds of marine origin than of terrigenous origin. The study of DOM distribution in a macro-tidal estuary demonstrated the limitations of PPL resin extraction in capturing an internal N-rich DOM production event at the time of sampling. Futhermore, the isotopic composition of the PPL resin retentate appears to depend on the extraction efficiency of the more hydrophobic compounds which changed along the salinity gradient. This study recommends careful interpretations of data that only rely on PPL extractions, particularly for works tracking the origin of DOM in estuaries and comparing DOM composition across ocean biogeochemical domains.

Using the end-member mixing model to evaluate biogeochemical reactivities of dissolved organic matter (DOM): autochthonous versus allochthonous origins

Dissolved organic matter (DOM) is an essential component of environmental systems. It usually originates from two end-members, including allochthonous and autochthonous sources. Previously, links have been established between DOM origins/sources and its biogeochemical reactivities. However, the influence of changes in DOM characteristics driven by end-member mixing on DOM biogeochemical reactivities has not been clarified. In this study, we investigated variations of DOM reactivities responding to the dynamics of DOM characteristics induced by different mixing ratios of two DOM end-members derived from humic acid (HA) and algae, respectively. Four biogeochemical reactivities of DOM were evaluated, including biodegradation, ·OH production, photodegradation, and redox capacity. Results showed that the variations of DOM characteristics due to the two end-members mixing significantly impact its biogeochemical reactivities. However, not all spectral parameters and reactivities followed the conservative mixing behavior. In contrast to reactivities of ·OH production and redox capacity, mixed samples showed apparent deviations from conservative linear relationships in biodegradation and photodegradation due to the interaction between the two end-members. Regarding the role of DOM properties influencing reactivity changes, peak A and M were recognized as the most stable parameters. However, peak C and SUVA254 were identified as the most vital contributors for explaining DOM reactivity variations. These findings suggest that a general model for describing the dynamic relationship between DOM source and reactivity cannot be proposed. Thus, the dynamics of DOM reactivity in diverse ecosystems cannot be estimated simply by the “plus or minus” of the reactivity from individual end-member. The effect of end-member mixing should be evaluated in a given reactivity instead of generalization. This study provides important insights for further understanding the dynamics of DOM's environmental role in different ecosystems influenced by variations of source inputs. In future, more field investigations are needed to further verify our findings in this study, especially in the scenario of end-member mixing.

Unified Modeling Approach for Quantifying the Proton and Metal Binding Ability of Soil Dissolved Organic Matter.

Soil dissolved organic matter (DOM) is composed of a mass of complex organic compounds in soil solutions and significantly affects a range of (bio)geochemical processes in soil environment. However, how the chemical complexity (i.e., heterogeneity and chemodiversity) of soil DOM molecules affects their proton and metal binding ability remains unclear, which limits our ability for predicting the environmental behavior of DOM and metals. In this study, we developed a unified modeling approach for quantifying the proton and metal binding ability of soil DOM based on Cu titration experiments, Fourier transform ion cyclotron resonance mass spectrometry data, and molecular modeling method. Although soil DOM samples from different regions have enormously heterogeneous and diverse properties, we found that the molecules of soil DOM can be divided into three representative groups according to their Cu binding capacity. Based on the molecular models for individual molecular groups and the relative contributions of each group in each soil DOM, we were able to further develop molecular models for all soil DOM to predict their molecular properties and proton and metal binding ability. Our results will help to develop mechanistic models for predicting the reactivity of soil DOM from various sources.

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.

The dominant role of sunlight in degrading winter dissolved organic matter from a thermokarst lake in a subarctic peatland

Abstract. Dissolved organic matter (DOM) leaching from thawing permafrost may promote a positive feedback on the climate if it is efficiently mineralized into greenhouse gases. However, many uncertainties remain on the extent of this mineralization, which depends on DOM lability that is seemingly quite variable across landscapes. Thermokarst peatlands are organic-rich systems where some of the largest greenhouse gas (GHG) emission rates have been measured. At spring turnover, anoxic waters release the GHG accumulated in winter, and the DOM pool is exposed to sunlight. Here, we present an experiment where DOM photoreactivity and bioreactivity were investigated in water collected from a thermokarst lake in a subarctic peatland during late winter (after 6 months of darkness). We applied treatment with or without light exposure, and manipulated the bacterial abundance with the aim to quantify the unique and combined effects of light and bacteria on DOM reactivity at ice-off in spring. We demonstrate that sunlight was clearly driving the transformation of the DOM pool, part of which went through a complete mineralization into CO2. Up to 18 % of the initial dissolved organic carbon (DOC, a loss of 3.9 mgC L−1) was lost over 18 d of sunlight exposure in a treatment where bacterial abundance was initially reduced by 95 %. However, sunlight considerably stimulated bacterial growth when grazers were eliminated, leading to the recovery of the original bacterial abundance in about 8 d, which may have contributed to the DOC loss. Indeed, the highest DOC loss was observed for the treatment with the full bacterial community exposed to sunlight (5.0 mgC L−1), indicating an indirect effect of light through the bacterial consumption of photoproducts. Dark incubations led to very limited changes in DOC, regardless of the bacterial abundance and activity. The results also show that only half of the light-associated DOC losses were converted into CO2, and we suggest that the rest potentially turned into particles through photoflocculation. Sunlight should therefore play a major role in DOM processing, CO2 production and carbon burial in peatland lakes during spring, likely lasting for the rest of the open season in mixing surface layers.

Oxygen availability driven trends in DOM molecular composition and reactivity in a seasonally stratified fjord

Ocean deoxygenation could potentially trigger substantial changes in the composition and reactivity of dissolved organic matter (DOM) pool, which plays an important role in the global carbon cycle. To evaluate links between DOM dynamics and oxygen availability, we investigated the DOM composition under varying levels of oxygen in a seasonally hypoxic fjord through a monthly time-series over two years. We used ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to characterize DOM on a molecular level. We find a clear trend both in diversity and molecular composition of the DOM along the oxygen gradient. As oxygen decreased, the chemodiversity was significantly increased, along with accumulation of relatively high-molecular-weight, reduced and unsaturated compounds enriched with carboxyl-group structures, which were also thermodynamically less favorable to biodegradation. Our results suggested that oxygen depletion selectively protected otherwise bioavailable compounds from decomposition and may promote the accumulation of a larger recalcitrant DOM pool in the global ocean, which could provide negative feedback to the ocean carbon sequestration and climate change.