Low Sulfate Research Articles

Low molecular weight chondroitin sulfate ameliorates pathological changes in 5XFAD mice by improving various functions in the brain

Our previous study found that low molecular weight chondroitin sulfate (LMWCS) had neuroprotective effects against the toxicity of amyloid-β (Aβ) peptides both in vitro and in vivo, and we speculated that the effects might be related with its anti-oxidative activities. In this study, the anti-Alzheimer′s disease (AD) activity of LMWCS was further studied in 5XFAD transgenic mice. After 4-month gavage, the levels of Aβ1-42 level, amyloid precursor protein (APP) and presenilin 1 (PS1) were significantly decreased in the brains of 5XFAD mice, indicating the alteration of APP metabolism by LMWCS. Besides, LMWCS inhibited the secretions of pro-inflammatory cytokines, including interleukin-1β (IL-1β), tumor necrosis factor-α (TNF-α) and IL-6. Furthermore, the suppression of neuroinflammation by LMWCS was supported by the decreased expressions of glial fibrillary acidic protein (GFAP) and toll-like receptor 2 (TLR2) in the brains. LMWCS also reduced the production of reactive oxygen species (ROS) and the level of phospho-tau (Ser404) in the brains. Nevertheless, the changes in the behavior tests were moderate. In conclusion, LMWCS administration ameliorated APP metabolism, neuroinflammation, ROS production and tau protein abnormality in the brains of 5XFAD mice, displaying the potential to improve the pathological changes of AD mouse brain. LMWCS could be considered as a promising anti-AD drug candidate, nonetheless, the therapy regimen need to be optimized to improve its pharmacotherapy efficacy.

Pore-Scale Oil Connectivity and Displacement by Controlled-Ionic-Composition Waterflooding Using Synchrotron X-Ray Microtomography

Summary Controlled-ionic-composition waterflooding is an economic and effective method to improve oil recovery in carbonate oil reservoirs. Recent studies show controlling the salinity and ionic composition of injection water can alter the wettability of carbonate mineral surfaces. The pore-scale oil connectivity and displacement by controlled-ionic-composition waterflooding in heterogeneous carbonate reservoirs, especially at the early stage, is still unclear. The goal of this study is to examine the role of ion concentrations and types in the oil displacement efficiency and investigate the impact of the waterflooding on the pore-scale oil displacement using the national synchrotron facility. A carbonate rock sample was flooded with synthetic high-salinity water and other water solutions with different sulfate concentrations. The waterflooding processes were visualized with synchrotron X-ray microtomography to follow the evolution of pore-scale oil/brine interactions at typical field flow rates. Experimental results show that the water with lower sulfate concentration and higher salinity did not change the wettability of the pore surfaces. Higher sulfate ion concentrations in the water, in contrast, altered the wettability of carbonate pore surfaces from oil-wet to neutral-wet within the first few minutes of waterflooding. Novel insight was gained on the ability of water with high-sulfate concentration to displace oil in the small pores and through abundant oil channels, which could consequently lead to higher oil recovery from the carbonate rock.

A novel preparation of high purity TiO2 from industrial low concentration TiOSO4 solution via short sulfate process

High purity TiO2 was prepared by authigenic seed thermal hydrolysis route from industrial low concentration titanyl sulfate solution via the short sulfate process. The hydrolysis conditions had important influences on the hydrolysis process. The appropriate induced water volume ratio and hydrolysis time were conducive to form appropriate quantity and quality of hydrolysis seeds, adjust and control the precipitation, crystal growth, particle growth and aggregation velocity for the hydrated TiO2, which could obtain the hydrated TiO2 with smaller average particle size and specific surface area. These effects were beneficial to reduce the adsorption of impurities, and improve the purity of TiO2. The hydrolysis conditions had internal influencing relationship between them. The optimized hydrolysis conditions were the induced water volume ratio was of 60%, the hydrolysis time was of 120 min, and the high purity, monodisperse titanium dioxide over 99.98% content could be obtained.

Effect of foliar application of the selenium-rich nutrient solution on the selenium accumulation in grains of Foxtail millet (Zhangzagu 10).

The foliar application of selenium (Se) is an effective method for biofortification of Se in crop grains in order to provide sufficient Se for human health. As a staple food in China, the foxtail millet (Setaria italica L.), which had been Se biofortification, would be helpful to overcome Se deficiency in the diet. The Se fertilizer and its application technology are vital for reducing environmental risk while enriching selenium. Hence, the Se-rich nutrient solution developed by ourselves was used, and the effect of its amount and growth stage applied on the accumulation of Se in grains of foxtail millet (Setaria italica L.) was studied in the present study. The results were as follows: (1) the Se concentration in grains increased with the Se application rate increasing, and the highest Se concentration in grains was 1.83 mg kg-1 at the sprayed concentration of 61.5 gSe hm-2; (2) the accumulation of Se sprayed in the grain-filling stage was 1.3-1.6 times higher than that in the joint stage; and (3) the organ damage could be found under low Se/S ratio, which happened in the rice leaves when the Se rate was higher than 76.875 gSe m-2 with the low sulfate application compared with the formulation. This Se-rich nutrient solution could be used to produce the Se-rich millet grains and foliar application in the reproductive stage to produce qualified Se-rich millet.

ILB® Attenuates Clinical Symptoms and Serum Biomarkers of Oxidative/Nitrosative Stress and Mitochondrial Dysfunction in Patients with Amyotrophic Lateral Sclerosis.

Oxidative/nitrosative stress and mitochondrial dysfunction is a hallmark of amyotrophic lateral sclerosis (ALS), an invariably fatal progressive neurodegenerative disease. Here, as an exploratory arm of a phase II clinical trial (EudraCT Number 2017-005065-47), we used high performance liquid chromatography(HPLC) to investigate changes in the metabolic profiles of serum from ALS patients treated weekly for 4 weeks with a repeated sub-cutaneous dose of 1 mg/kg of a proprietary low molecular weight dextran sulphate, called ILB®. A significant normalization of the serum levels of several key metabolites was observed over the treatment period, including N-acetylaspartate (NAA), oxypurines, biomarkers of oxidative/nitrosative stress and antioxidants. An improved serum metabolic profile was accompanied by significant amelioration of the patients’ clinical conditions, indicating a response to ILB® treatment that appears to be mediated by improvement of tissue bioenergetics, decrease of oxidative/nitrosative stress and attenuation of (neuro)inflammatory processes.

Quantification of the water footprint inventory in South African coal fuel cycle

Due to the scarcity of the water footprint inventory data for the coal mining industry in South Africa, water footprint studies that are supposed to provide quantified and categorized environmental impacts are scarce. Consequently, water uses ecological implications within the industry are not well understood, albeit public perceptions suggesting that the industry is a water guzzler and polluter. This manuscript proposes water footprint inventory data for the industry to enable researchers to conduct water footprint studies. The median total water loss intensities for surface mines with and without beneficiation are 331 and 276 L/ton, whereas those of underground mines with and without beneficiation are 420 and 262 L/ton, respectively. The water-intensive sinks are evaporation, dust suppression, and discharge into the environment. Water management practices, i.e., the high recycling rate in mines with excess water, non-segregation of clean and dirty water streams, and deficient water treatment infrastructure, are the root causes of the water pollution in collieries. Although low pH, high sulfates, and high total dissolved solids in coal effluents are congruent to other jurisdictions, the high cyanide, iron, manganese, and mercury content make the country's pollutants inventory data uniquely different. Misalignment between drinking water and effluent discharge limits are the causes of regulatory challenges. The voluntary disclosure practice prohibits transparency within the industry.

S and O isotope ratios of sulfate suggest enhanced monosulfides oxidation in a historical Pb–Zn mine site

Aqueous and solid tailings geochemistry of two contrasting depositional sites (water-saturated and subaerial) in a historical Pb–Zn mine tailings in Balya, Turkey were chemically and isotopically (δ34S and δ18O) characterized to trace source of sulfate and elucidate oxidation pathways of sulfide mixtures. Aqueous geochemistry data of water-soluble fractions (n = 15) obtained from the batch leaching tests applied on the subaerial mine tailings (SA-MT) revealed three geochemically distinct zones: i) oxidized zone (OXZ, 10–75 cm), ii) transition zone (TZ, 75–125 cm) and iii) unoxidized zone (U-OXZ, 125–350 cm). The OXZ is characterized by a sharp decrease in sulfur and metals contents of the tailing rocks while high sulfate and metals concentrations in their water-soluble fractions. In contrast, the TZ and U-OXZ zones are mainly characterized by low sulfate but relatively high metal concentrations with slightly acidic pH values (4.9–6.2). Compared to the SA-MT tailings geochemical profiles of the pore waters of the water-saturated tailings (S-MT) showed remarkably high sulfate, Fetot and metals concentrations with strong acidic pH values (1.9–3.8). The δ34S and δ18O values of sulfate suggest that galena and/or sphalerite are the main source of sulfate and metals at the tailings site. The differences in sulfur isotope values (Δ34SSO4-sulfide) appear to be reflective of the extend of oxidation of monosulfides (e.g. galena) under two contrasting conditions of the tailings. The large sulfur isotope differences (Δ34SSO4-sulfides ~ -4.5 ± 0.2‰) imply incomplete oxidation of monosulfides to sulfate with aqueous geochemistry record of low sulfate, high metal and slightly acidic pH values. In contrast, the small Δ34SSO4-sulfide (<1 ± 0.2‰) values indicate the tailings site where complete oxidation of monosulfides to sulfate occurred resulting in acidic condition having with high sulfate, metal concentrations. The δ18OSO4 values were enriched than those of background water in tailings sites with the similar Δ18OSO4–H2O values (+8.9 to +11‰). Based on field data revealing enhanced galena and/or sphalerite oxidation relative to pyrite, the observed Δ18OSO4–H2O (avg., 9‰) values coupled with the relationship between δ34SSO4 values and sulfate concentration can be reflective of oxidation of monosulfides in contrast to disulfide minerals (e.g, pyrite) within polymetallic rich AMD systems.

Sulfate-Controlled Heterogeneous CaCO3 Nucleation and Its Non-linear Interfacial Energy Evolution.

Unveiling the effects of an environmental abundant anion "sulfate" on the formation of calcium carbonate (CaCO3) is essential to understand the formation mechanisms of biominerals like corals and brachiopod shells, as well as the scale formation in desalination systems. However, it was experimentally challenging to elucidate the sulfate-CaCO3 interactions at the explicit first step of CaCO3 formation: nucleation. In addition, there is limited quantitative information on the precise control of nucleation kinetics. Here, heterogeneous CaCO3 nucleation is monitored in real time as a function of sulfate concentrations (0-10 mM Na2SO4) using synchrotron-based grazing incidence X-ray scattering techniques. The results showed that sulfate can be incorporated in the nuclei, resulting in a nearly 90% decrease in the CaCO3 nucleation rate, causing a 120% increase in the CaCO3 nucleus size, and inhibiting the vaterite-to-calcite phase transformation. Moreover, this work quantitatively relates sulfate concentrations to the effective interfacial energies of CaCO3 and finds a non-linear trend, suggesting that CaCO3 heterogeneous nucleation is more sensitive at a low sulfate concentration. This study can be readily extended to study other additives and obtain quantitative relationships between additive concentrations and CaCO3 interfacial energies, a key step toward achieving natural and engineered controls on CaCO3 nucleation.

Differences in MPS I and MPS II Disease Manifestations.

Mucopolysaccharidosis (MPS) type I and II are two closely related lysosomal storage diseases associated with disrupted glycosaminoglycan catabolism. In MPS II, the first step of degradation of heparan sulfate (HS) and dermatan sulfate (DS) is blocked by a deficiency in the lysosomal enzyme iduronate 2-sulfatase (IDS), while, in MPS I, blockage of the second step is caused by a deficiency in iduronidase (IDUA). The subsequent accumulation of HS and DS causes lysosomal hypertrophy and an increase in the number of lysosomes in cells, and impacts cellular functions, like cell adhesion, endocytosis, intracellular trafficking of different molecules, intracellular ionic balance, and inflammation. Characteristic phenotypical manifestations of both MPS I and II include skeletal disease, reflected in short stature, inguinal and umbilical hernias, hydrocephalus, hearing loss, coarse facial features, protruded abdomen with hepatosplenomegaly, and neurological involvement with varying functional concerns. However, a few manifestations are disease-specific, including corneal clouding in MPS I, epidermal manifestations in MPS II, and differences in the severity and nature of behavioral concerns. These phenotypic differences appear to be related to different ratios between DS and HS, and their sulfation levels. MPS I is characterized by higher DS/HS levels and lower sulfation levels, while HS levels dominate over DS levels in MPS II and sulfation levels are higher. The high presence of DS in the cornea and its involvement in the arrangement of collagen fibrils potentially causes corneal clouding to be prevalent in MPS I, but not in MPS II. The differences in neurological involvement may be due to the increased HS levels in MPS II, because of the involvement of HS in neuronal development. Current treatment options for patients with MPS II are often restricted to enzyme replacement therapy (ERT). While ERT has beneficial effects on respiratory and cardiopulmonary function and extends the lifespan of the patients, it does not significantly affect CNS manifestations, probably because the enzyme cannot pass the blood–brain barrier at sufficient levels. Many experimental therapies, therefore, aim at delivery of IDS to the CNS in an attempt to prevent neurocognitive decline in the patients.

Response to substrate limitation by a marine sulfate-reducing bacterium.

Sulfate-reducing microorganisms (SRM) in subsurface sediments live under constant substrate and energy limitation, yet little is known about how they adapt to this mode of life. We combined controlled chemostat cultivation and transcriptomics to examine how the marine sulfate reducer, Desulfobacterium autotrophicum, copes with substrate (sulfate or lactate) limitation. The half-saturation uptake constant (Km) for lactate was 1.2 µM, which is the first value reported for a marine SRM, while the Km for sulfate was 3 µM. The measured residual lactate concentration in our experiments matched values observed in situ in marine sediments, supporting a key role of SRM in the control of lactate concentrations. Lactate limitation resulted in complete lactate oxidation via the Wood-Ljungdahl pathway and differential overexpression of genes involved in uptake and metabolism of amino acids as an alternative carbon source. D. autotrophicum switched to incomplete lactate oxidation, rerouting carbon metabolism in response to sulfate limitation. The estimated free energy was significantly lower during sulfate limitation (-28 to -33 kJ mol-1 sulfate), suggesting that the observed metabolic switch is under thermodynamic control. Furthermore, we detected the upregulation of putative sulfate transporters involved in either high or low affinity uptake in response to low or high sulfate concentration.

Limnological Conditions and Photosynthetic Pigments in Clearwater Lakes of the Volga-Vyatka Karst Province

The features of summer stratification and vertical distribution of photosynthetic pigments (chlorophylls and bacteriochlorophylls) in five karst lakes in the Middle Volga region (Republics of Tatarstan and Mari-El) are studied. The water of the investigated lakes has low color and sulfate concentration and low-to-medium total dissolved salts content. Anoxic conditions develop in the hypolimnion in all lakes after the establishment of summer thermal stratification. Reduced iron and sulfur compounds are found in the anaerobic zones of most lakes. In these lakes, deep maxima of chlorophyll and bacteriochlorophylls are formed, indicating the presence of biomass maxima of microbial plankton, consisting of both oxygenic and anoxygenic phototrophs. The presented data demonstrate also a wide variety of features of both chemical stratification and vertical distribution of phototrophic organisms in the studied lakes, which are probably associated with differences in the limnological characteristics of lakes, their water composition, and the history of their existence.

Evaluating the performance of anaerobic moving bed bioreactor and upflow anaerobic hybrid reactor for treating textile desizing wastewater

Performance and kinetic analysis of anaerobic moving bed bioreactor (AnMBBR) and upflow anaerobic hybrid reactor (UAHR) were investigated for the treatment of synthetic textile desizing wastewater (TDW) under organic loading rate (OLR) of 0.6–12 kgCOD/m3/day at thermophilic temperature (55 °C). The effects of increase in temperature (from 35 to 55 °C) on anaerobic treatment efficiency were studied. In the kinetic study for COD removal, first order substrate removal, Grau second order and modified Stover-Kincannon models were applied. By increasing temperature from 35 °C to 55 °C, COD removal, volumetric biogas production and methane content were increased 1.22, 2.58 and 1.08 times in AnMBBR. Whilst in the case of UAHR the increment for the aforementioned parameters were 1.10, 2.51 and 1.10 times, respectively. By increasing OLR from 0.6 to 6 kgCOD/m3/day, above 60% and 70% COD removal was observed, while the biogas increased from 0.12 to 0.97 L/L.day and 0.13–1.22 L/L.day for AnMBBR and UAHR, respectively. Up to an optimum OLR (6 and 8 kgCOD/m3/day for AnMBBR and UAHR) volumetric biogas production was also increased, simultaneously. Grau second order and modified Stover-Kincannon were found to be the best fit models (R2 =0.99). Biogas production and methane content in biogas were comparatively better in the case of real textile desizing wastewater due to lower sulfate concentration in the feed.

Geochemical Characteristics of Late Ordovician Shales in the Upper Yangtze Platform, South China: Implications for Redox Environmental Evolution

Changes to the redox environment of seawater in the Late Ordovician affect the process of organic matter enrichment and biological evolution. However, the evolution of redox and its underlying causes remain unclear. This paper analyzed the vertical variability of main, trace elements and δ34Spy from a drill core section (well ZY5) in the Upper Yangtze Platform, and described the redox conditions, paleoproductivity and paleoclimate variability recorded in shale deposits of the P. pacificus zone and M. extraordinarius zone that accumulated during Wufeng Formation. The results showed that shale from well ZY5 in Late Ordovician was deposited under oxidized water environment, and there are more strongly reducing bottom water conditions of the M. extraordinarius zone compared with the P. pacificus zone. Excess silica (SiO2(exc)) and substitution index of paleoproductivity (Y) indicated that the P. pacificus zone had higher paleoproductivity whereas the M. extraordinarius zone was lower. The high productivity level controlled O2 release in the shallow water area as well as the oxidation degree of the P. pacificus zone. The decrease of productivity and the relatively stagnant water mass of the inner Yangtze Sea controlled the formation of relatively reduced water conditions in the M. extraordinarius zone. The chemical index of alteration (CIA) results suggested that palaeoclimatic conditions changed from warm and humid to cold and dry climate from the P. pacificus to the M. extraordinarius zones in the study area. A comparative analysis of the published Fe-S-C data for the Xiushan Datianba section showed that in the P. pacificus zone of the inner Yangtze Sea, warm and humid climate conditions drove high productivity, sulphate flux and low reactive iron flux, which promoted the expansion of oxic ocean-surface waters and mid-depth euxinic waters. In the M. extraordinarius zone, the cold and dry climate with significant uplift of the Xiang’e Submarine High led to the relative sea level decline, resulting in low productivity, sulfate flux and high reactive iron flux, which promoted the expansion of the mid-depth ferruginous waters and the shrinkage of oxic ocean-surface waters. The results offered new insights into the co-evolution of continents and oceans, and explained the role of continental weathering and uplift of the Xiang’e Submarine High in the exchange of sulfate flux and nutrients in the redox environment change of inner Yangtze Sea during the Late Ordovician.

Optimization of Heparin Monitoring with Anti-FXa Assays and the Impact of Dextran Sulfate for Measuring All Drug Activity.

Heparins, unfractionated or low molecular weight, are permanently in the spotlight of both clinical indications and laboratory monitoring. An accurate drug dosage is necessary for an efficient and safe therapy. The one-stage kinetic anti-FXa assays are the most widely and universally used with full automation for large series, without needing exogenous antithrombin. The WHO International Standards are available for UFH and LMWH, but external quality assessment surveys still report a high inter-assay variability. This heterogeneity results from the following: assay formulation, designed without or with dextran sulfate to measure all heparin in blood circulation; calibrators for testing UFH or LMWH with the same curve; and automation parameters. In this study, various factors which impact heparin measurements are reviewed, and we share our experience to optimize assays for testing all heparin anticoagulant activities in plasma. Evidence is provided on the usefulness of low molecular weight dextran sulfate to completely mobilize all of the drug present in blood circulation. Other key factors concern the adjustment of assay conditions to obtain fully superimposable calibration curves for UFH and LMWH, calibrators’ formulations, and automation parameters. In this study, we illustrate the performances of different anti-FXa assays used for testing heparin on UFH or LMWH treated patients’ plasmas and obtained using citrate or CTAD anticoagulants. Comparable results are obtained only when the CTAD anticoagulant is used. Using citrate as an anticoagulant, UFH is underestimated in the absence of dextran sulfate. Heparin calibrators, adjustment of automation parameters, and data treatment contribute to other smaller differences.

Exploiting diol reactivity for the access to unprecedented low molecular weight curdlan sulfate polysaccharides

Curdlan is a bacterial sourced polysaccharide, consisting of a linear backbone of β-1 → 3-linked glucose (Glc) units. The high interest in pharmaceutical applications of curdlan and derivatives thereof is fueling the study of multi-step sequences for regioselective modifications of its structure. Here we have developed semi-synthetic sequences based on a regioselective protection-sulfation-deprotection approach, allowing the access to some, new, low molecular weight curdlan polysaccharide derivatives with unprecedented sulfation patterns. Three different semi-synthetic schemes were investigated, all relying upon the installation of a cyclic benzylidene protecting group on Glc O-4,6-diols, followed by either direct sulfation and deprotection, or some additional steps – including a hydrolytic or oxidative cleavage of the benzylidene rings – prior to sulfation and deprotection. The six obtained polysaccharides were subjected to a detailed structural characterization by 2D-NMR analysis, revealing that some of them showed the majority of Glc units along the polymeric backbone decorated by unprecedented sulfation motifs.

Relative risk of groundwater-quality degradation near California (USA) oil fields estimated from 3H, 14C, and 4He

Relative risks of groundwater-quality degradation near selected California oil fields are estimated by examining spatial and temporal patterns in chemical and isotopic data in the context of groundwater-age categories defined by tritium and carbon-14. In the Coastal basins, western San Joaquin Valley (SJV), and eastern SJV; 82, 76, and 0% of samples are premodern (pre-1953 recharge), respectively; and 3, 0, and 31% are modern (recharged during or after 1953), respectively. Carbon-14 and helium-4 data indicate most premodern samples are 1000 to 10,000 (33%) or >10,000 (50%) years old. Organic chemicals that could be associated with deeper hydrocarbon reservoirs (e.g. thermogenic gases and benzene) occur most frequently in premodern groundwater, suggesting premodern groundwater has a higher risk of degradation from upward migration of hydrocarbons than modern and mixed-age groundwater. Low sulfate concentrations in some premodern groundwater containing high thermogenic-methane concentrations (>28 mg/L) indicate methane attenuation associated with sulfate reduction can be limited in premodern groundwater. The more common occurrence of manufactured compounds, like tetrachloroethene, in modern and mixed-age groundwater than in premodern groundwater indicates modern and mixed-age groundwater has a higher risk of degradation from land-surface sources than premodern groundwater. Time-series data for chloride in groundwater affected by disposal of oil-field water in unlined ponds indicate some modern and mixed-age groundwater are susceptible to chemical migration within 2–3 km of surface sources. Timescales for diluting chloride concentrations in groundwater with fresh recharge once disposal ponds are decommissioned are shorter in mixed-age groundwater with large fractions of modern water (9–14 years in one example) than in mixed-age groundwater with large fractions of premodern water (no evidence of dilution after 12 years of monitoring in one example). The presence of predominantly premodern groundwater in the Coastal basins and western SJV indicates these areas have relatively high risk from upward migration of hydrocarbons, reduced methane attenuation capacity, and long dilution times, whereas predominantly modern- and mixed-age groundwater in the eastern SJV indicates this area has relatively high risk from chemical migration from land-surface sources and subsequent extensive spreading. Age-based characterizations of relative risk could inform the design of groundwater-monitoring programs near oil fields in terms of the spatial distribution of monitoring points relative to source areas and monitoring frequency and duration.

Stabilizing LiNi0.8 Co0.15 Mn0.05 O2 Cathode by Doping Sulfate for Lithium-Ion Batteries.

Residual sulfate (SO4 2- ) in precursor Ni0.8 Co0.15 Mn0.05 (OH)2 (pre-NCM) is commonly regarded as being harmful to Li[Ni0.8 Co0.15 Mn0.05 ]O2 (NCM) performance, leading to significant performance losses and also hampering the electrode fabrication. Therefore, manufacturers try their best to lower sulfate contents in pre-NCM. However, how the sulfate affects the cathode materials is not systematically studied. To address these issues, NCM was synthesized with different amounts of intentionally added sulfate (NH4 )2 SO4 in pre-NCM. It was demonstrated that anionic SO4 2- doped in NCM could influence the grain size in sintering process and stabilize the layer structure during the charge-discharge process at a certain doping amount. The first-principles calculations suggested that the SO4 2- doped in the transition metal layer could effectively facilitate Li+ diffusion in the lattice. SO4 2- doping could reduce the energy barrier for Li+ migration and then suppress drastic contraction of the c axis during cycling. The phase transition of H2 to H3 caused by c axis contraction was suppressed and the cycling performance was enhanced. The capacity retention could reach 80.9 (0.2 C) and 80.4 % (1 C) after 380 and 240 cycles in coin cells, respectively. These findings illustrate that a certain amount of sulfate could be beneficial to NCM cathodes.

Sulfate-dependent reversibility of intracellular reactions explains the opposing isotope effects in the anaerobic oxidation of methane.

The anaerobic oxidation of methane (AOM) is performed by methanotrophic archaea (ANME) in distinct sulfate-methane interfaces of marine sediments. In these interfaces, AOM often appears to deplete methane in the heavy isotopes toward isotopic compositions similar to methanogenesis. Here, we shed light on this effect and its physiological underpinnings using a thermophilic ANME-1-dominated culture. At high sulfate concentrations, residual methane is enriched in both 13C and 2H (13α = 1.016 and 2α = 1.155), as observed previously. In contrast, at low sulfate concentrations, the residual methane is substantially depleted in 13C (13α = 0.977) and, to a lesser extent, in 2H. Using a biochemical-isotopic model, we explain the sulfate dependence of the net isotopic fractionation through the thermodynamic drive of the involved intracellular reactions. Our findings relate these isotopic patterns to the physiology and environment of the ANME, thereby explaining a commonly observed isotopic enigma.

Effects of Moderate Nitrate and Low Sulphate Depositions on the Status of Soil Base Cation Pools and Recent Mineral Soil Acidification at Forest Conversion Sites with European Beech (“Green Eyes”) Embedded in Norway Spruce and Scots Pine Stands

High N depositions of past decades brought changes to European forests including impacts on forest soil nutrition status. However, the ecosystem responses to declining atmospheric N inputs or moderate N depositions attracted only less attention so far. Our study investigated macronutrient (N, S, Ca2+, Mg2+, K+) pools and fluxes at forest conversion sites over 80 years old in Central Germany with European beech (so-called “Green Eyes” (GE)). The GE are embedded in large spruce and pine stands (coniferous stands: CS) and all investigated forest stands were exposed to moderate N deposition rates (6.8 ± 0.9 kg ha−1 yr−1) and acidic soil conditions (pHH2O &lt; 4.7). Since the understanding of forest soil chemical and macronutrient status is essential for the evaluation of forest conversion approaches, we linked patterns in water-bound nutrient fluxes (2001–2018) and in predicted macronutrient storage in the herbaceous and tree layer to patterns in litter fall (2016–2017) and in forest floor and mineral soil macronutrient stocks at GE and CS assessed in 2018. Our results exhibited 43% (Nt) and 21% (S) higher annual throughfall fluxes at CS than at GE. Seepage water at 100 cm mineral soil depth (2001–2018) of CS is characterized by up to fivefold higher NO3− (GE: 2 ± 0.7 µmolc L−1; CS: 9 ± 1.4 µmolc L−1) and sevenfold higher SO42− (GE: 492 ± 220 µmolc L−1; CS: 3672 ± 2613 µmolc L−1) concentrations. High base cation (∑ Ca2+, Mg2+, K+) concentrations in CS mineral soil seepage water (100 cm depth: 2224 ± 1297 µmolc L−1) show significant positive correlations with SO42−. Tree uptake of base cations at GE is associated especially with a Ca2+ depletion from deeper mineral soil. Foliar litter fall turns out to be the main pathway for litter base cation return to the topsoil at GE (&gt;59%) and CS (&gt;66%). The litter fall base cation return at GE (59 ± 6 kg ha−1 yr−1) is almost twice as large as the base cation deposition (30 ± 5 kg ha−1 yr−1) via throughfall and stemflow. At CS, base cation inputs to the topsoil via litter fall and depositions are at the same magnitude (24 ± 4 kg ha−1 yr−1). Macronutrient turnover is higher at GE and decomposition processes are hampered at CS maybe through higher N inputs. Due to its little biomass and only small coverage, the herbaceous layer at GE and CS do not exert a strong influence on macronutrient storage. Changes in soil base cation pools are tree species-, depth- and might be time-dependent, with recently growing forest floor stocks. An ongoing mineral soil acidification seems to be related to decreasing mineral soil base cation stocks (through NO3− and especially SO42− leaching as well as through tree uptake).

Separation of Fe from Mn in the Cryogenian Sedimentary Mn Deposit, South China: Insights from Ore Mineral Chemistry and S Isotopes from the Dawu Deposit

Manganese and Fe have similar geochemical properties in the supergene environment. Separation of Mn and Fe is an important process for the formation of high-grade sedimentary manganese deposits. Large-scale manganese carbonate deposits (total reserves of approximately 700 Mt) were formed during the interglacial of the Sturtian and Marinoan in South China. The orebodies are hosted in the black rock series at the basal Datangpo Formation of the Cryogenian period. The Fe contents in ores range from 1.15 to 7.18 wt.%, with an average of 2.80 wt.%, and the average Mn/Fe ratio is 8.9, indicating a complete separation of Mn and Fe during the formation of manganese ores. Here, we present element data of manganese carbonates and sulfur isotopes of pyrite from the Dawu deposit, Guizhou, China, aiming to investigate the separation mechanism of Mn and Fe and the ore genesis. The Fe in ores mainly occurs as carbonate (FeCO3) and pyrite (FeS2). The Mn, Ca, Mg and Fe exist in the form of isomorphic substitutions in manganese carbonate. The contents of FeCO3 in manganese carbonates are similar in different deposits, with averages of 2.6–2.8 wt.%. The whole-rock Fe and S contents have an obvious positive correlation (R = 0.69), indicating that the difference of whole-rock Fe content mainly comes from the pyrite content. The δ34SV-CDT of pyrite varies from 40.0 to 48.3‰, indicating that the pyrite formed in a restricted basin where sulfate supply was insufficient and the sulfate concentrations were extremely low. Additionally, the whole-rock Fe content is negatively correlated with the δ34S values of the whole-rock and pyrite, with correlation coefficients of −0.78 and −0.83, respectively. Two stages of separations of Mn and Fe might have occurred during the mineralization processes. The reduced seawater became oxidized gradually after the Sturtian glaciation, and Fe2+ was oxidized and precipitated before Mn2+, which resulted in the first-stage separation of Mn and Fe. The residual Mn-rich and Fe-poor seawater flowed into the restricted rift basin. Mn and Fe were then precipitated in sediments as oxyhydroxide as the seawater was oxidized. At the early stage of diagenesis, organic matter was oxidized, and manganese oxyhydroxide was reduced, forming the manganese carbonate. H2S was insufficient in the restricted basin due to the extremely low sulfate concentration. The Fe2+ was re-released due to the lack of H2S, resulting in the second-stage separation of Mn and Fe. Finally, the manganese carbonate deposit with low Fe and very high δ34S was formed in the restricted basin after the Sturtian glaciation.