High throughput identification of carbonyl compounds in natural organic matter by directional derivatization combined with ultra-high resolution mass spectrometry.

Carbonyl compounds are important components of natural organic matter (NOM) with high reactivity, so that play a pivotal role in the dynamic transformation of NOM. However, due to the lack of effective analytical methods, our understanding on the molecular composition of these carbonyl compounds is still limited. Here, we developed a high-throughput screening method to detect carbonyl molecules in complex NOM samples by combining chemical derivatization with electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS). In six different types of dissolved organic matter (DOM) samples tested in this study, 20-30 % of detected molecules contained at least one carbonyl group, with relative abundance accounted for 45-70 %. These carbonyl molecules displayed lower unsaturation level, lower molecular weight, and higher oxidation degree compared to non-carbonyl molecules. More importantly, the measured abundances of carbonyl molecules were consistent with the results of 13C nuclear magnetic resonance (NMR) analysis. Based on this method, we found that carbonyl molecules can be produced at DOM-ferrihydrite interface, thus playing a role in shaping the molecular diversity of DOM. This method has broad application prospects in screening carbonyl compounds from complex mixtures, and the same strategy can be used to directional identification of molecules with other functional groups as well.

Soil's Hidden Power: The Stable Soil Organic Carbon Pool Controls the Burden of Persistent Organic Pollutants in Background Soils.

Persistent organic pollutants (POPs) tend to accumulate in cold regions by cold condensation and global distillation. Soil organic matter is the main storage compartment for POPs in terrestrial ecosystems due to deposition and repeated air-surface exchange processes. Here, physicochemical properties and environmental factors were investigated for their role in influencing POPs accumulation in soils of the Tibetan Plateau and Antarctic and Arctic regions. The results showed that the soil burden of most POPs was closely coupled to stable mineral-associated organic carbon (MAOC). Combining the proportion of MAOC and physicochemical properties can explain much of the soil distribution characteristics of the POPs. The background levels of POPs were estimated in conjunction with the global soil database. It led to the proposition that the stable soil carbon pools are key controlling factors affecting the ultimate global distribution of POPs, so that the dynamic cycling of soil carbon acts to counteract the cold-trapping effects. In the future, soil carbon pool composition should be fully considered in a multimedia environmental model of POPs, and the risk of secondary release of POPs in soils under conditions such as climate change can be further assessed with soil organic carbon models.

Molecular composition and characteristics of Sediment-adsorbed Dissolved Organic Matter (SDOM) along the coast of China.

Sediment-adsorbed Dissolved Organic Matter (SDOM) in coast plays a crucial role in the terrestrial and marine carbon cycle processes of the global environment. However, understanding the transport dynamics of SDOM along the coast of China, particularly its interactions with sediments, remains elusive. In this study, we analyzed the δ13C and δ15N stable isotopic compositions, as well as the molecular characteristics of SDOM collected from coastal areas spanning the Bohai Sea (BS), Yellow Sea (YS), East China Sea (ECS), and South China Sea (SCS), by using isotope ratio mass spectrometry and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS). We identified the predominant sources of carbon and nitrogen in coastal sediments, revealing terrigenous origins for most C and N, while anthropogenic sources dominated in the SCS. Spatial variations in SDOM chemodiversity were observed, with diverse molecular components influenced by distinct environmental factors and sediment sources. Notably, lignins and saturated compounds (such as proteins/amino sugars) were the predominant molecular compounds detected in coastal SDOM. Through Mantel tests and Spearman's correlation analysis, we elucidated the significant influence of spatial environmental factors (temperature, DO, salinity, and depth) and sediment sources on SDOM molecular chemodiversity. These findings contribute to a more comprehensive understanding of the carbon cycle dynamics along the Chinese coast.

Soil organic matter degradation and methylmercury dynamics in Hg-contaminated soils: Relationships and driving factors.

Biodegradation of soil organic matter (SOM), which involves greenhouse gas (GHG) emissions, plays an essential role in the global carbon cycle. Over the past few decades, this has become an important research focus, particularly in natural ecosystems. SOM biodegradation significantly affects contaminants in the environment, such as mercury (Hg) methylation, producing highly toxic methylmercury (MeHg). However, the potential link between GHG production from SOM turnover in contaminated soils and biogeochemical processes involving contaminants remains unclear. In this study, we investigated the dynamics of GHG, MeHg production, and the relationship between biogeochemical processes in soils from two typical Hg mining sites. The two contaminated soils have different pathways, explaining the significant variations in GHG and MeHg production. The divergence of the microbial communities in these two biogeochemical processes is essential. In addition to the microbial role, abiotic factors such as Hg species can significantly affect MeHg production. On the other hand, we found an inverse relationship between CH4 and MeHg, suggesting that carbon emission reduction policies and management could inadvertently increase the MeHg levels. This highlights the need for an eclectic approach to organic carbon sequestration and contaminant containment. These findings suggest that it is difficult to establish a general pattern to describe and explain the SOM degradation and MeHg production in contaminated soils within the specific scenarios. However, this study provides a case study and helpful insights for further understanding the links between environmental risks and carbon turnover in Hg mining areas.

Natural Disinfection-like Process Unveiled in Soil Microenvironments by Enzyme-Catalyzed Chlorination.

Substantial natural chlorination processes are a growing concern in diverse terrestrial ecosystems, occurring through abiotic redox reactions or biological enzymatic reactions. Among these, exoenzymatically mediated chlorination is suggested to be an important pathway for producing organochlorines and converting chloride ions (Cl-) to reactive chlorine species (RCS) in the presence of reactive oxygen species like hydrogen peroxide (H2O2). However, the role of natural enzymatic chlorination in antibacterial activity occurring in soil microenvironments remains unexplored. Here, we conceptualized that heme-containing chloroperoxidase (CPO)-catalyzed chlorination functions as a naturally occurring disinfection process in soils. Combining antimicrobial experiments and microfluidic chip-based fluorescence imaging, we showed that the enzymatic chlorination process exhibited significantly enhanced antibacterial activity against Escherichia coli and Bacillus subtilis compared to H2O2. This enhancement was primarily attributed to in situ-formed RCS. Based on semiquantitative imaging of RCS distribution using a fluorescence probe, the effective distance of this antibacterial effect was estimated to be approximately 2 mm. Ultrahigh-resolution mass spectrometry analysis showed over 97% similarity between chlorine-containing formulas from CPO-catalyzed chlorination and abiotic chlorination (by sodium hypochlorite) of model dissolved organic matter, indicating a natural source of disinfection byproduct analogues. Our findings unveil a novel natural disinfection process in soils mediated by indigenous enzymes, which effectively links chlorine-carbon interactions and reactive species dynamics.

Unique dissolved organic matter molecules and microbial communities in rhizosphere of three typical crop soils and their significant associations based on FT-ICR-MS and high-throughput sequencing analysis.

Using cucumber, maize, and ryegrass as model plants, the diversity and uniqueness of the molecular compositions of dissolved organic matter (DOM) and the structures of microbial communities in typical crop rhizosphere soils, as well as their associations, were investigated based on high-resolution mass spectrometry combined with high-throughput sequencing. The results showed that the rhizosphere contained 2200 organic molecules that were not identified in the non-rhizosphere soils, as characterized by FT-ICR-MS. The rhizosphere DOM molecules generally contained more N, S, and P heteroatoms, stronger hydrophilicity, and more refractory organic matter, representing high and complex chemical diversity characteristics. 16SrRNA sequencing results demonstrated that Proteobacteria, Actinomycetes and Firmicutes were the dominant flora in the soils. Plant species could significantly change the composition and relative abundance of rhizosphere microbial populations. The microbial community structures of rhizosphere and non-rhizosphere soils showed significant differences at both the phylum and class levels. Multiple interactions between the microorganisms and DOM compositions formed a complex network of relationships. There were strong and remarkable positive or negative couplings between different sizes and categories of DOM molecules and the specific microbial groups (P < 0.05, |R| ≥ 0.9) in the rhizosphere soils as shown by network profiles. The correlations between DOM molecules and microbial groups in rhizosphere soils had plant species specificity. The results above emphasized the relationship between the heterogeneity of DOM and the diversity of microbial communities, and explored the molecular mechanisms of the biochemical associations in typical plant rhizosphere soils, providing a foundation for in-depth understanding of plant-soil-microbe interactions.

Uptake, accumulation and toxicity of short chain chlorinated paraffins to wheat (Triticum aestivum L.).

Short chain chlorinated paraffins (SCCPs) are ubiquitous persistent organic pollutants. They have been widely detected in plant-based foods and might cause adverse impacts on humans. Nevertheless, uptake and accumulation mechanisms of SCCPs in plants remain unclear. In this study, the soil culture data indicated that SCCPs were strongly absorbed by roots (root concentration factor, RCF>1) yet limited translocated to shoots (translocation factor<1). The uptake mechanism was explored by hydroponic exposure, showing that hydrophobicity and molecular size influenced the root uptake and translocation of SCCPs. RCFs were significantly correlated with logKow values and molecular weights in a parabolic curve relationship. Besides, it was extremely difficult for SCCPs to translocate from shoots back to roots via phloem. An active energy-dependent process was proposed to be involved in the root uptake of SCCPs, which was supported by the uptake inhibition by the low temperature and metabolic inhibitor. Though SCCPs at environmentally relevant concentrations had no negative impacts on root morphology and chlorophyll contents, it caused obvious changes in cellular ultrastructure of root tip cells and induced a significant increase in superoxide dismutase activity. This information may be beneficial to moderate crop contamination by SCCPs, and to remedy soils polluted by SCCPs with plants.

Online chemiluminescence determination of the hydroxyl radical using coumarin as a probe.

The hydroxyl radical (˙OH) is one of the strongest oxidizing species, which can react with a variety of organic and inorganic chemicals. Although ˙OH is widely used for degradation of environmental pollutants, detection of ˙OH remains a major challenge due to its high reactivity and short lifetime, especially online detection. In this study, a novel method for online detection of ˙OH by flow oxidization chemiluminescence (F-OCL) using coumarin as a probe was established. The concentrations of ˙OH determined by this new method were consistent with those determined by HPLC analysis. Because the new method has a short response speed, it was successfully used to quantify the dynamic change of ˙OH in the TiO2 photocatalytic process and Fenton reaction in real time. Furthermore, a combination of two chemiluminescence systems was developed to track the dynamics of ˙OH and hydrogen peroxide (H2O2) in homogeneous or heterogeneous Fenton reactions occurring in soil slurry. The proposed method and strategy have good application potential in online ROS monitoring of both natural and engineered systems.

Novel Insights into the Adverse Health Effects of per- and Polyfluoroalkyl Substances on the Kidney via Human Urine Metabolomics.

Per- and polyfluoroalkyl substances (PFAS) receive significant research attention due to their potential adverse effects on human health. Evidence shows that the kidney is one of the target organs of PFAS. In occupational exposure scenarios, high PFAS concentrations may adversely affect kidney metabolism, but whether this effect is reflected in the small metabolic molecules contained in urine remains unknown. In this study, 72 matched serum and urine samples from occupational workers of a fluorochemical manufactory as well as 153 urine samples from local residents were collected, and 23 PFAS levels were quantified. The concentrations of Σ23PFAS in the serum and urine samples of workers were 5.43 ± 1.02 µg/mL and 201 ± 46.9 ng/mL, respectively, while the Σ23PFAS concentration in the urine of the residents was 6.18 ± 0.76 ng/mL. For workers, high levels of urinary PFAS were strongly correlated with levels in serum (r = 0.57-0.93), indicating that urinary PFAS can be a good indicator for serum PFAS levels. Further, a urine nontargeted metabolomics study was conducted. The results of association models, including Bayesian kernel machine regression, demonstrated positive correlations between urinary PFAS levels and key small kidney molecules. A total of eight potential biomarkers associated with PFAS exposure were identified, and all of them showed significant positive correlations with markers of kidney function. These findings provide the first evidence that urine can serve as a matrix to indicate the adverse health effects of high levels of exposure to PFAS on the kidneys.

Molecular-Scale Investigation on the Formation of Brown Carbon Aerosol via Iron-Phenolic Compound Reactions in the Dark.

Brown carbon (BrC) is one of the most mysterious aerosol components responsible for global warming and air pollution. Iron (Fe)-induced catalytic oxidation of ubiquitous phenolic compounds has been considered as a potential pathway for BrC formation in the dark. However, the reaction mechanism and product composition are still poorly understood. Herein, 13 phenolic precursors were employed to react with Fe under environmentally relevant conditions. Using Fourier transform ion cyclotron resonance mass spectrometry, a total of 764 unique molecular formulas were identified, and over 85% of them can be found in atmospheric aerosols. In particular, products derived from precursors with catechol-, guaiacol-, and syringol-like-based structures can be distinguished by their optical and molecular characteristics, indicating the structure-dependent formation of BrC from phenolic precursors. Multiple pieces of evidence indicate that under acidic conditions, the contribution of either autoxidation or oxygen-induced free radical oxidation to BrC formation is extremely limited. Ligand-to-Fe charge transfer and subsequent phenoxy radical coupling reactions were the main mechanism for the formation of polymerization products with high molecular diversity, and the efficiency of BrC generation was linearly correlated with the ionization potential of phenolic precursors. The present study uncovered how chemically diverse BrC products were formed by the Fe-phenolic compound reactions at the molecular level and also provide a new paradigm for the study of the atmospheric aerosol formation mechanism.

Investigation with ESI FT-ICR MS on sorbent selectivity and comprehensive molecular composition of landfill leachate dissolved organic matter.

Molecular characterization of landfill leachate dissolved organic matter (LDOM) is essential for developing effective processing techniques. However, the molecular selectivity of extraction method and ionization modes often leads to the bias of molecular characterization of LDOM. Here, seven representative sorbents were selected and electrospray ionization negative ion mode (ESI (-)) and positive ion mode (ESI (+)) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were used to investigate the molecular composition of different LDOM samples. Obvious sorbent selectivity during extraction procedure was observed, resulting in the underestimation of molecular diversity of LDOM from 32.7% to 69.3%. Totally, 14,000-18,000 unique molecules were obtained in a single sample, indicating the unprecedented molecular diversity of LDOM. Lignins, proteins and lipids are three major molecular groups in LDOM, and N or S containing molecules occupied 83%. Although much of total organic carbon was removed during biochemical treatment process, the molecular diversity of LDOM was not reduced because a considerable of bio-recalcitrant molecules was produced. The results uncover the sorbents selectivity and ionization modes selectivity in LDOM analysis and provided a comprehensive change of LDOM molecular composition during biochemical treatment, which benefits the development of accurate methods to remove organic carbon in landfill leachate.

Carbon Sequestration Strategies in Soil Using Biochar: Advances, Challenges, and Opportunities.

Biochar, a carbon (C)-rich material obtained from the thermochemical conversion of biomass under oxygen-limited environments, has been proposed as one of the most promising materials for C sequestration and climate mitigation in soil. The C sequestration contribution of biochar hinges not only on its fused aromatic structure but also on its abiotic and biotic reactions with soil components across its entire life cycle in the environment. For instance, minerals and microorganisms can deeply participate in the mineralization or complexation of the labile (soluble and easily decomposable) and even recalcitrant fractions of biochar, thereby profoundly affecting C cycling and sequestration in soil. Here we identify five key issues closely related to the application of biochar for C sequestration in soil and review its outstanding advances. Specifically, the terms use of biochar, pyrochar, and hydrochar, the stability of biochar in soil, the effect of biochar on the flux and speciation changes of C in soil, the emission of nitrogen-containing greenhouse gases induced by biochar production and soil application, and the application barriers of biochar in soil are expounded. By elaborating on these critical issues, we discuss the challenges and knowledge gaps that hinder our understanding and application of biochar for C sequestration in soil and provide outlooks for future research directions. We suggest that combining the mechanistic understanding of biochar-to-soil interactions and long-term field studies, while considering the influence of multiple factors and processes, is essential to bridge these knowledge gaps. Further, the standards for biochar production and soil application should be widely implemented, and the threshold values of biochar application in soil should be urgently developed. Also needed are comprehensive and prospective life cycle assessments that are not restricted to soil C sequestration and account for the contributions of contamination remediation, soil quality improvement, and vegetation C sequestration to accurately reflect the total benefits of biochar on C sequestration in soil.

Changes of Soil Dissolved Organic Matter and Its Relationship with Microbial Community along the Hailuogou Glacier Forefield Chronosequence.

Glacier-retreated areas are ideal areas to study soil biogeochemical processes during vegetation succession, because of the limited effect of other environmental and climatic factors. In this study, the changes of soil dissolved organic matter (DOM) and its relationship with microbial communities along the Hailuogou Glacier forefield chronosequence were investigated. Both microbial diversity and DOM molecular chemodiversity recovered rapidly at the initial stage, indicating the pioneering role of microorganisms in soil formation and development. The chemical stability of soil organic matter enhanced with vegetation succession due to the retaining of compounds with high oxidation state and aromaticity. The molecular composition of DOM affected microbial communities, while microorganisms tended to utilize labile components to form refractory components. This complex relationship network between microorganisms and DOM components played an important role in the development of soil organic matter as well as the formation of stable soil carbon pool in glacier-retreated areas.

Influence of microplastics on the photodegradation of perfluorooctane sulfonamide (FOSA).

PFAS (per- and polyfluoroalkyl substances) are omnipresent in the environment and their transportation and transformation have attracted increased attention. Microplastics are another potential risk substances that can serve as a carrier for ubiquitous pollutants, thus affecting the presence of PFAS in the environment. In this study, the adsorption of perfluorooctane sulfonamide (FOSA) and perfluorooctanoic acid (PFOA) on four microplastics (PE, PVC, PS, and PTFE) and their effect on the photodegradation of FOSA were studied. The adsorption capacity of FOSA by PS was the highest, in similar, PS displayed the highest adsorption capacity in the presence of PFOA. Different effects of pH and salinity on the adsorption of FOSA and PFOA were observed among different microplastics indicating inconsistent interaction mechanisms. Furthermore, FOSA could be photodegraded, with PFOA as the main product, while the presence of microplastics had a negligible effect on the degradation of this contaminant. The results indicated that microplastics could act as PFAS concentrators. Moreover, their photochemical inertias make the pollutants enriched on microplastics more resistant to degradation.

Multiple Effects of Humic Components on Microbially Mediated Iron Redox Processes and Production of Hydroxyl Radicals.

Microbially mediated iron redox processes are of great significance in the biogeochemical cycles of elements, which are often coupled with soil organic matter (SOM) in the environment. Although the influences of SOM fractions on individual reduction or oxidation processes have been studied extensively, a comprehensive understanding is still lacking. Here, using ferrihydrite, Shewanella oneidensis MR-1, and operationally defined SOM components including fulvic acid (FA), humic acid (HA), and humin (HM) extracted from black soil and peat, we explored the SOM-mediated microbial iron reduction and hydroxyl radical (•OH) production processes. The results showed that the addition of SOM inhibited the transformation of ferrihydrite to highly crystalline iron oxides. Although FA and HA increased Fe(II) production over four times on average due to complexation and their high electron exchange capacities, HA inhibited 30-43% of the •OH yield, while FA had no significant influence on it. Superoxide (O2•-) was the predominant intermediate in •OH production in the FA-containing system, while one- and two-electron transfer processes were concurrent in HA- and HM-containing systems. These findings provide deep insights into the multiple mechanisms of SOM in regulating microbially mediated iron redox processes and •OH production.

Unexpected Persistent Production of Reactive Oxygen Species during the Degradation of Black Phosphorous in the Darkness.

Few-layer black phosphorus (FLBP) is easily degraded under ambient conditions which is problem that hinders the application of FLBP, but its degradation mechanism is not yet well understood. In this work, we surprisingly found that persistent generation of reactive oxygen species (ROS) was involved in FLBP degradation even in the dark. The ROS generation patterns and mechanism were revealed by chemiluminescence (CL) and density functional theory (DFT). Meanwhile, rhodamine B (RhB) and methyl orange (MO) can also be removed by FLBP under dark conditions, which further shows the ROS generation during FLBP self-degradation. This work provides new insights into the FLBP self-degradation mechanism and opens opportunities to practically implement FLBP for green catalytic application.

Unexpected molecular diversity of brown carbon formed by Maillard-like reactions in aqueous aerosols.

Atmospheric brown carbon (BrC) exerts a key impact on the global radiative balance due to its light-absorbing properties. Maillard-like reactions between carbonyl and amino compounds have been identified as an important pathway for forming secondary BrC. Although optical properties have been widely studied, the molecular composition of secondary BrC generated in Maillard chemistry remains unclear, resulting in a knowledge gap to understand its formation and light-absorbing mechanism. In this study, a combination of optical spectroscopy, 1H nuclear magnetic resonance (NMR), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was employed to comprehensively characterize the chemical and light-absorbing characteristics of secondary BrC. The results indicate that both the light-absorbing and molecular characteristics of secondary BrC were highly related to the structures of their precursors. Organic amine precursors consistently result in enhanced light-absorbing capacities of BrC compared to ammonium, but have inconsistent effects on the molecular diversity of BrC. Compared to amino precursors (i.e., glycine, ethylamine, propylamine, and ammonium), carbonyl precursors play a more important role in determining the molecular diversity of BrC. Different from black carbon, the light-absorbing products from Maillard-like reactions are mainly nitrogen-containing heterocycles. Unexpectedly, 35-64% of molecular formulae detected in real atmospheric samples were found in simulated Maillard reaction products, implying a potentially important contribution of Maillard chemistry to the atmospheric organic molecular pool. These results will improve our understanding of the formation and molecular diversity of BrC, and further help to manage emissions of secondary aerosol precursors.

Advances in Molecular and Microscale Characterization of Soil Organic Matter: Current Limitations and Future Prospects.

Soil organic matter (SOM) comprises a continuum of organic materials from granular organic debris to small organic molecules and contains more organic carbon than global vegetation and the atmosphere combined. It has remarkable effects on soil ecological functions and the global carbon cycle as well as the fate of pollutants in the terrestrial ecosystem. Therefore, characterization of SOM is an important topic in soil science, ecology, and environmental science. Chemical complexity and spatial heterogeneity are by far the two biggest challenges to our understanding of SOM. Recent developments in analytical techniques and methods provide the opportunity to reveal SOM composition at the molecular level and to observe its distribution in soils at micro- and nanoscales, which have greatly improved our understanding of SOM. This paper reviews the outstanding advances in SOM characterization regarding these two issues from target and nontarget analyses comprising molecular marker analysis, ultrahigh-resolution mass spectrometry analysis, and in situ microscopic imaging techniques such as synchrotron-based spectromicroscopy, nanoscale secondary ion mass spectrometry, and emerging electron and optical microscopic imaging techniques. However, current techniques and methods remain far from unlocking the unknown properties of SOM. We systematically point out the limitations of the current technologies and outline the future prospects for comprehensive characterization of SOM at the molecular level and micro- and nanoscales, paying particular attention to issues of environmental concern.

Bioaccumulation and biotransformation of tetrabromoethylcyclohexane (TBECH) in maize (Zea mays L.): Stereoselective driving roles of plant biomacromolecules.

The bioaccumulation and biotransformation of tetrabromoethylcyclohexane (TBECH) in maize were investigated. Furthermore, the roles of plant biomacromolecules such as lipid transfer proteins (LTPs), CYP and GST enzymes in driving the biological processes of TBECH stereoisomers were explored. The uptake and translocation of TBECH in maize were diastereo- and enantio-selective. Isomerization from α- to δ-TBECH and ß- to γ-TBECH, and metabolites of debromination, hydroxylation and TBECH-GSH adducts were identified in maize roots. The gene expressions of LTPs, CYPs and GSTs were extensively changed in maize after exposure to technical TBECH. CYP and GST enzyme activities as well as GST31 and CYP71C3v2 gene expressions were selectively induced or inhibited by TBECH diastereomers over time. TBECH was able to dock into the active sites and bind with specific residues of the typical biomacromolecules ZmLTP1.6, GST31 and CYP71C3v2, indicating their roles in the bioaccumulation and metabolization of TBECH. Binding modes and affinities to biomacromolecules were significantly different between α- and ß-TBECH, which contributed to their stereo-selectivity. This study provided a deep understanding of the biological fate of TBECH, and revealed the driving molecular mechanisms of the selectivity of TBECH stereoisomers in plants.