Reactivity Of Organic Matter Research Articles

Particulate Matter-Induced Emerging Health Effects Associated with Oxidative Stress and Inflammation.

Environmental pollution continues to increase with industrial development and has become a threat to human health. Atmospheric particulate matter (PM) was designated as a Group 1 carcinogen by the International Agency for Research on Cancer in 2013 and is an emerging global environmental risk factor that is a major cause of death related to cardiovascular and respiratory diseases. PM is a complex composed of highly reactive organic matter, chemicals, and metal components, which mainly cause excessive production of reactive oxygen species (ROS) that can lead to DNA and cell damage, endoplasmic reticulum stress, inflammatory responses, atherosclerosis, and airway remodeling, contributing to an increased susceptibility to and the exacerbation of various diseases and infections. PM has various effects on human health depending on the particle size, physical and chemical characteristics, source, and exposure period. PM smaller than 5 μm can penetrate and accumulate in the alveoli and circulatory system, causing harmful effects on the respiratory system, cardiovascular system, skin, and brain. In this review, we describe the relationship and mechanism of ROS-mediated cell damage, oxidative stress, and inflammatory responses caused by PM and the health effects on major organs, as well as comprehensively discuss the harmfulness of PM.

Occurrence characteristics of authigenic pyrite in the deep-sea environment and its paleoceanographic implications based on core sediments from IODP Expedition 342 Site U1406

Although authigenic pyrite (FeS2) in marine sediment is an important proxy for oxygen conditions and microbial activities at its formation site, very little is known about its morphological characteristics in the deep-sea (> 3500 m) environment and their paleoceanographic implications. Here, we report the occurrence characteristics of authigenic pyrite including texture, size distribution, and relative content in North Atlantic deep-sea sediments from Integrated Ocean Drilling Program (IODP) Expedition 342 Site U1406. The results of electron microscopy show octahedral pyrite microcrystals of 1.5–4.0 μm, the spherical texture of greigite (Fe3S4), and large pyrite framboids (average, 25 μm) relative to those of the continental margin. These features may demonstrate an unchanged supersaturation level of the pore water for octahedral pyrite after its initial formation, replacement of the precursor greigite by pyrite, and an expanded pyrite framboid formation zone with a low sulfate reduction rate in deep-sea sediments, respectively. Although the size distribution of pyrite framboids measured in this study falls into the range of pyrites formed in the sulfate–methane transition zone, based on onboard geochemical data and previous research, these pyrites most likely formed through organoclastic sulfate reduction during diagenesis. We assessed the implications of these findings for paleoceanographic changes, as the formation of diagenetic pyrite is controlled by the supply rate and reactivity of organic matter, which are closely related to ocean productivity and circulation. A comparison between the profiles of relative pyrite content and benthic foraminiferal oxygen isotope (δ18Obf) values indicated that these factors were anti-phased during the late Oligocene. Based on our results, we conclude that the formation of diagenetic pyrite was favored during interglacial periods due to increases in the amount and reactivity of organic matter driven by more energetic formation of proto-North Atlantic Deep Water. Our findings provide new insights into the formation of authigenic pyrite in deep-sea environments and its potential as a paleoceanographic proxy.

Microbial contribution to the formation of the Carboniferous sedimentary manganese deposits in northwestern China

There is an increasing consensus that microbes play a critical role in the genesis of sedimentary manganese (Mn) carbonate deposits. However, compelling evidence for the microbial involvement during sedimentary Mn metallogenesis remains insufficient, and the specific effects of microbial mediation need to be further elucidated. To advance our understanding of the microbial Mn metallogenesis, multi-scale petrographic observations and high-resolution mineralogical analyses (mainly based on Fourier transform infrared spectrometer and Raman spectroscopy) were conducted on the Carboniferous black shale-hosted Malkansu and limestone-hosted Zhaosu Mn ore deposits in northwestern China. Results show that the Mn ore samples are characterized by finely laminated texture with μm-scale cyclic variations of microbe-associated minerals including rhodochrosite, apatite, quartz, and organic matter as well. These features indicate the ubiquity of microbial mats during Mn mineralization. Microbial involvement is also supported by Mn carbonate aggregates with variable morphologies (filamentous with pearl necklace-like inner forms resembling vermiform morphologies and spheroidal, coccoid-like forms), as well as the annular organic matter that resembles bacterial cells. The cyclic occurrence of trace amounts of remnant Mn oxides verify that primary Mn accumulation took place under oxic bottom waters. The negative co-variation between Mn carbonates and organic matter on Raman profiles suggests that the former was formed during diagenesis via organic matter decomposition coupled with Mn oxide reduction. Combined with previous experimental simulations and natural observations, a two-step microbially mediated Mn metallogenic model is tentatively proposed for the studied Mn deposits: (1) Mn(II)-oxidizing bacteria effectively catalyzed the deposition of considerable Mn oxides under oxygenated bottom water columns, a process that was simultaneously sustained by oxygenic microbial mats such as cyanobacteria; (2) Buried Mn oxides were reduced by highly reactive organic matter sourced from dead biomats of Mn(II)-oxidizing bacteria and benthic phototrophs, a process mediated by Mn(IV)-reducing bacteria which not only promoted the reaction rate but also served as nucleation sites for Mn carbonate minerals. This model can also help to explain the occurrence of diverse authigenic accessory minerals (e.g., quartz, apatite, and talc) and remarkable enrichments of several specific elements (e.g., Co, Ce, and Mo) in the studied Mn ores, which were closely linked to the decomposed cells and extracellular polymeric substance (EPS). By comparing with previous microbial investigations on Mn deposits over geological history, we further highlight the fundamental role of microorganisms in regulating the formation of economic Mn carbonate deposits.

Monitoring natural organic matter in drinking water treatment with photoelectrochemical oxygen demand

AbstractConventional metrics such as total organic carbon (TOC) and ultraviolet absorbance at 254 nm (UV254) may oversee aspects of natural organic matter (NOM) reactivity in drinking water treatment. The novel photoelectrochemical oxygen demand (peCOD) analyzer indirectly measures the oxygen consumed during NOM oxidation with photo‐ and electrochemical methods, quantifying NOM reactivity. peCOD was valuable for tracking NOM degradation in nine drinking water treatment facilities, particularly in processes where conventional metrics failed to capture changes in NOM from partial oxidation (e.g., biofiltration and oxidation). However, peCOD exhibited moderate correlations with TOC (R2 = 0.67) and UV254 (R2 = 0.48), indicating the need for its concurrent use with conventional methods. While peCOD was not a significant predictor of disinfection by‐product formation potential (R2 < 0.20), its inclusion alongside standard NOM metrics improved the performance of multivariable regression models. Thus, peCOD provided a rapid, standardized, operator‐friendly, environmentally conscious, concentration‐based approach for evaluating NOM characteristics in drinking water samples.

Unraveling Environmental Forces Shaping Surface Sediment Geochemical “Isodrapes” in the East Asian Marginal Seas

AbstractAs major sites of carbon burial and remineralization, continental margins are key components of the global carbon cycle. However, heterogeneous sources of organic matter (OM) and depositional environments lead to complex spatial patterns in sedimentary organic carbon (OC) content and composition. To better constrain the processes that control OM cycling, we focus on the East Asian marginal seas as a model system, where we compiled extensive data on the OC content, bulk isotopic composition (δ13C and Δ14C), total nitrogen, and mineral surface area of surficial sediments from previous studies and new measurements. We developed a spatial machine learning modeling framework to predict the spatial distribution of these parameters and identify regions where sediments with similar geochemical signatures drape the seafloor (i.e., “isodrapes”). We demonstrate that both provenance (44%–77%) and hydrodynamic processes (22%–53%) govern the fate of OM in this margin. Hydrodynamic processes can either promote the degradation of OM in mobile mud‐belts or preserve it in stable mud‐deposits. The distinct isotopic composition of OC sources from marine productivity and individual rivers regulates the age and reactivity of OM deposited on the sea‐floor. The East Asian marginal seas can be separated into three main isodrapes: hydrodynamically energetic shelves with coarser‐grained sediment depleted in OC, OM‐enriched mud deposits, and a deep basin with fine‐grained sediments and aged OC affected by long oxygen exposure times and petrogenic input from rivers. This study confirms that both hydrodynamic processes and provenance should be accounted for to understand the fate of OC in continental margins.

Extracellular organic disulfide reduction by Shewanella oneidensis MR-1.

Microbial reduction of organic disulfides affects the macromolecular structure and chemical reactivity of natural organic matter. Currently, the enzymatic pathways that mediate disulfide bond reduction in soil and sedimentary organic matter are poorly understood. In this study, we examined the extracellular reduction of 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB) by Shewanella oneidensis strain MR-1. A transposon mutagenesis screen performed with S. oneidensis resulted in the isolation of a mutant that lost ~90% of its DTNB reduction activity. Genome sequencing of the mutant strain revealed that the transposon was inserted into the dsbD gene, which encodes for an oxidoreductase involved in cytochrome c maturation. Complementation of the mutant strain with the wild-type dsbD partially restored DTNB reduction activity. Because DsbD catalyzes a critical step in the assembly of multi-heme c-type cytochromes, we further investigated the role of extracellular electron transfer cytochromes in organic disulfide reduction. The results indicated that mutants lacking proteins in the Mtr system were severely impaired in their ability to reduce DTNB. These findings provide new insights into extracellular organic disulfide reduction and the enzymatic pathways of organic sulfur redox cycling.IMPORTANCEOrganic sulfur compounds in soils and sediments are held together by disulfide bonds. This study investigates how Shewanella oneidensis breaks apart extracellular organic sulfur compounds. The results show that an enzyme involved in the assembly of c-type cytochromes as well as proteins in the Mtr respiratory pathway is needed for S. oneidensis to transfer electrons from the cell surface to extracellular organic disulfides. These findings have important implications for understanding how organic sulfur decomposes in terrestrial ecosystems.

Hydrothermal activity fuels microbial sulfate reduction in deep and distal marine settings along the Arctic Mid Ocean Ridges

Microbial sulfate reduction is generally limited in the deep sea compared to shallower marine environments, but cold seeps and hydrothermal systems are considered an exception. Here, we report sulfate reduction rates and geochemical data from marine sediments and hydrothermal vent fields along the Arctic Mid Ocean Ridges (AMOR), to assess the significance of basalt-hosted hydrothermal activity on sulfate reduction in a distal deep marine setting. We find that cored marine sediments do not display evidence for sulfate reduction, apart from low rates in sediments from the Knipovich Ridge. This likely reflects the overall limited availability of reactive organic matter and low sedimentation rates along the AMOR, except for areas in the vicinity of Svalbard and Bear Island. In contrast, hydrothermal samples from the Seven Sisters, Jan Mayen and Loki’s Castle vent fields all demonstrate active microbial sulfate reduction. Rates increase from a few 10s to 100s of pmol SO42- cm-3 d-1 in active high-temperature hydrothermal chimneys, to 10s of nmol SO42- cm-3 d-1 in low-temperature barite chimneys and up to 110 nmol cm-3 d-1 in diffuse venting hydrothermal sediments in the Barite field at Loki’s Castle. Pore fluid and sediment geochemical data suggest that these high rates are sustained by organic compounds from microbial mats and vent fauna as well as methane supplied by high-temperature hydrothermal fluids. However, significant variation was observed between replicate hydrothermal samples and observation of high rates in seemingly inactive barite chimneys suggests that other electron donors may be important as well. Sediment sulfur isotope signatures concur with measured rates in the Barite field and indicate that microbial sulfate reduction has occurred in the hydrothermal sediments since the recent geological past. Our findings indicate that basalt-hosted vent fields provide sufficient electron donors to support microbial sulfate reduction in high- and low-temperature hydrothermal areas in settings that otherwise show very low sulfate reduction rates.

Predicting Methane Formation Rates of Freshwater Sediments in Different Biogeographic Regions

AbstractFreshwater lakes and reservoirs cover a small fraction of the Earth, however their emission of the greenhouse gas methane (CH4) from the sediment to the atmosphere is disproportionately high. Currently, there is still a limited understanding of the links between sediment characteristics and CH4 formation. Earlier studies have indicated that sediment age and nitrogen content are related to sediment CH4 formation rates, but it is uncertain such relationships are valid across gradients of sediment characteristics. We therefore measured potential CH4 formation rates in multiple layers of sediment sampled from nine lakes situated in the temperate, boreal and alpine biogeographic regions of Sweden, thus differing in productivity, catchment and climate properties. Potential CH4 formation varied over 3 orders of magnitude, and was broadly related to the quantity and reactivity of organic matter, and generally decreased with sediment depth. Sediment age and total nitrogen content were found to be the key controlling factors of potential CH4 formation rates, together explaining 62% of its variability. Moreover, the model developed from the Swedish lake sediment data was able to successfully predict the potential CH4 formation rates in reservoirs situated in different biogeographic regions of Brazil (R2 = 0.62). Therefore, potential CH4 formation rates in sediments of highly contrasting lakes and reservoirs, from Amazonia to alpine tundra, could be accurately predicted using one common model (RMSE = 1.6 in ln‐units). Our model provides a valuable tool to improve estimates of CH4 emission from lakes and reservoirs, and illustrates the fundamental regulation of microbial CH4 formation by organic matter characteristics.

Interpretable Machine Learning and Reactomics Assisted Isotopically Labeled FT-ICR-MS for Exploring the Reactivity and Transformation of Natural Organic Matter during Ultraviolet Photolysis.

Isotopically labeled FT-ICR-MS combined with multiple post-analyses, including interpretable machine learning (IML) and a paired mass distance (PMD) network, was employed to unravel the reactivity and transformation of natural organic matter (NOM) during ultraviolet (UV) irradiation. FT-ICR-MS analysis was used to assign formulas, which were classified on the basis of their molecular compositions and structural categories. Isotope (deuterium, D) labeling was utilized to unequivocally determine the photochemical products and examine the development of OD radical-mediated NOM transformation. With regard to the reactive molecular formulas, CHOS formulas exhibited the highest reactivity (86.5% of precursors disappeared) followed by CHON (53.4%) and CHO (24.6%) formulas. With regard to structural categories, the degree of reactivity decreased in the following order: tannins > condensed aromatics > lignin/CRAMs. The IML algorithm demonstrated that the crucial features governing the reactivity of formulas were the molecular weight, DBE-O, NOSC, and the presence of heteroatoms (i.e., N and S), suggesting that the large and unsaturated compounds containing S and N are more prone to photodegradation. The reactomics approach using the PMD network further indicated that 11 specific molecular formulas in the CHOS and CHO class served as hubs, implying a higher photoreactivity and participation in a range of transformations. The isotope labeling analyses also found that, among the reactions observed, hydroxylation (i.e., +OD) is dominant for lignin/CRAMs and condensed aromatics, and formulas containing ≤10 D atoms were developed. Overall, this study, by adopting rigorous and interpretable techniques, could provide in-depth insights into the molecular-level dynamics of NOM under UV irradiation.

Source, composition and molecular diversity of dissolved and particulate organic matter varied with riparian land use in tropical coastal headstreams

Source, composition and molecular diversity determine the reactivity and stabilization of organic matter (OM, dissolved [DOM]/particulate [POM]), affecting its behavior and fate. Here, multiple spectral and mass spectrometry techniques were applied to examine how riparian land-use shaped the source, composition and molecular diversity of POM and DOM (HDOM) in adjacent headstreams. Compared to HDOM with abundant lignins, microbially-transformed heteroatoms and carboxyl-rich alicyclic acids (CRAMs), POM exhibited higher allochthonous characteristics and more bioactive components, but lower molecular weight and diversity in different land-use-dominated streams. Compared to wetland-dominated headstreams, both POM and HDOM exhibited more terrestrial origin and condensed aromatics/tannins molecules for agriculture-impacted headstreams and bio-labile lipids, proteins and carbohydrates for forest-impacted headstreams. Structural equation mode (SEM) showed that soil-derived DOM (SDOM) showed the most prominent influence on the source, composition and molecular diversity of POM and the source of HDOM. The molecular composition and diversity of HDOM were mainly influenced by soil properties/SDOM and aquatic microorganisms, respectively. Redundancy analysis (RDA) revealed that autochthonous, bio-labile compositions of POM in forest and wetland streams were positively related to aquatic Bacteroidetes/Cyanobacteria, and carbohydrates/biogenic index of SDOM, while that of HDOM were positively linked with aquatic Bacteroidetes/Cyanobacteria, and SDOM molecular diversity. Terrestrial and aromatic POM in agricultural headstreams were associated with aquatic total nitrogen/Actinobacteria, and humification degree, aromatic/phenolic substances of SDOM, while that of HDOM were mainly regulated by aquatic nitrate/total nitrogen/Actinobacteria, and aromatic/carboxylic-containing moieties of SDOM. Noteworthily, the molecular diversity of agricultural OM increased along the soil-stream continuum due to the input of soil condensed aromatics and tannins. The opposite trend was observed in forest and wetland streams due to the input of bioactive carbohydrates and the microbial-degradation in-stream. These results are helpful to predict the behavior and fate of OM and determine effective management strategies in tropical coastal regions undergoing intense anthropogenic alterations.

Spatial Distribution and Factors Influencing the Various Forms of Iron in Alluvial–Lacustrine Clayey Aquitard

The compression release of pore water in clayey aquitards has a significant impact on groundwater quality. Iron is an active variable element that mediates biochemical reactions in groundwater systems, but its transformation mechanisms in clayey aquitards remain unclear. The sediment and pore water samples from the shallow clayey aquitard (thickness = ~20 m) in the Chen Lake area of China were collected in three boreholes. The spatial distribution and influencing factors of Fe occurrence in the aquitard were revealed using hierarchical extraction, statistical analysis, and simulation calculations. The results indicate that the background value of alluvial–lacustrine sediments primarily affects the Fe concentration of clayey sediments. The dissimilatory reduction in free Fe oxide was the main source of Fe ions in pore water, resulting in a major percentage of Fe2+ in the total Fe concentration (0.07−5.91 mg/L). The abundant organic matter in organic-rich clay promoted a dissimilatory reduction in Fe (III) oxides, while the Fe concentrations of sediment and pore water were lower in the sand-rich stratum because of its weak adsorption capacity. The impact of human reclamation activities on the aquitard was mainly concentrated in the shallow layer (>−3 m), resulting in water drainage and O2 and CO2 input, which induced the crystallization of poorly crystalline Fe oxides. The input of reactive organic matter from reclaimed crops promoted the dissimilatory reduction in Fe oxides and the enrichment of Fe in deep pore water. The copious Fe2+ in deep stratum pore water tended to interact with CO32− and S2− to form coprecipitation with Fe (II). The concentrations of As, Cr, Sr, Zn, and Mn in pore water followed a similar variation trend to the Fe ion concentration, and their release could be attributed to the reduction dissolution of sediment Fe (III) oxides.

The Effects of Water Column Dissolved Oxygen Concentrations on Lake Methane Emissions—Results From a Whole‐Lake Oxygenation Experiment

AbstractLakes contribute 9%–19% of global methane (CH4) emissions to the atmosphere. Dissolved molecular oxygen (DO) in lakes can inhibit the production of CH4 and promote CH4 oxidation. DO is therefore often considered an important regulator of CH4 emissions from lakes. Presence or absence of DO in the water above the sediments can affect CH4 production and emissions by (a) influencing if methane production can be fueled by the most reactive organic matter in the top sediment layer or rely on deeper and less degradable organic matter, and (b) enabling CH4 accumulation in deep waters and potentially large emissions upon water column turnover. However, the relative importance of these two DO effects on CH4 fluxes is still unclear. We assessed CH4 fluxes from two connected lake basins in northern boreal Sweden where one was experimentally oxygenated. Results showed no clear difference in summer CH4 emissions attributable to water column DO concentrations. Large amounts of CH4 accumulated in the anoxic hypolimnion of the reference basin but little of this may have been emitted because of incomplete mixing, and effective methane oxidation of stored CH4 reaching oxic water layers. Accordingly, ≤24% of the stored CH4 was likely emitted in the experimental lake. Overall, our results suggest that hypolimnetic DO and water column CH4 storage might have a smaller impact on CH4 emissions in boreal forest lakes than previous estimates, yet potential fluxes associated with water column turnover events remain a significant uncertainty in lake CH4 emission estimates.

THE INFLUENCE OF THE PRESENCE OF IRON IN HIGHLY ALKALINE POLYALUMINIUM CHLORIDES ON THE EFFECTIVENESS OF PRECURSORS OF DISINFECTION BY-PRODUCTS REMOVAL

The mechanism of coagulation with highly alkaline polyaluminum chlorides is well understood, but there is a lack of information on the effect of the presence of iron in these coagulants on the efficiency of purifying water with increased contents of natural organic matters among which humic substances are precursors of disinfection by-products. The dissolved forms of organic substances are the most problematic with regard to water treatment because major concern is the formation of disinfection by products resulting from reactions between dissolved organic matter fractions and disinfectants. The aim of this study was to evaluate the effectiveness of precursors of disinfection by-products removal using highly alkaline polyaluminium chlorides that had different alkalinity and iron content. In the water after the coagulation process a value of SUVA254 was calculated because this indicator correlates well with dissolved organic matter reactivity and disinfection by-products. The analysis of the obtained results showed that the effectiveness of dissolved organic matter removal was determined by the formation of colored iron-organic complexes.

Regional and Global Patterns of Apparent Organic Matter Reactivity in Marine Sediments

AbstractOrganic matter (OM) degradation in marine sediments is fundamental to understanding and constraining global biogeochemical cycling, whereby OM reactivity is at its core. Here, we use benthic diffusive oxygen uptake (DOU) rates as a proxy for OM reactivity. We apply an analytical diagenetic model to inversely determine OM reactivities in marine sediments (i.e., Reactive Continuum Model parameters a and ν) using data sets of global DOU, surface sediment OM contents, and seafloor boundary conditions. Simulated oxygen depth profiles show good agreement with observations, increasing confidence in our reactivity estimates. Inversely determined reactivities vary over orders of magnitude between individual sites ranging from high (k = 0.252 year−1) for sediments in the Polar region to extremely low (k = 7.96 ⋅ 10−5 year−1) in South Pacific. Our findings highlight the heterogeneity of OM reactivities, revealing regional patterns that broadly agree with observations and prior assessments. In general, high benthic reactivity can be linked to limited pelagic OM degradation favored by either a rapid vertical or lateral OM transport to the sediment or environmental factors, such as low oxygen concentrations or low temperature, slowing pelagic OM degradation. Finally, we develop a set of transfer functions that allow estimating OM reactivity as a function of DOU, OM content and water depths, and use one to derive the first global maps of benthic OM reactivity based on two global DOU maps. Despite the inherent observational biases in the data sets, our results provide a good first‐order estimate of the apparent benthic OM reactivity agreeing with our current mechanistic understanding and observations.

Dissolved fluxes of nutrients and carbon at the sediment-water interface in the Adriatic Sea: review of early data and methods from the Italian National Research Council (CNR)

We report the measurement of the Fluxes of Dissolved Compounds at the Sediment-Water Interface (DFSWIs), obtained by analyzing data collected in the Italian Exclusive Economic Zone (EEZ) of the Northern and Central Adriatic Sea from 1982. We also describe the methods, honed by Italy’s Consiglio Nazionale delle Ricerche (CNR), employed to measure and calculate DFSWIs, including benthic chambers and landers, sediment-water interface micro-profiling, on-board incubation, and pore water modeling. Data analysis demonstrated that in situ measurements are the most reliable approaches, but that on-board collected data also supply interesting results. The DFSWI data allowed to divide the Adriatic seafloor into areas with similar DFSWI types and intensities and to define the role of sediments as sources or sinks of chemicals such as nutrients, Dissolved Inorganic Carbon (DIC), and metals. DFSWIs mainly depend on dissolved and solid river inputs, Marine Organic Matter (mOM) production, and sediment reworking. They show a seasonal temperature-related trend, which in summer induces increased chemical reaction kinetics and microbial activity. DFSWIs decline from the Po River mouths southward, along the Holocene mud wedge. North of the Po River Delta, the DFSWIs are weaker and confined to the areas in front of the major river mouths, due to poor Organic Matter (OM) inputs and strong reworking of bottom sediments. The area south of the Po Delta cusp is characterized by strong DFSWIs, due to the high deposition of solid inputs from the Po River, strong primary production, and protection from the Western Adriatic Current and Bora storms; in summer, higher temperatures, and calm hydrodynamic conditions generate near-bottom hypoxic to anoxic environments in this area. In Northern and Central Adriatic offshore areas, negative DIC and phosphate fluxes are due to poorly reactive OM reaching this area and to the mainly carbonate composition and oxic environment of local bottom sediments. DFSWI data analysis highlighted the important contribution of sediments to marine carbon and nutrient cycles. This is particularly important for carbon, which plays a major role in seawater acidification and global climate change. The study also provides average DFSWI data for each diagenetic area, which allow calculating the carbon and nutrient budgets in the Adriatic Sea.

Assessing global-scale organic matter reactivity patterns in marine sediments using a lognormal reactive continuum model

Abstract. Organic matter (OM) degradation in marine sediments is largely controlled by its reactivity and profoundly affects the global carbon cycle. Yet, there is currently no general framework that can constrain OM reactivity on a global scale. In this study, we propose a reactive continuum model based on a lognormal distribution (l-RCM), where OM reactivity is fully described by parameters μ (the mean reactivity of the initial OM bulk mixture) and σ (the variance of OM components around the mean reactivity). We use the l-RCM to inversely determine μ and σ at 123 sites across the global ocean. The results show that the apparent OM reactivity (〈k〉=μ⋅exp⁡(σ2/2)) decreases with decreasing sedimentation rate (ω) and that OM reactivity is more than 3 orders of magnitude higher in shelf than in abyssal regions. Despite the general global trends, higher than expected OM reactivity is observed in certain ocean regions characterized by great water depth or pronounced oxygen minimum zones, such as the eastern–western coastal equatorial Pacific and the Arabian Sea, emphasizing the complex control of the depositional environment (e.g., OM flux, oxygen content in the water column) on benthic OM reactivity. Notably, the l-RCM can also highlight the variability in OM reactivity in these regions. Based on inverse modeling results in our dataset, we establish the significant statistical relationships between 〈k〉 and ω and further map the global OM reactivity distribution. The novelty of this study lies in its unifying view but also in contributing a new framework that allows predicting OM reactivity in data-poor areas based on readily available (or more easily obtainable) information. Such a framework is currently lacking and limits our abilities to constrain OM reactivity in global biogeochemical or Earth system models.

Codes and datasets for assessing global-scale organic matter reactivity patterns in marine sediments using a lognormal reactive continuum model

Codes and datasets for assessing global-scale organic matter reactivity patterns in marine sediments using a lognormal reactive continuum model

On the increasing competitiveness of UV/Cl to UV/H2O2 advanced oxidation as the organic carbon concentration increases

UV/Cl and UV/H2O2 are advanced oxidation processes (AOPs) used for drinking water treatment and water reuse. This work explored the hypothesis that UV/Cl becomes more competitive to UV/H2O2 at neutral-to-high pH as the concentration of total organic carbon (TOC) increases. Lab experiments and kinetic modelling were used to compare initial pseudo first-order contaminant decay rate coefficients between the AOPs at various pH and TOC conditions. The relative effect of increasing TOC concentrations on UV/Cl vs. UV/H2O2 depended on the pH, contaminant, and organic matter reactivity towards radicals. For example, while the reaction rate coefficients during both AOPs generally decreased with increasing TOC, the UV/Cl reaction rate coefficients for the solely •OH-reactive sucralose decreased 41–138% less than the UV/H2O2 coefficients as the TOC concentration was increased from 0 to 5 mg-C L−1. However, UV/Cl was more affected than UV/H2O2 when targeting caffeine (a contaminant reactive to chlorine radicals). The data were used to define TOC-pH conditions for which either AOP would be more energy-efficient, under a set of standard conditions. The results suggest that UV/Cl may be competitive to UV/H2O2 under a wider range of treatment scenarios than has been conventionally thought based on tests in pure water.

Risks of nutrients and metal(loid)s mobilization triggered by groundwater recharge containing reactive organic matter

The potential risk of multiple contaminants mobilization from sediment was evaluated under the infiltration of reactive organic matter (OM) during groundwater recharge. Significant NH4-N, PO43−, As, Fe, and Mn release were observed which show elevated peaks in the initial stage (0–19 d) and declines afterwards until reach quite low and stable content (20–37 d). When re-oxidize with SO42− (38–65 d), the reducing condition is stimulated to release more Fe and Mn however no As, NH4-N and PO43−. The microbial reductive Fe oxides dissolution is the main driving force for NH4-N, PO43−, As, Fe, and Mn release. The NH4-N and PO43− release was attributed by passive mobilization from Fe/Mn oxides due to its dissolution. The cation exchange also works significantly on NH4+ release while desorption works on PO43− as well. Microorganism responses to the infiltration reactive OM and further impacts the mobilization of multiple contaminants. The precipitation of secondary Fe/Mn minerals accompanied by co-precipitation and/or re-absorption lower down their aqueous levels. However, this aqueous contamination risk was hidden in solid reactive secondary minerals when oxidizer like SO42− perturbs the recurrence of Fe and Mn contamination occurs. This shows the perennial release of nutrients and trace elements should be paid attention in areas with reactive OM infiltration followed by redox/groundwater chemistry fluctuations, potentially in hyporheic zone of river/lake, managed aquifer recharge zone, etc.

Rapid Cycling of Bacterial Particulate Organic Matter in the Upper Layer of the Western Pacific Warm Pool

AbstractBacterial metabolism largely drives the sequestration of refractory organic matter in the ocean. However, a lack of understanding exists regarding the abundance and reactivity of bacterial particulate organic matter (POM). Here we report the bacterial contributions to suspended POM collected in the oligotrophic Western Pacific Warm Pool (WPWP). Around 27% of particulate organic carbon (POC) and ∼39% of particulate nitrogen (PN) in the surface ocean were derived from bacteria. Most of the bacterial POM (∼87%) was labile or semi‐labile, and ∼85% of bacterial POM was removed between depths of ∼100–300 m. Bacterial POM constituted only ∼8% and ∼13% of refractory POC and PN, respectively. The rapid cycling of bacterial POM in upper waters was likely related to oligotrophic conditions and facilitated by higher temperatures in the WPWP. Taken together, these observations indicate that bacterial POM plays a crucial role in supplying energy for bacterial respiration.