Abiotic Reactions Research Articles

Coprecipitation mechanisms of Zn by birnessite formation and its mineralogy under neutral pH conditions

Birnessite (δ-Mn(IV)O2) is a great manganese (Mn) adsorbent for dissolved divalent metals. In this study, we investigated the coprecipitation mechanism of δ-MnO2 in the presence of Zn(II) and an oxidizing agent (sodium hypochlorite) under two neutral pH values (6.0 and 7.5). The mineralogical characteristics and Zn–Mn mixed products were compared with simple surface complexation by adsorption modeling and structural analysis. Batch coprecipitation experiments at different Zn/Mn molar ratios showed a Langmuir-type isotherm at pH 6.0, which was similar to the result of adsorption experiments at pH 6.0 and 7.5. X-ray diffraction and X-ray absorption fine structure analysis revealed triple-corner-sharing inner-sphere complexation on the vacant sites was the dominant Zn sorption mechanism on δ-MnO2 under these experimental conditions. A coprecipitation experiment at pH 6.0 produced some hetaerolite (ZnMn(III)2O4) and manganite (γ-Mn(III)OOH), but only at low Zn/Mn molar ratios (< 1). These secondary precipitates disappeared because of crystal dissolution at higher Zn/Mn molar ratios because they were thermodynamically unstable. Woodruffite (ZnMn(IV)3O7•2H2O) was produced in the coprecipitation experiment at pH 7.5 with a high Zn/Mn molar ratio of 5. This resulted in a Brunauer–Emmett–Teller (BET)-type sorption isotherm, in which formation was explained by transformation of the crystalline structure of δ-MnO2 to a tunnel structure. Our experiments demonstrate that abiotic coprecipitation reactions can induce Zn–Mn compound formation on the δ-MnO2 surface, and that the pH is an important controlling factor for the crystalline structures and thermodynamic stabilities.

Reactive Oxygen Species in Plants: From Source to Sink.

Reactive oxygen species (ROS, partial reduction or derivatives of free radicals) are highly reactive, dangerous and can cause oxidative cell death. In addition to their role as toxic by-products of aerobic metabolism, ROS play a role in the control and regulation of biological processes such as growth, the cell cycle, programmed cell death, hormone signaling, biotic and abiotic stress reactions and development. ROS always arise in plants as a by-product of several metabolic processes that are located in different cell compartments, or as a result of the inevitable escape of electrons to oxygen from the electron transport activities of chloroplasts, mitochondria and plasma membranes. These reactive species are formed in chloroplasts, mitochondria, plasma membranes, peroxisomes, apoplasts, the endoplasmic reticulum and cell walls. The action of many non-enzymatic and enzymatic antioxidants present in tissues is required for efficient scavenging of ROS generated during various environmental stressors. The current review provides an in-depth look at the fate of ROS in plants, a beneficial role in managing stress and other irregularities. The production sites are also explained with their negative effects. In addition, the biochemical properties and sources of ROS generation, capture systems, the influence of ROS on cell biochemistry and the crosstalk of ROS with other signaling molecules/pathways are discussed.

BioRT-Flux-PIHM v1.0: a biogeochemical reactive transport model at the watershed scale

Abstract. Watersheds are the fundamental Earth surface functioning units that connect the land to aquatic systems. Many watershed-scale models represent hydrological processes but not biogeochemical reactive transport processes. This has limited our capability to understand and predict solute export, water chemistry and quality, and Earth system response to changing climate and anthropogenic conditions. Here we present a recently developed BioRT-Flux-PIHM (BioRT hereafter) v1.0, a watershed-scale biogeochemical reactive transport model. The model augments the previously developed RT-Flux-PIHM that integrates land-surface interactions, surface hydrology, and abiotic geochemical reactions. It enables the simulation of (1) shallow and deep-water partitioning to represent surface runoff, shallow soil water, and deeper groundwater and of (2) biotic processes including plant uptake, soil respiration, and nutrient transformation. The reactive transport part of the code has been verified against the widely used reactive transport code CrunchTope. BioRT-Flux-PIHM v1.0 has recently been applied in multiple watersheds under diverse climate, vegetation, and geological conditions. This paper briefly introduces the governing equations and model structure with a focus on new aspects of the model. It also showcases one hydrology example that simulates shallow and deep-water interactions and two biogeochemical examples relevant to nitrate and dissolved organic carbon (DOC). These examples are illustrated in two simulation modes of complexity. One is the spatially lumped mode (i.e., two land cells connected by one river segment) that focuses on processes and average behavior of a watershed. Another is the spatially distributed mode (i.e., hundreds of cells) that includes details of topography, land cover, and soil properties. Whereas the spatially lumped mode represents averaged properties and processes and temporal variations, the spatially distributed mode can be used to understand the impacts of spatial structure and identify hot spots of biogeochemical reactions. The model can be used to mechanistically understand coupled hydrological and biogeochemical processes under gradients of climate, vegetation, geology, and land use conditions.

Tight benthic-pelagic coupling drives seasonal and interannual changes in iron‑sulfur cycling in Arctic fjord sediments (Kongsfjorden, Svalbard)

Glaciated fjords are dynamic systems dominated by seasonal events such as spring phytoplankton blooms and pulses of glacial sediment-bearing meltwater delivery. These fjords are also characterized by strong spatial gradients in environmental factors such as sedimentation rate and primary productivity from the glacier-influenced head to the marine-influenced mouth. Such seasonal variations and spatial gradients, combined with the ongoing influence of climate change, generate non-steady state conditions, which have a strong impact on the mineralization of organic carbon in the fjord sediments and the flux of nutrients from the seabed. In order to investigate the role of fjord seasonal events and variability on diagenetic cycling of iron (Fe) and sulfur (S), we sampled Kongsfjorden (Svalbard, 79°N) in the spring, mid-summer, and late summer. We investigated sediment structure and biogeochemistry, conducted laboratory experiments to determine reaction rates, and compared these findings to water column productivity and turbidity. We found that rapid sedimentation near the glacial input buried algal matter-rich layers that fueled sub-surface peaks in mineralization rates over multi-year timescales. Sulfate reduction rates were limited by organic carbon availability and competition with Fe-reducers, while Fe reduction was controlled by the availability of reactive Fe(III) oxides. Pore water Fe 2+ concentrations were influenced by sulfur cycling pathways and abiotic reactions such as carbonate precipitation and potentially reverse weathering. Seasonal changes in sedimentation and organic carbon supply caused lower sulfate reduction and sulfide production rates in spring, driving generally higher spring fluxes of Fe 2+ from the sediment. The results of this study reveal the potential for an increased benthic source of nutrients such as Fe with continued benthic remineralization over winter in Kongsfjorden. Interannual changes in primary productivity, which are likely to intensify with global warming, and shifts in glacial sediment delivery have immediate impacts on the benthic cycling of Fe and S in this tightly coupled system, with a long term trend likely toward decreased benthic Fe fluxes. With the glacial retreat and changes in productivity predicted due to climate change, glaciated fjords such as Kongsfjorden may become a less efficient carbon sink by burying less terrestrial and marine-sourced organic matter in the deep sediments. • Investigation of seasonal Fe-S-C cycling in Arctic fjord sediments and water column. • Results show benthic respiration and increased benthic Fe 2+ flux over winter. • Findings suggest that fjord sediments respond rapidly to water column changes. • With glacial retreat, fjords may produce less benthic Fe and sequester less carbon.

An open source computational workflow for the discovery of autocatalytic networks in abiotic reactions.

A central question in origins of life research is how non-entailed chemical processes, which simply dissipate chemical energy because they can do so due to immediate reaction kinetics and thermodynamics, enabled the origin of highly-entailed ones, in which concatenated kinetically and thermodynamically favorable processes enhanced some processes over others. Some degree of molecular complexity likely had to be supplied by environmental processes to produce entailed self-replicating processes. The origin of entailment, therefore, must connect to fundamental chemistry that builds molecular complexity. We present here an open-source chemoinformatic workflow to model abiological chemistry to discover such entailment. This pipeline automates generation of chemical reaction networks and their analysis to discover novel compounds and autocatalytic processes. We demonstrate this pipeline's capabilities against a well-studied model system by vetting it against experimental data. This workflow can enable rapid identification of products of complex chemistries and their underlying synthetic relationships to help identify autocatalysis, and potentially self-organization, in such systems. The algorithms used in this study are open-source and reconfigurable by other user-developed workflows.

Pyrogenic carbon-promoted haloacetic acid decarboxylation to trihalomethanes in drinking water

Drinking water disinfection by chlorination or chloramination can result in the formation of disinfection byproducts (DBPs) such as haloacetic acids (HAAs) and trihalomethanes (THMs). Pyrogenic carbonaceous matter (PCM), such as activated carbon (AC), is commonly used as an ostensibly inert adsorbent to remove HAAs from water. HAA degradation has been mainly attributed to biological factors. This study, for the first time, revealed that abiotic HAA degradation in the presence of PCM could be important under water treatment conditions. Specifically, we observed complete destruction of Br3AA, a model HAA, in the presence of powder AC at pH 7 within 30 min. To understand the role of PCM and the reaction mechanism, we performed a systematic study using a suite of HAAs and various PCM types. We found that PCM significantly accelerated the transformation of three HAAs (Br3AA, BrCl2AA, Br2ClAA) at pH 7. Product characterization indicated an approximately 1:1 HAA molar transformation into their respective THMs following a decarboxylation pathway with PCM. The Br3AA activation energy (Ea) was measured by kinetic experiments at 15–45 °C with and without a model PCM, wherein a significant decrease in Ea from 25.7 ± 3.2 to 13.6 ± 2.2 kcal•mol−1 was observed. We further demonstrated that oxygenated functional groups on PCM (e.g., -COOH) can accelerate HAA decarboxylation using synthesized polymers to resemble PCM. Density functional theory simulations were performed to determine the enthalpy of activation (ΔH‡) for Br3AA decarboxylation with H3O+ and formic acid (HCOOH). The presence of HCOOH significantly lowered the overall ΔH‡ value for Br3AA decarboxylation, supporting the hypothesis that -COOH catalyzes the C-C bond breaking in Br3AA. Overall, our study demonstrated the importance of a previously overlooked abiotic reaction pathway, where HAAs can be quickly converted to THMs with PCM under water treatment relevant conditions. These findings have substantial implications for DBP mitigation in water quality control, particularly for potable water reuse or pre-chlorinated water that allow direct contact between HAAs and AC during filtration as well as PAC fines traveling with finished water in water distribution systems. As such, the volatilization and relative low toxicity of volatile THMs may be considered as a detoxification process to mitigate adverse DBP effects in drinking water, thereby lowering potential health risks to consumers.

Resistance of perfluorooctanoic acid to degradation by the microbially driven Fenton reaction.

Per- and polyfluoroalkyl substances (PFAS) such as perfluorooctanoic acid (PFOA) have received recent heightened attention as emerging contaminants. Due to widespread application in household products and aqueousfilm-formingfoams, PFAS are globally distributed in the environment, and bioaccumulate in the blood and tissues of mammals including humans. The microbially driven Fenton reaction, a hybrid biotic/abiotic hydroxyl radical (HO•)-generating system, previously degraded a wide variety of persistant organic pollutants. In the present study, the microbially driven Fenton reaction was employed to attempt degradation of PFOA. Batch cultures of the facultatively anaerobic bacteria Shewanella oneidensis were amended with PFOA and Fe(III)-citrate. Under aerobic conditions, S. oneidensis reduced oxygen to hydrogen peroxide (H2O2), while under anaerobic conditions, S. oneidensis reduced Fe(III) to Fe(II). During aerobic-to-anaerobic transition periods, Fe(II) and H2O2 interacted chemically via the Fenton reaction to produce HO• radicals, which in turn interacted with PFOA. Batch reactors were cycled between aerobic and anaerobic phases for four cycles, residual PFOA was extracted via liquid-liquid extraction and analyzed by liquid chromatography combined with tandem mass spectrometry. Unlike degradation of other organic pollutants, PFOA concentrations remained unchanged, which indicated that PFOA was resistant to degradation by the microbially-driven Fenton reaction. Similar to abiotic (purely chemical) Fenton reaction systems, these results most likely reflect the inability of HO• radicals to oxidatively degrade PFOA.

Temperature dependence of nitrate-reducing Fe(II) oxidation by Acidovorax strain BoFeN1 - evaluating the role of enzymatic vs. abiotic Fe(II) oxidation by nitrite.

Fe(II) oxidation coupled to nitrate reduction is a widely observed metabolism. However, to what extent the observed Fe(II) oxidation is driven enzymatically or abiotically by metabolically produced nitrite remains puzzling. To distinguish between biotic and abiotic reactions, we cultivated the mixotrophic nitrate-reducing Fe(II)-oxidizing Acidovorax strain BoFeN1 over a wide range of temperatures and compared it to abiotic Fe(II) oxidation by nitrite at temperatures up to 60°C. The collected experimental data were subsequently analyzed through biogeochemical modeling. At 5°C, BoFeN1 cultures consumed acetate and reduced nitrate but did not significantly oxidize Fe(II). Abiotic Fe(II) oxidation by nitrite at different temperatures showed an Arrhenius-type behavior with an activation energy of 80±7kJ/mol.Above 40°C, the kinetics of Fe(II) oxidation were abiotically driven, whereas at 30°C, where BoFeN1 can actively metabolize, the model-based interpretation strongly suggested that an enzymatic pathway was responsible for a large fraction (ca. 62%) of the oxidation. This result was reproduced even when no additional carbon source was present. Our results show that at below 30°C, i.e. at temperatures representing most natural environments, biological Fe(II) oxidation was largely responsible for overall Fe(II) oxidation, while abiotic Fe(II) oxidation by nitrite played a less important role.

Degradation of sulfamethoxazole by the heterogeneous Fenton-like reaction between gallic acid and ferrihydrite

In soils, the Fenton-like reaction can be initiated when phenolic acids (PCs) existed simultaneously with iron oxides and dissolved O2, which would have great impact on transformation of organic pollutants. This study probed the mechanism of the Fenton-like reaction that occurs in a heterogeneous system containing ferrihydrite (Fh) and gallic acid (GA), and evaluated its performance in sulfamethoxazole (SMX) degradation. In the absence of dissolved O2, only reductive dissolution of Fh by GA occurred. It was further showed that Fh is capable of catalyzing the oxidation of GA by O2, in which the Fenton-like reaction was involved with the formation of reactive oxygen species (ROS) (semiquinone free radicals, superoxide, singlet oxygen, hydroxyl radical and H2O2) together with the adsorbed and aqueous Fe(II). At pH 4.0, this Fenton-like reaction could lead to SMX degradation at a rate of 38.2% and 65.6% when GA concentration were set at 0.1 and 0.2 mM, respectively. Elevating pH inhibited SMX degradation process. Citric acid had no effect on SMX degradation, while ascorbic acid showed a promotive effect. Moreover, HPLC-MS showed the presence of 12 intermediate products, and the proposed pathways for SMX degradation included cleavage, demethylation, oxidation and electrophilic substitution. This work could enhance our understanding on how the abiotic soil Fenton-like reaction controls the fate of SMX in soil environments.

Chemically Oscillating Reactions during the Diagenetic Formation of Ediacaran Siliceous and Carbonate Botryoids

Chemically oscillating reactions are abiotic reactions that produce characteristic, periodic patterns during the oxidation of carboxylic acids. They have been proposed to occur during the early diagenesis of sediments that contain organic matter and to partly explain the patterns of some enigmatic spheroids in malachite, phosphorite, jasper chert, and stromatolitic chert from the rock record. In this work, circularly concentric self-similar patterns are shown to form in new chemically oscillating reaction experiments with variable mixtures of carboxylic acids and colloidal silica. This is carried out to best simulate in vitro the diagenetic formation of botryoidal quartz and carbonate in two Ediacaran-age geological formations deposited after the Marinoan–Nantuo snowball Earth event in South China. Experiments performed with alkaline colloidal silica (pH of 12) show that this compound directly participates in pattern formation, whereas those with humic acid particles did not. These experiments are particularly noteworthy since they show that pattern formation is not inhibited by strong pH gradients, since the classical Belousov–Zhabotinsky reaction occurs in solution with a pH around 2. Our documentation of hundreds of classical Belousov–Zhabotinsky experiments yields a number of self-similar patterns akin to those in concretionary structures after the Marinoan–Nantuo snowball Earth event. Morphological, compositional, and size dimensional comparisons are thus established between patterns from these experiments and in botryoidal quartz and carbonate from the Doushantuo and Denying formations. Selected specimens exhibit circularly concentric layers and disseminations of organic matter in quartz and carbonate, which also occurs in association with sub-micron-size pyrite and sub-millimetre iron oxides within these patterns. X-ray absorption near edge structure (XANES) analyses of organic matter extracted from dolomite concretions in slightly younger, early Cambrian Niutitang Formation reveal the presence of carboxylic and N-bearing molecular functional groups. Such mineral assemblages, patterns, and compositions collectively suggest that diagenetic redox reactions take place during the abiotic decay of biomass, and that they involve Fe, sulphate, and organic matter, similarly to the pattern-forming experiments. It is concluded that chemically oscillating reactions are at least partly responsible for the formation of diagenetic siliceous spheroids and concretionary carbonate, which can relate to various other persistent problems in Earth and planetary sciences.

Soil nitrification response to dairy digestate and inorganic ammonium sources depends on soil pH and nitrifier abundances

AbstractTo reduce CH4 emissions, some dairy operations use manure as feedstock for anaerobic digesters, after which the nonvolatilized portion forms a digestate effluent with high NH4+ content that is used as fertilizer. When applied to soil, N fertilizers are subject to nitrification, where NH3–oxidizing archaea (AOA) and bacteria (AOB) oxidize NH3 to NO2–, NO2––oxidizing bacteria (NOB) oxidize NO2– to NO3−, and N oxides are produced from biotic and abiotic reactions. This study used soil microcosms to evaluate the properties of nitrification in response to the addition of N as digestate vs. NH4Cl in soils from the different climatic regions of the western Oregon coastal plain (CP) and eastern Oregon Columbia River basin (CRB). In each soil, properties of NH3 oxidation or N oxide accumulation did not differ when N was provided via digestate or NH4Cl over the normal temperature range; however, nitrification rates, communities, and products differed between soils. The average nitrification rate in CP soil was almost twofold higher than in CRB soil (P ≤ .001), despite no significant differences in AOB activity or AOB amoA copy numbers. With N addition, AOA activity also increased in CP soil, where AOA amoA copy numbers were fivefold higher than CRB soil (P &lt; .002). Accumulation of NO2– only in CRB soil was likely due to NOB inhibition by high NH3 concentrations (∼560 μM) present at the high pH of CRB soil (8.5). Overall, nitrification was dictated by differences in edaphic properties, temperature, and nitrifier communities more than N source.

Redox Heterogeneity Entangles Soil and Climate Interactions

Interactions between soils and climate impact wider environmental sustainability. Soil heterogeneity intricately regulates these interactions over short spatiotemporal scales and therefore needs to be more finely examined. This paper examines how redox heterogeneity at the level of minerals, microbial cells, organic matter, and the rhizosphere entangles biogeochemical cycles in soil with climate change. Redox heterogeneity is used to develop a conceptual framework that encompasses soil microsites (anaerobic and aerobic) and cryptic biogeochemical cycling, helping to explain poorly understood processes such as methanogenesis in oxygenated soils. This framework is further shown to disentangle global carbon (C) and nitrogen (N) pathways that include CO2, CH4, and N2O. Climate-driven redox perturbations are discussed using wetlands and tropical forests as model systems. Powerful analytical methods are proposed to be combined and used more extensively to study coupled abiotic and biotic reactions that are affected by redox heterogeneity. A core view is that emerging and future research will benefit substantially from developing multifaceted analyses of redox heterogeneity over short spatiotemporal scales in soil. Taking a leap in our understanding of soil and climate interactions and their evolving influence on environmental sustainability then depends on greater collaborative efforts to comprehensively investigate redox heterogeneity spanning the domain of microscopic soil interfaces.

Co-precipitation induces changes to iron and carbon chemistry and spatial distribution at the nanometer scale

Association of organic matter (OM) with mineral phases via co-precipitation is expected to be a widespread process in environments with high OM input and frequent mineral dissolution and re-precipitation. In contrast to surface area-limited adsorption processes, co-precipitation may allow for greater carbon (C) accumulation. However, the potential sub-micrometer scale structural and compositional differences that affect the bioavailability of co-precipitated C are largely unknown. In this study, we used a combination of high-resolution analytical electron microscopy and bulk spectroscopy to probe interactions between a mineral phase (ferrihydrite, nominally Fe2O3•0.5H2O) and organic soil-derived water-extractable OM (WEOM). In co-precipitated WEOM-Fe, nanometer-scale scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) revealed increased Fe(II) and less Fe aggregation relative to adsorbed WEOM-Fe. Spatially distinct lower- and higher-energy C regions were detected in both adsorbed and co-precipitated WEOM-Fe. In co-precipitates, lower-energy aromatic and/or substituted aromatic C was spatially associated with reduced Fe(II), but higher-energy oxidized C was enriched at the oxidized Fe(III) interface. Therefore, we show that co-precipitation does not constitute a non-specific physical encapsulation of C that only affects Fe chemistry and spatial distribution, but may cause a bi-directional set of reactions that lead to spatial separation and transformation of both Fe and C forms. In particular, we propose that abiotic redox reactions between Fe and C via substituted aromatic groups (e.g., hydroquinones) play a role in creating distinct co-precipitate composition, with potential implications for its mineralization.

Exporting Metal‐Carbene Chemistry to Live Mammalian Cells: Copper‐Catalyzed Intracellular Synthesis of Quinoxalines Enabled by N−H Carbene Insertions

AbstractImplementing catalytic organometallic transformations in living settings can offer unprecedented opportunities in chemical biology and medicine. Unfortunately, the number of biocompatible reactions so far discovered is very limited, and essentially restricted to uncaging processes. Here, we demonstrate the viability of performing metal carbene transfer reactions in live mammalian cells. In particular, we show that copper (II) catalysts can promote the intracellular annulation of alpha‐keto diazocarbenes with ortho‐amino arylamines, in a process that is initiated by an N‐H carbene insertion. The potential of this transformation is underscored by the in cellulo synthesis of a product that alters mitochondrial functions, and by demonstrating cell selective biological responses using targeted copper catalysts. Considering the wide reactivity spectrum of metal carbenes, this work opens the door to significantly expanding the repertoire of life‐compatible abiotic reactions.

How biochar works, and when it doesn't: A review of mechanisms controlling soil and plant responses to biochar

AbstractWe synthesized 20 years of research to explain the interrelated processes that determine soil and plant responses to biochar. The properties of biochar and its effects within agricultural ecosystems largely depend on feedstock and pyrolysis conditions. We describe three stages of reactions of biochar in soil: dissolution (1–3 weeks); reactive surface development (1–6 months); and aging (beyond 6 months). As biochar ages, it is incorporated into soil aggregates, protecting the biochar carbon and promoting the stabilization of rhizodeposits and microbial products. Biochar carbon persists in soil for hundreds to thousands of years. By increasing pH, porosity, and water availability, biochars can create favorable conditions for root development and microbial functions. Biochars can catalyze biotic and abiotic reactions, particularly in the rhizosphere, that increase nutrient supply and uptake by plants, reduce phytotoxins, stimulate plant development, and increase resilience to disease and environmental stressors. Meta‐analyses found that, on average, biochars increase P availability by a factor of 4.6; decrease plant tissue concentration of heavy metals by 17%–39%; build soil organic carbon through negative priming by 3.8% (range −21% to +20%); and reduce non‐CO2 greenhouse gas emissions from soil by 12%–50%. Meta‐analyses show average crop yield increases of 10%–42% with biochar addition, with greatest increases in low‐nutrient P‐sorbing acidic soils (common in the tropics), and in sandy soils in drylands due to increase in nutrient retention and water holding capacity. Studies report a wide range of plant responses to biochars due to the diversity of biochars and contexts in which biochars have been applied. Crop yields increase strongly if site‐specific soil constraints and nutrient and water limitations are mitigated by appropriate biochar formulations. Biochars can be tailored to address site constraints through feedstock selection, by modifying pyrolysis conditions, through pre‐ or post‐production treatments, or co‐application with organic or mineral fertilizers. We demonstrate how, when used wisely, biochar mitigates climate change and supports food security and the circular economy.

Exporting Metal-Carbene Chemistry to Live Mammalian Cells: Copper-Catalyzed Intracellular Synthesis of Quinoxalines Enabled by N-H Carbene Insertions.

Implementing catalytic organometallic transformations in living settings can offer unprecedented opportunities in chemical biology and medicine. Unfortunately, the number of biocompatible reactions so far discovered is very limited, and essentially restricted to uncaging processes. Here, we demonstrate the viability of performing metal carbene transfer reactions in live mammalian cells. In particular, we show that copper (II) catalysts can promote the intracellular annulation of alpha‐keto diazocarbenes with ortho‐amino arylamines, in a process that is initiated by an N‐H carbene insertion. The potential of this transformation is underscored by the in cellulo synthesis of a product that alters mitochondrial functions, and by demonstrating cell selective biological responses using targeted copper catalysts. Considering the wide reactivity spectrum of metal carbenes, this work opens the door to significantly expanding the repertoire of life‐compatible abiotic reactions.

Long-term seasonal and temporal changes of hydrogen peroxide from cyanobacterial blooms in fresh waters

In water, hydrogen peroxide (H2O2) is produced through abiotic and biotic reactions with organic matter, including algal cells. The production of H2O2 is influenced by harmful algal cell communities and toxicity. However, only a few studies have been conducted on H2O2 concentrations in natural water. Particularly, the seasonal and temporal patterns of H2O2 concentration suggest that H2O2 generation from aquatic microorganisms could be identified to compare of photochemical production from dissolved organic matter. Study area is a source of raw water and is a large artificial lake located near a metropolitan city. Due to various environmental conditions, harmful algal blooms frequently occur in summer. The purpose of this study was to trace the H2O2 concentration and water quality parameters of study area where algal bloom occurs and what factors directly affect the H2O2 concentration. Experiments were performed on the influencing factors via water samples from study area and lab-scale culture tank. The lake produces an average of 553 nM H2O2, which increases by more than three times (1460 nM) in summer compared the winter. The lake (18.6–23.8 nMh−1) produced more H2O2 than streams (7.4–9.0 nMh−1) during daylight hours. All water sites presented the lowest production rates in dark conditions (1.1–1.5 nMh−1). Daytime environment increased the generation rate more than the nighttime. The trend of H2O2 produced by algal cells was similar to that of the growth of algal cells. The exposure to external substances (heavy metals and antibiotics) increased the incidence by approximately five times; antibiotics were more influential than heavy metals.

Oxygen isotope exchange rates between phosphate and water catalyzed by inorganic pyrophosphatase: Implications for the biogeochemical cycle of phosphorus

The oxygen isotope composition of phosphate (δ18OPO4) has been widely used as (paleo)temperature and bio-signature proxies and a tracer of biogeochemical cycling of phosphorus (P). In natural aqueous systems, reactive inorganic phosphorus is dominantly present as dissolved inorganic phosphate (DIP), and reactions involving DIP are primarily carried out by microorganisms and catalyzed by enzymes. One enzyme suggested to dominate P-cycling in nature is inorganic pyrophosphatase (PPase), a ubiquitous intracellular enzyme that catalyzes oxygen (O) isotope exchange between DIP and water. Herein, we determined PPase-catalyzed O-isotope exchange rates between DIP and water over the range of typical Earth surface temperatures (3 - 37°C) using isotope ratio mass spectrometry (IRMS). Exchange rates determined at pH 7.4 and between 3 and 37°C, were described by first-order reaction kinetics (rate constant k = 1.51E-05 to 3.13E-04 sec−1; half-life of reaction t1/2 = 37 to 765 minutes), and strongly dependent on temperature. The temperature dependence of the exchange reaction was fitted by the Arrhenius equation, with an activation energy of 61.8 kJ/mole. The rate of PPase-catalyzed O-isotope exchange is ca. 7 - 8 orders of magnitude faster than the rate of abiotic reactions (pH 5) at 37°C calculated by the extrapolation of high-temperature rate data. The results of this study can be used to improve the interpretation of measured δ18O values of phosphate preserved in the rock record or during biogeochemical reactions (e.g., deconvolution of simultaneous abiotic and enzymatic/microbial processes).

Enhanced abiotic integrated polyphenol-Maillard humification by Mg/Fe layered double hydroxide (LDH): Role of Fe(III)-polyphenol complexation

Abiotic humification can be facilitated by iron-containing minerals or oxides, but most studies have focused on well-crystallized and stable iron phases, the catalytic effect of which is generally unremarkable. In the present study, we report an enhanced abiotic integrated polyphenol-Maillard humification reaction catalysed by Mg/Fe-layered double hydroxide (Mg/Fe-LDH) with high surface reactivity. The results demonstrated that Mg/Fe-LDH could effectively promote the humification reaction at a lower dosage compared with Fe2O3. As an iron-chelating ligand, catechol rapidly induced iron dissolution from Mg/Fe-LDH through the formation of an Fe(III)-catechol complex, which strengthened the catalytic effect of Fe(III). The photochemical behaviour of Fe(III)-catechol complex and its impact on the Fe(III)-catalysed humification process were investigated. Under light irradiation, environmentally persistent free radicals (EPFRs) originated from the Fe(III)-catechol complex were formed and stabilized in the presence of Mg/Fe-LDH particles, which inhibited the oxidation of catechol and the humification process. Hence, the formation of humic substances (HS) catalysed by Mg/Fe-LDH was more efficient under darkness. Iron redox cycling and generation of reactive oxygen species (ROS), HO• and O2•-, were also involved. According to transformation products (TPs) analysis, ortho-aminophenol was proposed to be a key product in the humification reaction. Self-coupling of catechol radical and ortho-aminophenol radical, ring cleavage were likely to occur in the Fe(III)-catalysed humification process. Higher relative abundance of CHO products was observed in the presence of Mg/Fe-LDH by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), suggesting that iron is effective on promoting C–C bonds formation. The above results provide more comprehensive insights into Fe(III)-catalysed humification and a guidance to improve the efficiency of HS formation and carbon sequestration in organic wastes utilization.

Lignin-enhanced reduction of structural Fe(III) in nontronite: Dual roles of lignin as electron shuttle and donor

Lignin is a major component of plant-derived soil organic matter (SOM) in soils and sediments. Fe-bearing clay minerals are widely distributed in these environments and often co-exist with lignin. While previous studies have reported the electron shuttling and donating roles of certain redox-active SOM in the dissimilatory reduction of structural Fe(III) in Fe-bearing clay minerals, the role of lignin in this process remains unknown. Here we studied this role by incubating an Fe-rich smectite (nontronite NAu-2) with two types of lignin (soluble and insoluble) in the absence and presence of an Fe(III)-reducing bacterium Shewanella putrefaciens CN32 under anaerobic condition. Lactate was added in some experiments as an extra electron donor. The results demonstrated that both soluble and insoluble lignins abiotically reduced structural Fe(III) in NAu-2. The reduction extent was proportional to lignin concentration. After abiotic reaction, lignin served as either electron shuttle or electron donor in the presence of CN32: (1) When lactate was present, lignin served as an electron shuttle to enhance the rate of Fe(III) reduction; (2) When lactate was absent, lignin served as an electron donor for Fe(III) reduction. Although the ultimate biotic Fe(III) reduction extents were similar in the presence of either soluble or insoluble lignin, the reduction rates with soluble lignin were higher than those with insoluble lignin, likely owing to their different electron transfer mechanisms. After interaction with NAu-2 and/or CN32, soluble lignin structure largely remained intact, but with some decreases of humic/fulvic acid-like and protein-like compounds, aromatic functional groups (e.g., CH, CO, COOH), and aliphatic/aromatic compounds. An increase of semiquinone-like organic radicals was observed after lignin interaction with NAu-2. These chemical changes of lignin were likely coupled with the reduction of structural Fe(III) in nontronite. Upon reduction, the nontronite did not display much dissolution and mineral transformation. The findings of this study provide insights into the role of lignin in promoting mineral-microbe interactions and have significant implications for coupled Fe and C biogeochemical cycles in soils and sediments.