Oxic Conditions Research Articles

Influence of Iron Substitution and Solution Composition on Brucite Carbonation.

Carbon neutral or negative mining can potentially be achieved by integrating carbon mineralization processes into the mine design, operations, and closure plans. Brucite [Mg(OH)2] is a highly reactive mineral present in some ultramafic mine tailings with the potential to be rapidly carbonated and can contain significant amounts of ferrous iron [Fe(II)] substituted for Mg; however, the influence of this substitution on carbon mineralization reaction products and efficiency has not been thoroughly constrained. To better assess the efficiency of carbon storage in brucite-bearing tailings, we performed carbonation experiments using synthetic Fe(II)-substituted brucite (0, 6, 23, and 44 mol % Fe) slurries in oxic and anoxic conditions with 10% CO2. Additionally, the carbonation process was evaluated using different background electrolytes (NaCl, Na2SO4, and Na4SiO4). Our results indicate that carbonation efficiency decreases with increasing Fe(II) substitution. In oxic conditions, precipitation of ferrihydrite [Fe10IIIO14(OH)2] and layered double hydroxides {e.g., pyroaurite [Mg6Fe2III(OH)16CO3·4H2O]} limited carbonation efficiency. Carbonation in anoxic environments led to the formation of Fe(II)-substituted nesquehonite (MgCO3·3H2O) and dypingite [Mg5(CO3)4(OH)2·∼5H2O], as well as chukanovite [Fe2IICO3(OH)2] in the case of 23 and 44 mol % Fe(II)-brucite carbonation. Carbonation efficiencies were consistent between chloride- and sulfate-rich solutions but declined in the presence of dissolved Si due to the formation of amorphous SiO2·nH2O and Fe-Mg silicates. Overall, our results indicate that carbonation efficiency and the long-term fate of stored CO2 may depend on the amount of substituted Fe(II) in both feedstock minerals and carbonate products.

Immobilization of hexavalent uranium U(VI) by hydroxyapatite under oxic conditions

The immobilization of hexavalent uranium U(VI) by hydroxyapatite (HAP) was investigated under oxic conditions as a function of pH and surface loading ([U(VI)]0/[HAP]0) to evaluate the applicability of HAP as migration barriers or waste forms in nuclear waste repositories. This study focused on the retention mechanisms, which were sought by integrating the solid-phase characterization (e.g., X-ray diffraction, scanning electron microscopy with energy dispersive spectroscopy, and U LIII-edge X-ray absorption spectroscopy) with the solution-phase analysis of dissolved Ca, P, and U. At acidic pH, due to the increasing solubility of HAP, U(VI) retention is mainly controlled by the formation of a uranyl phosphate following HAP dissolution. Importantly, this phosphate is in the form of a solid solution with Na meta-autunite being the principal component, which considerably expands the stable domain of uranyl phosphates compared to the pure phases (e.g., chernikovite, Na meta-autunite, and meta-autunite). At neutral to basic pH, however, the uranyl phosphate formation does not prevail till [U(VI)]0/[HAP]0 = 25 mg/g, below which the formation of U(VI)-phosphate ternary surface complexes mainly accounts for U(VI) retention. At basic pH, the surface substitution of PO43− for CO32− and the dominance of uranyl carbonate species make surface complexation less favorable under this pH condition. In this study, the initially present U(VI) is near completely immobilized (> 99.99%) by HAP, with the greatest retention noted at circumneutral pH, thus demonstrating the effectiveness of HAP for the containment of U(VI) under ambient geochemical conditions.

Transformation of Precursor Iron(III) Minerals in Diagenetic Fluids: Potential Origin of Gray Hematite at Vera Rubin Ridge

AbstractCoarse‐grained (>3–5 μm) gray hematite particles occur at Vera Rubin ridge (VRR) within Gale crater, Mars. VRR has likely undergone multiple episodes of diagenesis, at least one of which resulted in the formation of gray hematite. The precursor mineralogy and nature of the diagenetic fluids that produced coarse‐grained hematite remain unknown. Analog laboratory experiments were performed on a variety of iron(III) minerals to assess the potential fluid conditions and precursor mineralogy that form coarse‐grained hematite. Gray hematite formed from the transformation of jarosite after 20 days at 200°C. Conversion was complete in chloride‐rich fluids; however, modeling indicates that at lower jarosite‐to‐water ratios, conversion is complete even in chloride‐free, sulfate‐rich conditions. No transformations of jarosite occurred when aged at 98°C. All other precursor minerals (akaganeite, ferrihydrite, goethite, and schwertmannite) did not transform or produced red, fine‐grained hematite under all conditions assessed. Additionally, seeding precursor iron(III) phases with red hematite and coarsening pre‐existing red hematite failed to produce gray hematite. These results suggest that jarosite could have been the precursor of gray hematite at VRR and that transformation is possible in both sulfate‐bearing and chloride‐bearing fluids. Jarosite produces gray hematite because the acidic conditions it generates yield both a low degree of hematite supersaturation, producing few nuclei, and high dissolved iron concentrations, enabling rapid hematite growth. Gray hematite readily forms under oxic conditions and its occurrence at VRR is not a marker for a redox interface. The associated diagenetic event was thus unlikely to have generated substantial new chemical energy for life.

Mobilization of heavy metals from floodplain sediments of the Yellow River during redox fluctuations

The floodplain of the Yellow River is a typical area characterized by redox fluctuations and heavy metal pollution. However, the mobilization behavior of heavy metals in floodplain sediments during redox fluctuations remains poorly understood. In this study, reductive mobilization of Fe and Mn was observed under reducing environments through reduction and dissolution, leading to the subsequent release of adsorbed As. In contrast, the mobilization of U occurred under oxic conditions, as the oxidative state of U(VI) has higher solubility. Furthermore, insignificant effects on the mobilization of Cd, Cu, Pb, and Hg were noticed during redox fluctuations, indicating higher stability of these heavy metals. Additionally, we demonstrated that carbon sources can play a key role in the mobilization of heavy metals in floodplain sediments, amplifying the reductive mobilization of Fe, Mn, As and the oxidative mobilization of U. Our findings contribute to the understanding of the biogeochemical cycling of heavy metal in floodplain sediments of the Yellow River and the factors that control this cycling.

Biostimulation of sulfate reduction for in-situ metal(loid) precipitation at an industrial site in Flanders, Belgium

A 30-month pilot study was conducted to evaluate the potential of in-situ metal(loid) removal through biostimulation of sulfate-reducing processes. The study took place at an industrial site in Flanders, Belgium, known for metal(loid) contamination in soil and groundwater. Biostimulation involved two incorporations of an organic substrate (emulsified vegetable oil) as electron donor and potassium bicarbonate to raise the pH of the groundwater by 1–1.5 units. The study focused on the most impacted permeable fine sand aquifer (8–9 m below groundwater level) confined by layers of non-permeable clay. The fine sands exhibited initially oxic conditions (50–200 mV), an acidic pH of 4.5 and sulfate concentrations ranging from 600 to 800 mg/L. At the central monitoring well, anoxic conditions (−200 to −400 mV) and a pH of 5.9 established shortly after the second substrate and reagent injection. Over the course of 12 months, there was a significant decrease in the concentration of arsenic (from 2500 to 12 μg/L), nickel (from 360 to <2 μg/L), zinc (from 78,000 to <2 μg/L), and sulfate (from 930 to 450 mg/L). Low levels of metal(loid)s were still present after 34 months (end of study). Mineralogical analysis indicated that the precipitates formed were amorphous in nature. Evidence for biologically driven metal(loid) precipitation was provided by compound specific stable isotope analysis of sulfate. In addition, changes in microbial populations were assessed using next-generation sequencing, revealing stimulation of native sulfate-reducing bacteria. These results highlight the potential of biostimulation for long-term in situ metal(loid) plume treatment/containment.

Uncovering the role of oxygen on organic carbon cycling: insights from a continuous culture study with a facultative anaerobic bacterioplankton species (Shewanella baltica)

Deoxygenation is tied to organic carbon (Corg) supply and utilization in marine systems. Under oxygen-depletion, bacteria maintain Corg respiration using alternative electron acceptors such as nitrate. Since anaerobic respiration’s energy yield is lower, Corg remineralization may be reduced and its residence time increased. We investigated the influence of oxygen and alternative electron acceptors’ availability on Corg cycling by heterotrophic bacteria during a continuous culture experiment with Shewanella baltica, a facultative anaerobic γ-Proteobacteria in the Baltic Sea. We tested six different oxygen levels, from suboxic (&amp;lt;5 µmol L-1) to fully oxic conditions, using a brackish (salinity=14 g L-1) media supplied with high (HighN) or low (LowN) inorganic nitrogen concentrations relative to glucose as labile Corg source. Our results show that suboxia limited DOC (glucose) uptake and cell growth only under LowN, while higher availability of alternative electron acceptors seemingly compensated oxygen limitation under HighN. N-loss was observed under suboxia in both nitrogen treatments. Under HighN, N-loss was highest and a C:N loss ratio of ~2.0 indicated that Corg was remineralized via denitrification. Under LowN, the C:N loss ratio under suboxia was higher (~5.5), suggesting the dominance of other anaerobic respiration pathways, such as dissimilatory nitrate reduction to ammonium (DNRA). Bacterial growth efficiency was independent of oxygen concentration but higher under LowN (34 ± 3.0%) than HighN (26 ± 1.6%). Oxygen concentration also affected dissolved organic matter (DOM) cycling. Under oxic conditions, the release of dissolved combined carbohydrates was enhanced, and the amino acid-based degradation index (DI) pointed to more diagenetically altered DOM. Our results suggest bacterial Corg uptake in low-oxygen systems dominated by S. baltica can be limited by oxygen but compensated by high nitrate availability. Hence, suboxia diminishes Corg remineralisation only when alternative electron acceptors are lacking. Under high nitrate:Corg supply, denitrification leads to a higher N:C loss ratio, potentially counteracting eutrophication in the long run. Low nitrate:Corg supply may favour other anaerobic respiration pathways like DNRA, which sustains labile nitrogen in the system, potentially intensifying the cycle of eutrophication. Going forward, it will be crucial to establish the validity of our findings for S. baltica in natural systems with diverse organic substrates and microbial consortia.

Abundance, distribution, and ecological/environmental risks of critical rare earth elements (REE) in phosphate ore, soil, tailings, and sediments: application of spectroscopic fingerprinting

Abstract Purposes This research focuses on the characterization of phosphate ore, its solid effluents, and nearby contaminated soils in the southwest Tunisia (Gafsa-Metlaoui Basin). It aims also at evaluating the vertical distribution and abundance of critical rare earth elements (REE) in the different materials and their ecological and environmental risks. Materials and methods The sampled materials went through physical, chemical, and mineralogical characterization which involved XRF, XPS, XRD, and ICP-MS analyses. The REE anomalies and the environmental and ecological indices were calculated. Results and discussions Results show relatively high concentrations of nine rare REEs, following the sequence La &gt; Ce &gt; Nd &gt; Y &gt; Gd &gt; Eu &gt; Sm &gt; Yb &gt; Tb and trace metal elements (TME) such as Cd, Cr, Mn, Zn, Co, Fe, Sr, Cu, Ni, Pb, Ba that surpass, in some cases, international standards. The vertical distribution of the studied elements within a sediment, tailings, and soil profiles (beyond 20 cm of depth) indicates their likely in-depth migration. TME- and REE-bearing phosphate samples reflect mostly oxic conditions in the southern area with high positive Eu anomalies signifying possible mixing of sources. The environmental assessment indicate no contamination and a moderate enrichment of REEs, except for Eu, which displays significant contamination and extreme enrichment. Whereas, a deficiency of Y has been detected in most of the studied samples except for sludge sample which was also found significantly enriched with REE. Conclusions There are fundamental similarities between the different studied samples with high carbonate mineral concentrations. Statistical analysis confirmed the spectroscopic fingerprints demonstrating that the different materials share a similar composition. All of these similarities are most likely linked to the impact of mining activities on sediments and soils. Overall, our findings highlight the global effect of ore processing in determining the geochemical and the mineralogical characteristics of the surrounding environments of mines.

Mineralogical and geochemical characteristics of the Nkoteng-Mbandjock alluvial clays from Sanaga valley deposits (Cameroon, Central Africa): Implications for source weathering and provenance

This research investigates the physico-chemical, mineralogical and geochemical attributes of alluvial clayey sediments in the Nkoteng-Mbandjock regions of the Sanaga valley, Cameroon. The primary objective is to elucidate the source area-weathering and provenance of these sediments. Grain size distribution analyses were conducted using the Robinson-Kӧln's pipetting method. The physico-chemical parameters were evaluated by an HACH-HQ11d brand electric pH meter, while the mineralogical compositions were determined by X-ray Diffraction. Major and trace element concentrations were measured employing X-ray Fluorescence and Inductively Coupled Plasmas-Mass Spectrometry. Textural classification identified the Sanaga valley alluvial clay deposits as predominantly silty clayey and clayey muddy. Geochemical classification diagram positioned them in the shale and Fe-shale fields. Weathering indices of alteration exhibited a consistent trend indicating a high degree of weathering in the source rock. A low Na2O/K2O ratio (average 0.18) and a high Index of Compositional Variability (ICV; average 2.29) suggested immature sediments. Additionally, low SiO2/Al2O3 ratio (average 3.93) implied an origin from stable settings with recycled inputs. These characteristics were further supported by elemental ratios such as Zr/Sc (average 47.12), U/Th (average 0.24) and Th/Sc (average 1.48). Furthermore, indicators like V/Cr (average 1.17), U/Th (average 0.24) and authigenic U (average −1.67) values suggested the deposition of the Sanaga valley alluvial clay under oxic conditions. The collective analysis of major and trace element distribution revealed felsic sources with minimal contributions from mafic rocks. These findings contribute to a comprehensive understanding of the geological processes and conditions influencing the composition and characteristics of the studied alluvial clay deposits in the Sanaga valley.

High hydrostatic pressure stimulates microbial nitrate reduction in hadal trench sediments under oxic conditions

Hadal trenches are extreme environments situated over 6000 m below sea surface, where enormous hydrostatic pressure affects the biochemical cycling of elements. Recent studies have indicated that hadal trenches may represent a previously overlooked source of fixed nitrogen loss; however, the mechanisms and role of hydrostatic pressure in this process are still being debated. To this end, we investigate the effects of hydrostatic pressure (0.1 to 115 MPa) on the chemical profile, microbial community structure and functions of surface sediments from the Mariana Trench using a Deep Ocean Experimental Simulator supplied with nitrate and oxygen. We observe enhanced denitrification activity at high hydrostatic pressure under oxic conditions, while the anaerobic ammonium oxidation – a previously recognized dominant nitrogen loss pathway – is not detected. Additionally, we further confirm the simultaneous occurrence of nitrate reduction and aerobic respiration using a metatranscriptomic dataset from in situ RNA-fixed sediments in the Mariana Trench. Taken together, our findings demonstrate that hydrostatic pressure can influence microbial contributions to nitrogen cycling and that the hadal trenches are a potential nitrogen loss hotspot. Knowledge of the influence of hydrostatic pressure on anaerobic processes in oxygenated surface sediments can greatly broaden our understanding of element cycling in hadal trenches.

Evaluation of Phosphorus Enrichment in Groundwater by Legacy Phosphorus in Orchard Soils with High Phosphorus Adsorption Capacity Using Phosphate Oxygen Isotope Analysis.

Long-term phosphorus (P) fertilization results in P accumulation in agricultural soil and increases the risk of P leaching into water bodies. However, evaluating P leaching into groundwater is challenging, especially in clay soil with a high P sorption capacity. This study examined whether the combination of PO4 oxygen isotope (δ18OPO4) analysis and the P saturation ratio (PSR) was useful to identify P enrichment mechanisms in groundwater. We investigated the groundwater and possible P sources in Kubi, western Japan, with intensive citrus cultivation. Shallow groundwater had oxic conditions with high PO4 concentrations, and orchard soil P accumulation was high compared with forest soil. Although the soil had a high P sorption capacity, the PSR was above the threshold, indicating a high risk of P leaching from the surface orchard soil. The shallow groundwater δ18OPO4 values were higher than the expected isotopic equilibrium with pyrophosphatase. The high PSR and δ18OPO4 orchard soil values indicated that P leaching from orchard soil was the major P enrichment mechanism. The Bayesian mixing model estimated that 76.6% of the P supplied from the orchard soil was recycled by microorganisms. This demonstrates the utility of δ18OPO4 and the PSR to evaluate the P source and biological recycling in groundwater.

Effects of dissolved oxygen changes in the benthic environment on phosphorus flux at the sediment-water interface in a coastal brackish lake

In semi-enclosed coastal brackish lakes, changes in dissolved oxygen in the bottom layer due to salinity stratification can affect the flux of phosphorus (P) at the sediment-water interface, resulting in short- and long-term water quality fluctuations in the water column. In this study, the physicochemical properties of the water layers and sediments at five sites in Saemangeum Lake were analyzed in spring and autumn for four years, and phosphorus release experiments from sediments were conducted for 20 days under oxic and anoxic conditions during the same period. Sediment total phosphorus (T-P) decreased in autumn compared to spring due to mineralization of organic bound phosphorus, which was the most dominant P fraction. This may be related to the increase in the ratio of PO4–P to T-P in bottom waters in autumn, when hypoxia was frequently observed. The difference in P fluxes between oxic and anoxic conditions indicated that during autumn, as compared to spring, the release of phosphorus could have a more immediate impact on the water column during the formation of hypoxia/anoxia. The main factors influencing changes in P fluxes from sediments were identified through redundancy analysis. Additionally, based on the results of multiple regression analysis, sediment TOC, sediment non-apatite phosphorus, porewater pH, and porewater PO4–P were determined to be the most significant factors affecting P fluxes from sediments, depending on the season or redox conditions. Recently, the increased influx of seawater into Saemangeum Lake has been shown to contribute to water quality improvements in the water column due to a strong dilution effect. However, the sediment environment has shifted towards a more reduced state, leading to increased P release under anoxic conditions. Therefore, for future water quality management within the lake, it is necessary to consistently address the recurring hypoxia and continuously monitor phosphorus dynamics.

Internal phosphorus loading in a chain of eutrophic hardwater lakes in Saskatchewan, Canada

Sediments can act as a source or sink of phosphorus (P) for the water column of lakes. In iron (Fe)-rich softwater lakes, redox processes are important contributors to sediment P flux. However, the contribution of redox processes to P flux in hardwater lakes, with high pH and high concentrations of redox-insensitive calcium (Ca) is unknown. Intact sediment cores, collected in different seasons (summer or fall) from a chain of eutrophic hardwater lakes in southeastern Saskatchewan, Canada, were used to quantify sediment P fluxes in laboratory incubations under hypoxic or oxic conditions at temperatures consistent with the season of sample collection. Geochemical analyses determined concentrations of sediment total (TP) and organic P (TPo), organic matter (OM), total Ca and magnesium, and total and extractable manganese, Fe and aluminum. Sediment P pools were determined using sequential fractionation and solution 31P nuclear magnetic resonance spectroscopy. Sediment P fluxes were significantly higher in sediment cores incubated under hypoxic conditions (−24.4 to 28.5 mg P m−2 d−1) than oxic conditions (−60.3 to 14.2 mg P m−2 d−1). There were significant seasonal and lake differences for TP, TPo and cation concentrations, with Ca the dominant cation in all but one lake. Phosphate bound in the redox-sensitive pool was the only sediment P fraction that significantly differed among the lakes (0.10 to 0.18 mg P g−1 d.w.; 9 to 16 % of TP), with an inverse relationship to sediment P flux. Principal component analysis suggests that high concentrations of internally-generated TPo forms and OM in surface sediments play a key role in internal P loading in these lakes. However, sediment Ca appears to have an overriding effect on sediment P, partially masking the impact of redox control on internal P loading in these hardwater prairie lakes.

Predicting Redox Conditions in Groundwater at a National Scale Using Random Forest Classification.

Redox conditions in groundwater may markedly affect the fate and transport of nutrients, volatile organic compounds, and trace metals, with significant implications for human health. While many local assessments of redox conditions have been made, the spatial variability of redox reaction rates makes the determination of redox conditions at regional or national scales problematic. In this study, redox conditions in groundwater were predicted for the contiguous United States using random forest classification by relating measured water quality data from over 30,000 wells to natural and anthropogenic factors. The model correctly predicted the oxic/suboxic classification for 78 and 79% of the samples in the out-of-bag and hold-out data sets, respectively. Variables describing geology, hydrology, soil properties, and hydrologic position were among the most important factors affecting the likelihood of oxic conditions in groundwater. Important model variables tended to relate to aquifer recharge, groundwater travel time, or prevalence of electron donors, which are key drivers of redox conditions in groundwater. Partial dependence plots suggested that the likelihood of oxic conditions in groundwater decreased sharply as streams were approached and gradually as the depth below the water table increased. The probability of oxic groundwater increased as base flow index values increased, likely due to the prevalence of well-drained soils and geologic materials in high base flow index areas. The likelihood of oxic conditions increased as topographic wetness index (TWI) values decreased. High topographic wetness index values occur in areas with a propensity for standing water and overland flow, conditions that limit the delivery of dissolved oxygen to groundwater by recharge; higher TWI values also tend to occur in discharge areas, which may contain groundwater with long travel times. A second model was developed to predict the probability of elevated manganese (Mn) concentrations in groundwater (i.e., ≥50 μg/L). The Mn model relied on many of the same variables as the oxic/suboxic model and may be used to identify areas where Mn-reducing conditions occur and where there is an increased risk to domestic water supplies due to high Mn concentrations. Model predictions of redox conditions in groundwater produced in this study may help identify regions of the country with elevated groundwater vulnerability and stream vulnerability to groundwater-derived contaminants.

Re‐Evaluating Hydrogen Sulfide as a Sink for Cadmium and Zinc in the Oxic to Suboxic Upper Water Column of the Pacific Ocean

AbstractHydrogen sulfide is produced by heterotrophic bacteria in anoxic waters and via carbonyl sulfide hydrolysis and phytoplankton emissions under oxic conditions. Apparent losses of dissolved cadmium (dCd) and zinc (dZn) in oxygen minimum zones (OMZs) of the Atlantic and Pacific Oceans have been attributed to metal‐sulfide precipitation formed via dissimilatory sulfate reduction. It has also been argued that such a removal process could be a globally important sink for dCd and dZn. However, our studies from the North Pacific OMZ show that dissolved and particulate sulfide concentrations are insufficient to support the removal of dCd via precipitation. In contrast, apparent dCd and dZn deficits in the eastern tropical South Pacific OMZ do reside in the oxycline with particulate sulfide maxima, but they also coincide with the secondary fluorescence maxima, suggesting that removal via sulfide precipitation may be due to a combination of dissimilatory and assimilatory sulfate reduction. Notably, dCd loss via precipitation with sulfide from assimilatory reduction was found in upper oxic waters of the North Pacific. While dissimilatory sulfate reduction may explain local dCd and dZn losses in some OMZs, our evaluation of North Pacific OMZs demonstrates that dCd and dZn losses are unlikely to be a globally relevant sink. Nevertheless, metal sulfide losses due to assimilatory sulfate reduction in surface waters should be considered in future biogeochemical models of oceanic Cd (and perhaps Zn) cycling.

Mineralogical and geochemical facets of the massive deposition of stibnite-metastibnite at a seafloor hydrothermal field (Wakamiko Crater, Kagoshima Bay, Ryukyu Volcanic Arc)

Abstract Stibnite precipitates in the form of massive boulders at two active hydrothermal mounds in the submarine Wakamiko Crater (Ryukyu Volcanic Arc) as opposed to commonly observed accessory stibnite in the seafloor hydrothermal deposits. The stibnite dimorph, metastibnite, found here for the first time on the seafloor, appears to always form whenever stibnite is precipitated under submarine hydrothermal conditions. Our study shows that hydrothermal conditions of low temperatures (&amp;lt;50 °C) and low values of pH (&amp;lt;6) are favorable for the precipitation of stibnite on the seafloor. The stibnite probably does not precipitate at the measured vent fluid temperatures (i.e., 177.6 – 187.0 °C) along the chimney conduits, but rather at temperatures &amp;lt;50 °C and at slightly reduced to slightly oxic conditions (Eh = -0.5 to +0.5 V) within the chimney walls and hydrothermal mounds. Metastibnite deposition appears to be the result of rapid quenching of hot hydrothermal fluid when mixed with cold seawater and rapid precipitation at the interface between stibnite and vent fluid. The low concentrations (usually below detection limits) of the trace elements (Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, P, Pb, Sr, V, Zn) in the stibnite deposits from Wakamiko Crater are likely a result of decreased metal-transporting capacity of the precipitating vent fluid due to its low chlorinity. Low-chlorinity venting implies sub-seafloor boiling and phase separation of the hydrothermal fluid. Sluggish hydrothermal fluid/seawater mixing within the walls of the chimneys and mounds favors the reduction of sulfate dissolved in the hydrothermal fluids and results in a heavy S isotope composition of the sulfate in the vent fluids. Sulfate reduction and disproportionation of magmatic SO2, both leading to heavy S isotope composition of sulfate in the vent fluids, seem to be common processes in volcanic arc/back-arc submarine hydrothermal settings.

Geochemistry of Liquid Hydrocarbons and Natural Gases Combined with 1D Basin Modeling of the Oligocene Shale Source Rock System in the Offshore Nile Delta, Egypt.

The current study aims to integrate the geochemical characteristics of the Oligocene shale source rock system, oil, condensate, and natural gas samples in the Oligocene sandstone reservoirs from three exploration wells located in the offshore Nile Delta, East Mediterranean Sea, using organic geochemistry and a 1D basin modeling scheme. The Tineh shales exhibit total organic carbon values ranging between 0.90 and 1.89 wt %, along with hydrogen index values in the range of 54-240 mg hydrocarbon/g rock. The geochemical characterization suggests that the shale intervals of the Oligocene Tineh Formation contain type II-III and type III kerogens and, thereby, could be regarded as promising oil- and gas-prone source rocks with high contributions of gas generation potential. The study also reconstructs the 1D thermal and burial history models, showing that the Oligocene Tineh source rock system is in the main oil and wet gas generation phases from the late Miocene to the present time. The simulated basin models reveal the transformation (TR) of 10-50% kerogen to oil during the late Miocene-early Pliocene period and that the Oligocene Tineh source rock system has larger oil generation and expulsion competency, with a TR value of up to 65% during the early Pliocene-Pleistocene time period. The thermogenic gas was also formed during this time and continued to the present day. This study also investigated the presence of oil and condensate in the Oligocene sandstone reservoir samples and revealed that they were generated from mature source rock, ranging from moderately to highly mature stages. This source rock unit was deposited in fluvial to fluvial-deltaic environments under oxic mixed organic conditions and accumulated during the Tertiary time, as evidenced by the presence of the oleanane biomarker dating indicator. The molecular and isotope compositions of natural gases revealed that most of the natural gases in the Oligocene sandstone reservoir are mainly thermogenic methane gases that were generated from mainly mixed organic matter. The thermogenic methane gases were formed mainly from secondary cracking of oil and gas, with small contributions of primary kerogen cracking. The properties of natural gases together with oil and condensate in the Oligocene reservoir rocks suggest that most of the thermogenic methane gases and associated liquid hydrocarbons are derived primarily from the Oligocene shale source rock system and formed by primary kerogen cracking and secondary oil and oil/gas cracking in different thermal maturity stages. Therefore, the Oligocene Tineh Formation can be regarded as self-source generation and self-reservoir rock; hence, an intensive oil exploration and production program can be recommended whenever the Tineh source rock system is is well developed and deeply buried.

Carbon Fate, Iron Dissolution, and Molecular Characterization of Dissolved Organic Matter in Thawed Yedoma Permafrost under Varying Redox Conditions.

Permafrost soils store ∼50% of terrestrial C, with Yedoma permafrost containing ∼25% of the total C. Permafrost is undergoing degradation due to thawing, with potentially hazardous effects on landscape stability and water resources. Complicating ongoing efforts to project the ultimate fate of deep permafrost C is the poorly constrained role of the redox environment, Fe-minerals, and its redox-active phases, which may modulate organic C-abundance, composition, and reactivity through complexation and catalytic processes. We characterized C fate, Fe fractions, and dissolved organic matter (DOM) isolates from permafrost-thaw under varying redox conditions. Under anoxic incubation conditions, 33% of the initial C was lost as gaseous species within 21 days, while under oxic conditions, 58% of C was lost. Under anoxic incubation, 42% of the total initial C was preserved in a dissolved fraction. Lignin-like compounds dominated permafrost-thaw, followed by lipid- and protein-like compounds. However, under anoxic incubation conditions, there was accumulation of lipid-like compounds and reduction in the nominal oxidation state of C over time, regardless of the compound classes. DOM dynamics may be affected by microbial activity and abiotic processes mediated by Fe-minerals related to selective DOM fractionation and/or its oxidation. Chemodiversity DOM signatures could serve as valuable proxies to track redox conditions with permafrost-thaw.

Blue carbon additionality: New insights from the radiocarbon content of saltmarsh soils and their respired CO2

AbstractInternational policy frameworks recognize the net drawdown and storage of atmospheric greenhouse gases through management interventions on blue carbon ecosystems (saltmarshes, mangroves, seagrasses) as potential emissions offset strategies. However, key questions remain around the “additionality” of the carbon sequestered by these ecosystems, and whether some fraction of the organic carbon (OC) that does not derive from in situ production (allochthonous) should be included in carbon budgets. This study compares the radiocarbon (14C) contents of saltmarsh soils and CO2 evolved from aerobic laboratory incubations to show that young OC is preferentially respired over aged OC, and that the latter is also vulnerable to remineralization under oxic conditions. This highlights that management interventions which reduce the exposure of saltmarsh soils to oxic conditions support the inclusion of some portion of allochthonous OC in carbon budgets. Elevated temperature incubations provide preliminary evidence that the predominant source of respired OC will not change under predicted future warmer conditions. Saltmarsh typology also influences the 14C content of both the bulk soil and respired CO2, highlighting the importance of site selection for optimized blue carbon additionality.

Redox cycling of straw-amended soil simultaneously increases iron oxide crystallinity and the content of highly disordered organo-iron(III) solids

Iron speciation in soils is influenced largely by its redox state, but the extent of and controls on Fe speciation during recurrent reduction and oxidation events are not fully understood. To investigate the effects of organic matter (OM) inputs and the frequency and duration of redox oscillations on soil Fe speciation, we conducted redox-oscillation experiments with topsoil from a Fluvisol mixed with rice straw (0, 10, 50 g/kg organic carbon, OC). The soil was initially dominated by short-range ordered (SRO) Fe(III) solids and subjected to 14- and 28-day reduction–oxidation cycles for 112 days, with the time spent under anoxic and oxic conditions maintained at 6:1. Reduction was initiated by flooding reactors with artificial river water. To simulate leaching conditions, soil re-oxidation was achieved by air-drying soil after removal of reacted solutions. Fresh river water was then added for each new redox cycle. We monitored changes in solution composition (Eh, pH, Fe(II), total Fe, OC, and Si) and assessed changes of solid-phase Fe speciation by selective extractions, X-ray absorption spectroscopy, and 57Fe Mössbauer spectroscopy. Dissolved OC and Fe increased with increasing straw addition, but decreased in each treatment through consecutive reduction intervals. Release rates of dissolved Fe and OC were highly correlated, implying that microbial reduction of soil Fe(III) solids was fostered by straw amendments. Reduction-induced losses of OC and Fe from straw amended soil were amplified at high redox frequency. Ferrous Fe did not detectably accumulate in the solid phase upon repeated soil oxidation. Although Fe(III)-poor phyllosilicates gained in relative importance in redox-cycled soils, their fraction was hardly affected during redox cycling. Instead, straw additions led to an enhanced depletion of ferrihydrite during soil redox cycling and a relative enrichment of highly disordered Fe(III) species [‘very SRO (vSRO) Fe(III) solids’], which remained only partially ordered in 5-K Mössbauer spectra and likely consisted predominantly of polynuclear organic Fe complexes. The depletion of ferrihydrite in straw-amended soils after 112 days was greater in the 14-day cycle than in the 28-day cycle experiment and accompanied by a less pronounced enrichment of vSRO Fe(III) solids. The crystallinity of distinct Fe oxides (ferrihydrite, lepidocrocite, and hematite) increased during soil redox cycling especially in straw-amended soils, but without noticeable ferrihydrite conversion into crystalline Fe oxides. The increase in the crystallinity of distinct Fe oxides after 112 days was greater at low redox frequency in straw-free soil, however this frequency effect was suppressed by straw additions. Longer soil redox cycling (112 vs. 56 days) increased the crystallinity of distinct Fe oxides, which was most pronounced at high straw levels and low redox frequency. Our results imply that redox changes in SRO Fe oxide- and OM-rich soils can cause a relative enrichment of more crystalline Fe oxides, while still maintaining a pool of vSRO Fe(III) solids. We conclude that soil redox oscillations can lead to divergent transformation pathways of Fe oxides, which concomitantly increase bulk Fe-oxide crystallinity and generate increasing fractions of highly disordered Fe(III) solids on comparatively short time scales. In addition, our study suggests that faster redox cycling in soils with ample electron donor supply and water leaching leads to higher element exports (e.g., OC, metal(loid)s) from soil due to weekly redox pulsing than more slowly alternating redox conditions.

Fate of sulfamethoxazole in wetland sediment under controlled redox conditions

Redox condition is an important controlling factor for contaminant removal in constructed wetlands; however, the redox-sensitivity of antibiotic removal in wetland sediments under controlled conditions with specific electron acceptors remains unclear. Here, using a 14C radioactive tracer, we explored fate of sulfamethoxazole (SMX) in a wetland sediment slurry under oxic, nitrate-reducing, iron-reducing, and methanogenic conditions. In the sterile treatment, unlike the comparable SMX dissipation from the water phase under four redox conditions, non-extractable residues (NERs) of SMX was highest formed in the sediment under oxic condition, mainly in sequestered and ester/amide-linked forms. Microorganisms markedly promoted SMX transformation in the slurry. The dissipation rate of SMX and its transformation products (TPs) followed the order: oxic ≈ iron-reducing > methanogenic >> nitrate-reducing conditions, being consistent with the dynamics of microbial community in the sediment, where microbial diversity was greater and networks connectivity linking dominant bacteria to SMX transformation were more complex under oxic and iron-reducing conditions. Kinetic modeling indicated that the transformation trend of SMX and its TPs into the endpoint pool NERs depended on the redox conditions. Addition of wetland plant exudates and sediment dissolved organic matter at environmental concentrations affected neither the abiotic nor the biotic transformation of SMX. Overall, the iron-reducing condition was proven the most favorable and eco-friendly for SMX transformation, as it resulted in a high rate of SMX dissipation from water without an increase in toxicity and subsequent formation of significant stable NERs in sediment. Our study comprehensively revealed the abiotic and biotic transformation processes of SMX under controlled redox conditions and demonstrated iron-reducing condition allowing optimal removal of SMX in constructed wetlands.