Oxidation Of Organic Carbon Research Articles

An insight into the sorption kinetics of boscalid onto soils: Effect of general soil properties

Boscalid is a carboxamide fungicide widely used for crop protection, however owing to its high persistence, it is detected in high concentrations in various environments. Since the fate of such xenobiotics is strongly influenced by its interaction with soil components a better understanding of its adsorption onto soils of varying properties could allow the adjustment of its application in a given agro-ecological region to limit the consequent environmental burden. The present investigation was carried out to examine the kinetics of boscalid adsorption onto ten Indian soils of varying physico-chemical properties. Kinetic data of boscalid for all soils under investigation fitted well to both pseudo-first-order and pseudo-second-order kinetic models. However, based on the standard error of estimate (S.E.est.) values pseudo-first-order model was better for all soil samples, except one soil which had the lowest readily oxidizable organic carbon. Adsorption of boscalid by soils appeared to be controlled by the diffusion-chemisorption process while for soils especially rich in readily oxidizable organic carbon or clay + silt content the intra-particle diffusion process seemed to be more important. Stepwise regression of kinetic parameters on soil properties revealed that the inclusion of a set of some soil properties could help better prediction of adsorbed amounts of boscalid and kinetic constants. These findings may help assess the fate and possible transport of boscalid fungicide in different soils.

Deep root activity overprints weathering of petrogenic organic carbon in shale

The oxidation of organic carbon in sedimentary bedrock (petrogenic OC, OCpetro) is increasingly recognized as a potential source of CO2 to the atmosphere. Recent studies provide evidence for the mobilization and oxidation of OCpetro in sedimentary bedrock during rock weathering. However, the mechanisms and rates remain uncertain, particularly where overlying soils and vegetation drive contemporaneous oxidation of recently fixed organic carbon. Here, we quantify OCpetro weathering across a 16 m shale depth profile in a steep, rapidly eroding forested hillslope in the Northern California Coast Ranges. We report solid and gas phase radiocarbon and stable isotope analyses of samples extracted from specialized in-situ samplers, and a supporting laboratory incubation experiment of the shale regolith. OCpetro is removed from the weathered bedrock at a rate of approximately 0.12 gC/m3yr, which is orders of magnitude lower than the rate of OCpetro oxidation we achieved in the laboratory with crushed samples (557.1 gC/m3/yr). This disparity occurs despite high O2(g) content across the depth profile, indicating that physical accessibility of OCpetro can regulate oxidative weathering. There is no direct radiocarbon evidence of OCpetro oxidation in CO2(g) across the upper 13 m of the weathering profile during both wet and dry seasons. Instead, vadose zone CO2(g) production at the site is dominated by respiration of recently fixed carbon associated with deep rooting. OCpetro is clearly mobilized across the vadose zone during weathering in this rapidly eroding, oxygen-rich, biologically dynamic hillslope, but at rates far below what can be measured given the contribution of root-derived CO2(g).

Low rates of rock organic carbon oxidation and anthropogenic cycling of rhenium in a slowly denuding landscape

AbstractThe oxidation of petrogenic organic carbon (OCpetro) is a source of carbon dioxide to the atmosphere over geological timescales. The rates of OCpetro oxidation in locations that experience low rates of denudation remain poorly constrained, despite these landscapes dominating Earth's continental surface area. Here, we track OCpetro oxidation using radiocarbon and the trace element rhenium (Re) in the deep weathering profiles, soils and stream waters of the Susquehanna Shale Hills Critical Zone Observatory (PA, USA). In a ridge‐top borehole, radiocarbon measurements reveal the presence of a broad OCpetro weathering front, with a first‐order assessment of ~40% loss occurring over ~6 m. However, the low OCpetro concentration (< 0.05 wt%) and inputs of radiocarbon throughout the deepest parts of the profile complicate the assessment of OCpetro loss. The OCpetro weathering front coincides with a zone of Re depletion (~90% loss), and we estimate that > 80% of Re in the rock is associated with OCpetro, based on Re/Na and Re/S ratios. Using estimates of long‐term denudation rates, the observed OCpetro loss and the Re proxy are equivalent to a low OCpetro oxidation yield of < 1.7 × 10−2 tC km−2 yr−1. This is consistent with the low OCpetro concentrations and low denudation rates at this location. In addition, we find the surface cycle of Re is decoupled from that of deep weathering, with an enrichment of Re in surface soils and elevated Re concentrations in stream water, precipitation, and shallow groundwater. A mass balance model shows that this can be explained by a historical anthropogenic contribution of Re through atmospheric deposition. We estimate that the topsoil Re pool could take decades to centuries to deplete and call for a renewed focus on anthropogenic perturbation of the surface Re cycle in low denudation rate settings.

Reactive iron, not fungal community, drives organic carbon oxidation potential in floodplain soils

Wetlands host ∼20% of terrestrial organic carbon and serve as a major sink for atmospheric carbon. Anoxic soils and sediments accrue soil organic carbon (SOC) partly by hampering the activity of extracellular oxidative enzymes that break down phenolic polymers. Upon aeration, fungal-driven oxidative enzymatic depolymerization and microbial respiration of released monomers ensue. Redox-active metals can simultaneously catalyze abiotic nonspecific oxidation of SOC, notable examples including Mn(III) or Fe(II) through Fenton-like, hydrogen peroxide-catalyzed oxidative radical production. However, the extent of reactive metal contributions to biotic and abiotic SOC degradation is not understood in the context of natural environments with diverse redox chemistry. We tested the relative contributions of fungi, Mn(III) and Fe(II) to phenolic substrate (L-DOPA) oxidation in floodplain soils representing a range of transient redox conditions driven by permanent vs. periodic flooding. Phenol oxidative potential was highest in permanently flooded soils with fewer fungal taxa known for observed (per)oxidase activity and instead correlated with HCl-extractable Fe(II), Fe(total) and Fe(II)/Fe(total), suggesting a specific role of Fe(II). Fe(II) additions enhanced phenol oxidative potential in sterilized and non-sterilized soils in the presence of hydrogen peroxide, indicating abiotic Fe-mediated radical chemistry could significantly enhance wetland SOC oxidative depolymerization throughout redox-active floodplain soils. Fungal community composition did not correlate to phenol oxidative potential overall and only more oxic soils adjacent to the river with diverse fungal communities showed declining oxidative potential after sterilization. Mn(III) addition did not significantly enhance phenol oxidative potential across all soils, although it appeared to drive fungal-mediated oxidative potential in the most aerated floodplain soils. Understanding how metals mediate SOC depolymerization as abiotic oxidants or microbially-harnessed enzyme cofactors and substrates in soils under variable hydrologic controls will improve our ability to represent depolymerization in terrestrial carbon models in wetland and other frequently saturated soils.

Assessment of potential mobility of selected micropollutants in agricultural soils of the Czech Republic using their sorption predicted from soil properties

The sorption of organic contaminants in soils and sediment is a crucial factor affecting their mobility in the vadose zone environment. The Freundlich sorption isotherms were evaluated for eleven micropollutants and eight soils. The highest Freundlich sorption coefficients, KF, were obtained for triclosan (324 ± 153 cm3/nμg1–1/ng−1) followed by sertraline (120 ± 74), venlafaxine (74.3 ± 41.2), telmisartan (33.3 ± 13.6), atorvastatin (8.66 ± 4.78), bisphenol S (8.03 ± 4.87), lamotrigine (6.92 ± 3.02), 2-phenylbenzimidazole-5-sulfonic acid (3.77 ± 2.25), memantine (3.42 ± 1.64), 1-methyl-1H-benzotriazole (2.05 ± 0.99), and valsartan (0.88 ± 0.89). The KF values for the individual compounds were correlated with soil properties. Multiple linear regressions were used to derive equations for predicting the KF values using the soil properties. The first set of equations contained mainly properties with the strongest correlations with the KF values, e.g., a base cation saturation for positively charged compounds or a hydrolytic acidity for negatively charged compounds. The second set of equations contained properties included in the map of agricultural soils of the Czech Republic. These equations always indicated positive correlations with oxidizable organic carbon and clay content. They also included either a negative or positive correlation with pHKCl. A positive correlation with pHKCl was obtained for venlafaxine, memantine, and sertraline, which were mostly positively charged. A negative correlation with pHKCl was obtained for the remaining compounds. The second set of equations, the soil map, and the database of soil properties were used to predict the KF value distributions within the Czech agricultural soils. It resulted in similar KF distributions' patterns for valsartan, lamotrigine, atorvastatin, and telmisartan (with a positive correlation between KF and hydrolytic acidity), which considerably differed from the KF patterns for the other compounds. These maps were used to delineate areas with a leaching potential of the compounds toward groundwater that will serve as a tool for assessing a potential groundwater vulnerability.

Increased Soil Aggregate Stability by Altering Contents and Chemical Composition of Organic Carbon Fractions via Seven Years of Manure Addition in Mollisols

Mollisols include an abundance of soil organic carbon (SOC) which is easily influenced by fertilization management. Manure addition could enhance soil aggregate stability; however, the dominating factor affecting its stabilization remains controversial. The fertilization practices were initiated in 2012 to investigate the influences of different fertilization managements on the contents and molecular characterization of organic carbon (OC) fractions, and to clarify the underlying mechanism of soil aggregate stability change. NoF (non-fertilizer), CF (only chemical fertilizer), CF + DM (chemical fertilizer plus single dairy manure at 15 t ha−1), and CF + 2DM (chemical fertilizer plus double dairy manure at 30 t ha−1) treatments were established. This research was aimed at exploring the potential mechanism that affects aggregate stability in Mollisols through the variation of contents and chemical composition of OC fractions, and screening out the appropriate fertilization practice on promoting SOC stabilization and crop yield under 7-year manure addition. Compared to CF, 7-year manure addition significantly enhanced SOC content by 17.4–35.9% at 0–10 cm depth, which was evidenced from the contribution of increased aromatic compounds with 4.3–19.9%. Simultaneously, compared with CF, CF + DM and CF + 2DM both significantly enhanced dissolved organic carbon and easily oxidizable organic carbon contents by 12.5–37.7% at a 0–30 cm soil layer. In regard to soil aggregates, the increased OC content and mass percentage of macroaggregates, and the decreased mass percentage of free microaggregates both improved aggregate stability under manure addition at 0-30 cm soil layer, which was proven to be the increment in mean weight diameter (MWD) and geometric mean diameter (GMD) values by 17.6–22.1%. Moreover, CF + DM and CF + 2DM raised aromatic compound amounts of POM fractions within macroaggregates [M(c)POM] by 5.6–11.6% and within free microaggregates (Fm-POM) by 4.3–10%. Furthermore, CF + DM and CF + 2DM both significantly increased maize yield by 5.7% and 4.2% compared to CF, but no significant difference was observed between CF + DM and CF + 2DM treatments. Collectively, physical protection through the occlusion within aggregates of POM might be the central mechanism for soil aggregate stability of manure addition in Mollisols. The manure addition of 15 t ha−1 was the effective management method to enhance SOC stabilization and crop yield in Mollisols.

Effects of C/Mn Ratios on the Sorption and Oxidative Degradation of Small Organic Molecules on Mn-Oxides

Manganese (Mn) oxides have a high surface area and redox potential that facilitate sorption and/or oxidation of organic carbon (OC), but their role in regulating soil C storage is relatively unexplored. Small OC compounds with distinct structures were reacted with Mn(III/IV)-oxides to investigate the effects of OC/Mn molar ratios on Mn-OC interaction mechanisms. Dissolved and solid-phase OC and Mn were measured to quantify the OC sorption to and/or the redox reaction with Mn-oxides. Mineral transformation was evaluated using X-ray diffraction and X-ray absorption spectroscopy. Higher OC/Mn ratios resulted in higher sorption and/or redox transformation; however, interaction mechanisms differed at low or high OC/Mn ratios for some OC. Citrate, pyruvate, ascorbate, and catechol induced Mn-oxide dissolution. The average oxidation state of Mn in the solid phase did not change during the reaction with citrate, suggesting ligand-promoted mineral dissolution, but decreased significantly during reactions with the other compounds, suggesting reductive dissolution mechanisms. Phthalate primarily sorbed on Mn-oxides with no detectable formation of redox products. Mn-OC interactions led primarily to C loss through OC oxidation into inorganic C, except phthalate, which was predominantly immobilized in the solid phase. Together, these results provided detailed fundamental insights into reactions happening at organo-mineral interfaces in soils.

New insights into the carbon cycle and depositional models of the Eocene saline lake, Jianghan basin, China

Geochemical characteristics and sedimentary processes of sediments, especially mixed sediments, have long been hot topics of research in basin systems, which can be used to infer runoff, evaporation, productivity, precipitation patterns of the paleoenvironment, as well as records of a diverse range of climate-related signs. However, compared with shallow marine mixed siliciclastic-carbonate sediments, the study of lacustrine mixed sedimentary systems in combination with geochemical information is relatively limited. Also, model-based study on the reconstruction of the lacustrine carbon biogeochemical cycle is defective, especially in saline lacustrine environments. In this work, a total of 26 mixed siliciclastic–carbonate sediment core samples from Well BX-7 in the Qianjiang Depression were sequentially selected for scanning electron microscope observation, major and minor element test, and isotope measurements (e.g., δ13Ccarb, δ18Ocarb, and δ34SCAS). Two types of mixed sediments were generated in the overall inflow/outflow balance of water within the saline basin during the Eocene: siliciclastic-dominated mixed sediment (SDMS) and carbonate-dominated mixed sediment (CDMS). The δ13Ccarb values of SDMS and CDMS samples range from −7.13‰ to −4.52‰ (average −5.82‰) and −9.00‰ to −6.11‰ (average −7.48‰), respectively. The δ18Ocarb values of SDMS and CDMS samples range from −10.26‰ to −1.40‰ (average −4.73‰) and −3.80‰ to −0.96‰ (average −1.55‰), respectively. In addition, combining the geochemical parameters of sedimentation rate, Mn2+ content in carbonate lattice ([Mncarb]), carbonate mass fraction, and [Mg2+]/[Ca2+] ratio, we established a lacustrine δ13C variation model at the sediment-water interface (SWI) with the aim of accurately reflecting δ13Ccarb changes during carbonate formation. Based on the sedimentary processes and geochemical characteristics, we established two depositional models for these two types of mixed sediments in a saline lacustrine basin in the overall inflow/outflow balance of water. Model I illustrates SDMS sedimentary processes with a relative low salinity, low FluxDIC-O, high water inflow, and the organic carbon oxidation is dominated by Fe (III) reduction. Model II demonstrates CDMS sedimentary processes with a high salinity, high FluxDIC-O, high water outflow, and the organic carbon oxidation is dominated by sulfate reduction.

Effects of Understory Vegetation Heterogeneity on Soil Organic Carbon Components in Cunninghamia lanceolata Plantation

As one of the important factors affecting forest soil organic carbon stocks, the effect of understory vegetation types on soil organic carbon and its components was explored to provide a theoretical basis for understory vegetation management and sustainable management in plantation forests. In order to determine the characteristics of soil organic carbon and its components under different understory vegetation types in Subtropical Cunninghamia lanceolata plantation, Indocalamus tessellatus, Diplazium donianum and Oreocnide frutescenssp were taken as research objects. The mass fractions of total organic carbon, recalcitrant organic carbon, readily oxidizable organic carbon, microbial biomass carbon and dissolved organic carbon in each soil layer at 0–10, 10–20, 20–40 and 40–60 cm were measured, and the change characteristics of soil organic carbon components were also studied and compared. The results showed that: (1) The mass fractions of total organic carbon, recalcitrant organic carbon, readily oxidizable organic carbon and microbial biomass carbon in the soils of the three understory vegetation types showed significant decreasing trends along the profile, while the mass fraction of dissolved organic carbon in 0–40 cm soil layer was significantly higher than those in 40–60 cm soil layer. (2) The mass fraction of total organic carbon (5.98–20.66 g·kg−1) had no significant difference among understory vegetation types. The mass fraction and proportion of microbial biomass carbon were higher in the 0–60 cm soil layer under cover of Indocalamus tessellatus, and the mass fractions of recalcitrant organic carbon in the 20–40 cm soil layer under Indocalamus tessellatus cover (8.57 g·kg−1) was significantly higher than that of Oreocnide frutescenssp (5.73 g·kg−1). The soil layer of 0–20 cm under the Diplazium donianum community has a higher mass fraction and proportion of readily oxidizable organic carbon. (3) Correlation analysis showed that soil organic carbon and its components were positively correlated with total nitrogen, dissolved total nitrogen, dissolved organic nitrogen and microbial biomass nitrogen. There is a significant positive correlation among the components of soil organic carbon. (4) Redundancy analysis showed that soil bulk density (41.6%), microbial biomass nitrogen (41.2%), dissolved total nitrogen (43.7%), total nitrogen (9.9%), dissolved organic nitrogen (43.6%) and pH (6.6%) were the most significant environmental factors affecting organic carbon components in four soil layers. Understory vegetation type can influence the distribution characteristics of soil organic carbon components in Cunninghamia lanceolata plantation, and soil active organic carbon components are more susceptible to the influence of understory vegetation type than total organic carbon and recalcitrant organic carbon.

Distribution pattern of mercury in northern Barents Sea and Eurasian Basin surface sediment.

Marine sediment is a significant sink for the global pollutant mercury. In a rapidly changing Arctic region, mercury (Hg) bioaccumulation in the marine ecosystem remains a prominent environmental issue. Here, we report surface sediment (0-2cm) concentrations of Hg and other toxic elements of interest (Cr, Ni, Zn, Cu, As, Cd, Pb) in the northern Barents Sea and Eurasian Basin. We observed average Hg concentrations of 65±23ng/g with the highest concentration of 116ng/g in the Eurasian Basin. Our calculated enrichment factors suggest low anthropogenic enrichment for mercury, chromium, nickel, and copper. Mercury and trace element geographic patterns are best explained by the origin and transportation of fine grain sediment towards the Eurasian Basin, with scavenging by both particulate organic carbon and metal oxides as significant delivery mechanisms.

Deglacial release of petrogenic and permafrost carbon from the Canadian Arctic impacting the carbon cycle

The changes in atmospheric pCO2 provide evidence for the release of large amounts of ancient carbon during the last deglaciation. However, the sources and mechanisms that contributed to this process remain unresolved. Here, we present evidence for substantial ancient terrestrial carbon remobilization in the Canadian Arctic following the Laurentide Ice Sheet retreat. Glacial-retreat-induced physical erosion of bedrock has mobilized petrogenic carbon, as revealed by sedimentary records of radiocarbon dates and thermal maturity of organic carbon from the Canadian Beaufort Sea. Additionally, coastal erosion during the meltwater pulses 1a and 1b has remobilized pre-aged carbon from permafrost. Assuming extensive petrogenic organic carbon oxidation during the glacial retreat, a model-based assessment suggests that the combined processes have contributed 12 ppm to the deglacial CO2 rise. Our findings suggest potentially positive climate feedback of ice-sheet retreat by accelerating terrestrial organic carbon remobilization and subsequent oxidation during the glacial-interglacial transition.

Distribution of Organic Carbon Fractions in Soil Aggregates and Their Contribution to Soil Aggregate Formation of Paddy Soils

ABSTRACT Different soil organic matter fractions play different roles in governing soil aggregation. Therefore, this study determined the distribution of labile organic carbon (OC) and stable OC fractions in soil aggregates and their contribution to the soil aggregation of paddy soils in the Central Plain of Thailand. Quantitative analysis of the OC fractions in soil aggregates was determined using wet oxidation method and their changes in the chemical composition of organic compounds were investigated using FTIR spectroscopy. The results showed that the large macroaggregate (LMA: 2–8 mm) content of studied soils generally increased with increasing soil organic carbon, clay, polyvalent cations and aluminum (Al) oxides contents. Generally, both the labile OC and stable OC fractions increased with increasing aggregate size classes, suggesting a hierarchical order of soil aggregation and physical protection of organic matter against microbial decomposition. The labile OC fraction in all aggregate size classes was positively correlated with the content of LMA (r = 0.54*–0.77**), suggesting that the labile OC fraction represented a major organic cementing agent that contributed to LMA formation. FTIR analysis revealed that the labile OC fraction mainly consisted of plant-derived and microbial-derived polysaccharides. Therefore, paddy soils with higher organic cementing agent (labile OC fraction) and inorganic cementing/flocculating agents may provide a stronger intimate association of these transient binding agents, particularly the microbial-derived polysaccharides with clay mineral surfaces and metal cations/Al oxides. In turn, the greater amounts of stabilized, microbial-derived polysaccharides also efficiently promoted the formation of LMA from a combination of microaggregates.

Origin of sodium bicarbonate groundwaters, Southern Hills Aquifer System, USA by silicate hydrolysis

Groundwaters dominated by sodium-bicarbonate represent an important end-member continental water type. The Southern Hills aquifer system in southwestern Mississippi and southeastern Louisiana, USA provides an excellent field laboratory for studying the origin and evolution of Na–HCO3 groundwaters in siliciclastic aquifers. Our research, which is based on establishing spatial variations in water chemistry, mass balance relations, and thermodynamic considerations, supports the hypothesis that the process of generating Na–HCO3 groundwaters in the Southern Hills aquifer system is driven by irreversible dissolution-precipitation reactions primarily involving silicate minerals, not by calcite dissolution and cation exchange, as has been proposed by others. The evidence supports the following scenario: oxidation of organic carbon produces organic acids which react with detrital plagioclase feldspars having an average bulk composition of approximately Ab0.70An0.30. In the up-gradient part of the system, the incongruent dissolution of plagioclase produces a kaolinite phase and releases dissolved silica, Na, Ca, and HCO3 into solution. As the silica concentration and the sodium/hydrogen ion activity ratio in the waters increase down gradient, the waters become saturated with respect to a (Na,Ca)-smectite. As plagioclase hydrolysis continues as a result of production of carbonic acid, there is a progressive increase in (Na+/H+) and (Ca2+/(H+)2) activity ratios and now a progressive decrease in dissolved H4SiO40 as a result of buffering by kaolinite-smectite. It is likely that some Ca is preferentially removed from solution over Na by adsorption on newly-formed smectite. In the most distal parts of the aquifer system the high bicarbonate alkalinity and high pH result in the waters becoming saturated with respect to calcite, and the precipitation of calcite is another probable sink for Ca. Using dissolved bicarbonate as a reaction progress variable provides a useful technique for evaluating controls on groundwater compositions. It is also clear that the evolution of groundwater compositions in this and similar systems cannot be understood without understanding the controls on dissolved silica.

Oxidation of petrogenic organic carbon in a large river-dominated estuary

Riverine export of petrogenic organic carbon (OCpetro) from continents to coastal oceans is a dynamic component of the global carbon budget and affects the long-term atmospheric carbon reservoir. In large fluvial systems, oxidation of OCpetro during transit releases a large flux of carbon dioxide to the atmosphere, influencing climate changes; however, the transport and fate of OCpetro and their controls along the fluvial–marine transition remain poorly constrained. Here, we combined Raman spectral, radiocarbon activity (F14C), mineralogical, and sedimentological techniques with multiple geochemical analyses to characterize the dynamics of OCpetro in the water column and sediment particles from the Yangtze River channel–estuary–shelf continuum systems.Our data show that much of the OCpetro present in suspended sediment (POCpetro) exported by the Yangtze River is “labile” fractions (mostly disordered materials) that can be degraded or lost during transport across the estuarine continuum, whereas the OCpetro deposited in seabed sediment are characterized by highly recalcitrant, unreactive, and graphitic carbon phases. As discrete “free” particles, coarse plant debris (>63 μm) with ages of several thousand years observed in the proximal delta of the Yangtze River exhibit nearly identical characteristics of disordered materials, and the presence of aged vascular plant detritus (carbon-rich and 14C-depleted materials) may lead to an overestimate of OCpetro in marine sediments. Using a Bayesian endmember mixing approach, a binary mixing model, and the ratio of fraction modern carbon (F14C) to Al/OC, we found a large decrease in POCpetro concentration and loading from the suspended sediments to seabed sediments, suggesting a loss of mineral-bound OCpetro fraction during sediment transport through the estuary and deposition on the shelf. We estimated that, on average, 46 ± 35 % of the POCpetro initially present in suspended sediments delivered to the Yangtze River Estuary during a flood event was primarily oxidized at the sediment–water interface, leaving the most graphitic carbon components transported laterally and efficiently reburied in shelf sediments. We found that during estuarine mixing, flocculation process-induced microaggregates may provide transient physical protection for POCpetro in the form of inclusions/aggregates with carbonate minerals; however, when POCpetro is physically and chemically separated from its mineral matrix via disaggregation and dissolution, it may be easily oxidized by microbial activity. In contrast, OC-phyllosilicates interactions exert a first-order control on the preservation of OCpetro in marine sediments. Our findings suggest that the importance of POCpetro oxidation and loss in carbon cycling and budget assessments of estuaries may be underestimated.

Geochemistry of the Neoarchean Dodguni carbonates of Chitradurga greenstone belt, Dharwar Craton, India: Implications on depositional environment

The carbonates of the Dodguni area of the Chitradurga greenstone belt, Dharwar Craton, India were studied to understand the Archean diagenetic and palaeo‐depositional conditions using carbon and oxygen isotopes along with whole‐rock geochemistry. These carbonates show significant variation in δ13C and δ18O (−1.73‰ Vienna Peedee Belemnite [VPDB] to −0.45‰ VPDB and δ18O vary from −13.51‰ VPDB to −8.46‰ VPDB, respectively). The rare earth element (REE) + Y (rare earth elements and yttrium) of the studied carbonate rocks exhibit flat and uniform patterns (PrSN/YbSN = 0.4–1), slight positive La, Eu and Gd anomalies (CeSN/CeSN* = 0.8–0.9; EuSN/EuSN* = 0.7–1.4 and GdSN/GdSN* = 2–2.3, respectively) with slight positive Ce anomalies (PrSN/PrSN* = 0.84–0.86) and superchondritic Y/Ho ratios (Y/Ho = 29–45; chondritic Y/Ho = 28). Their negative δ13C (−1.75‰ to −0.45‰) values are attributed to the influence of higher bio‐productivity during their deposition and oxidation of organic carbon. The geochemical and isotopic systematics suggest that the Dodguni limestones are not affected by the diagenetic and metamorphic processes and record the REE geochemistry of the ancient seawater in which they were precipitated. The comprehensive geochemical including the isotopic studies of the Archean carbonate rocks of the Dharwar Craton, indicate their deposition in shallow marine conditions, precipitation in high temperatures with significant hydrothermal input under the influence of high bio‐productivity, thereby providing valuable constraints on the palaeoceanography and geochemical evolution of the Archean sea.

Improvement of tensile strength and durability of mortar through bio cementation

Throughout the field of construction, intrinsic brittleness of the mortar that lead to cracking, especially after plastering, has been frequently observed, which makes it a common hurdle in most of the constructed structures, due to the significant loss of water tightness and durability. Cementous structures are subject to damage continuously by harassment conditions. Therefore, special biological systems can be exploited to overcome such problems. Many bacterial species have been employed to precipitate calcium carbonate through the oxidation of organic carbon, changing the properties of the construction material. The oxidation process would fill the pores between cement matrices, which shows significant decrease in the porosity, permeability and capillary water penetration. Deposition of calcium carbonate by bacteria is a phenomenon known as microbiologically induced calcite precipitation (MICP), biomineralization, or bio cementation, which considered as natural and eco-friendly process. Such deposition is a promising practice for integrating and protecting various building materials. The strength refinement is due to growth of filler material inside the pores of the cement matrix. In addition, a modification in pores’ size, distribution, and total volume are also noted, that could enhance durability properties. Due to the relative dryness and shortage of nutrients required for bacterial growth in concrete, those common bacteria unable to thrive. Some extremophiles spore forming species are able to survive in such hostile environment and boost the durability, compressive strength, and self-healing and repairing of micro-cracks in the cement concrete. Bacillus spizizenii 6633 was added to cement mortar, and found that the tensile strength was increased up to 12.6%, and the deterioration was decreased through the reduction of the microcracks by self-healing process.

Insight into Source and Evolution of Oxalic Acid: Characterization of Particulate Organic Diacids in a Mega-City, Shanghai from 2008 to 2020

Organic acids are important aerosol compositions with significant implications on particle formation, growth, acidity, phase state, and environmental impacts. Oxalic acid was found to be the most abundant particulate organic diacid in Shanghai during the study period, accounting for ~58% of the total dicarboxylic acids (C2–C10). Biomass burning (BB) explained a small but non-negligible fraction (less than 10%) of oxalate. Significant correlations between oxalate and sulfate indicated a potentially synergistic formation mechanism of oxalate and sulfate. In addition, meteorological factors such as ambient temperature and relative humidity were found to influence the formation of oxalate. Higher oxalate relative to inorganic particulate content was found in summer. Potential source contribution function analysis suggested that most of the oxalate observed in Shanghai was produced locally. The formation of oxalate was largely impacted by atmospheric oxidation capacity as indicated by its significant correlations with both secondary organic carbon (SOC) and sulfur oxidation ratio (SOR). The evolution of oxalate, oxalate/sulfate, oxalate/organic carbon were consistent with the emission trend of volatile organic carbons (VOCs) in recent years, indicating that oxalate may be derived from secondary oxidation of VOCs, which is further confirmed by a positive relationship between Ox and oxalate/VOCs over the study period. With a detailed characterization of oxalate in Shanghai, our study highlights the importance of regulating primary emissions, such as VOCs, as well as mitigation of atmospheric oxidation capacity in controlling air pollution in a coastal megacity.

Mixed application of biochar, maize straw, and nitrogen can improve organic carbon fractions and available nutrients of a sandy soil

Biochar with maize straw and nitrogen application may provide better crop growth conditions with respect to soil C/N, organic carbon fractions, and available nutrients than biochar applied alone. An incubation experiment was conducted in which biochar of maize straw pyrolyzed at 500 °C was applied with maize straw and nitrogen over 150 days. The treatments consisted of three rates of biochar applied at 0 (BC), 30 (BC3), and 60 g kg−1 (BC6), two rates (0 and 2 g kg−1) of maize straw (S), and two rates (0 and 0.1 g kg−1) of nitrogen (N) fertilizer (ammonium bicarbonate). The control (CK) was blank soil unfertilized with BC, N, and S. Sampling was done at 30, 60, and 150 days, respectively. The treatments of BC3 and BC6 significantly increased the content of soil total organic carbon by 840–1735%, oxidizable organic carbon (KMnO4–C) by 151–250%, dissolved organic carbon (DOC) by 221–976%, microbial biomass carbon (MBC) by 113–274%, available phosphorus (AP) by 969–4820%, and available potassium (AK) by 715–2413% in the sandy soil. Biochar reduced the ammonium nitrogen and nitrate nitrogen (NH4 +–N and NO3 −–N) contents, while it increased the carbon-nitrogen ratio (C/N) to 42. Nitrogen addition increased the contents of NH4 +–N by 395% and NO3 −–N by 661% compared with the CK after 30 days. Straw only affected the contents of DOC and MBC. The S + N treatment increased the content of MBC and available nitrogen compared with the CK. The contents of KMnO4–C, DOC, MBC, NH4 +–N, NO3 −–N, AP, and AK in the BC + N and BC + S treatments were higher than those in the BC treatments. The BC + N and BC + S treatments could decrease the high C/N that resulted from biochar alone. The contents of KMnO4–C, DOC, MBC, NH4 +–N, NO3 −–N, AP, and AK in the BC + S + N treatment were higher than those in the BC + S and BC + N treatments. Therefore, we recommend using BC6 + S + N to improve the organic carbon fractions and available nutrients in sandy soil. If straw is lacking in the field, BC6 + N is a suitable alternative.

Geochemical Characterization of Groundwater in the Confined and Unconfined Aquifers of the Northern Italy

Having an accurate and easily accessible geochemical database is crucial for a correct groundwater management. Here, for the first time in Italy, chemico-physical data of groundwater collected by different Environmental Protection Agencies during the 2018 were integrated into a single database to assess the geochemical status of a wide and complex aquifer system. Data were assembled, reformatted, corrected, homogenized, and then grouped according to the aquifer type (phreatic, semi-confined, and confined) and the sampling seasons. A total of 3671 validated samples were classified into hydrochemical facies; inorganic N compounds and trace elements were also evaluated. The water were classified mainly as Ca-HCO3 and Ca-Mg-HCO3 (90%); locally, Na-HCO3, Mg-HCO3, Ca-SO4, Na-Cl, and Ca-Cl types were detected. In the phreatic aquifers, NO3 contamination and high concentrations of Na+, K+, and NH4+ were found and linked to anthropogenic sources, such as agricultural and livestock activities. Along the Adriatic coast, Na-Cl water confirmed saltwater intrusion phenomena. Landward, evaporitic rocks dissolution, and the upconing of relict marine water explained high EC, Na+, K+, Cl−, and SO42− concentrations. The dissolution of Fe-Mn oxide-hydroxides coupled with organic carbon oxidation under reducing environment justified high NH4+, Fe, Mn, and As recorded in the semi-confined and confined aquifers.

Lignin and fungal abundance modify manganese effects on soil organic carbon persistence at the continental scale

Manganese (Mn) may play an outsized role in soil biogeochemical cycles relative to its abundance. The role of Mn-facilitated oxidation of biomacromolecules during litter decomposition is well-established, but the balance between Mn-promoted soil organic carbon (SOC) oxidation and long-term SOC protection in mineral soils is unknown, especially in subsoils. In this study, we used soils collected across the US National Ecological Observatory Network (NEON) to assess the distribution of Mn and relationships between Mn abundance and SOC concentration, potential mineralization, and persistence at a continental spatial scale. Total reducible Mn was not spatially correlated to site moisture (Spearman’s Rho = 0.24), highlighting that Mn abundance may influence SOC cycling independently from other moisture-driven soil chemical properties (e.g., reactive iron and aluminum). However, Mn effects on SOC cycling depended on depth, soil, or site-level properties. In particular, fungal:bacterial biomass ratio, proportion of SOC in the free light fraction, lignin abundance, and/or proportion of undegraded organic matter mediated the effect of Mn on SOC cycling metrics. For example, the effect of Mn on SOC concentration in subsoils shifted from positive (approximately +270 % relative to mean subsoil SOC) to negative (−125 %) with increasing fungal:bacterial ratio. We propose that convergence of high Mn, lignin-rich substrates, and fungal:bacterial ratio amplifies lignin mineralization in surface soils, but does not result in higher net SOC turnover due to fungal biomass stabilization. In contrast, we suggest that Mn abundance promotes smaller, but more persistent SOC stocks in subsoils by accelerating SOC transformation from particulate to microbial biomass pools.