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Uranium(IV) oxide clusters, colloids, and materials are designed and studied for 1) nuclear materials applications, 2) understanding the environmental fate and transport of actinides, and 3) exploring the complex bonding behavior of open‐shell f‐elements. UIV‐oxyhydroxsulfate clusters are particularly relevant in industrial processes and in nature. Recent studies have shown that counter‐cations to these polynuclear anions differentiate rich structural topologies in the solid‐state. Herein, we present nine different structures with wheel‐shaped [U70(OH)36(O)64(SO4)60]4− (U70) linked into one‐ and two‐dimensional frameworks with sulfate, divalent transition metals (CrII, FeII, CoII, NiII) and UV. Small‐angle X‐ray scattering of these phases dissolved in butylamine reveals differing supramolecular assembly of U70 clusters, controlled primarily by sulfates. However, observed trends in transition metal linking guide future design of U70 materials with different topologies. Finally, U70 linking via UIV‐O‐UV‐O‐UIV bridges presents a rare example of mixed‐oxidation‐state uranium oxides without disorder. [ABSTRACT FROM AUTHOR]

A regio‐ and chemoselective method for the preparation of 6‐trifluoromethyl‐5‐benzoyl‐2‐methylsulfanyl pyrimidines and their pyrimidin‐4(3H)‐one analogues, from the cyclocondensation reaction of trifluoromethyl β‐enamino diketones with non‐symmetric 2‐methylisothiourea sulfates is reported. These diketones functioned as dual substrates by providing both products with high regioselectivity (only N3‐substituted isomer was observed) and high chemoselectivity. A new feature provided by the starting material proposed herein is the possibility to either maintain or eliminate the trifluoromethyl group, by choosing the solvent. [ABSTRACT FROM AUTHOR]

Vibrational spectroscopy has been used to characterize the three uncommon complex iron sulfates clairite, (NH4)2Fe3(SO4)4(OH)3 3H2O, metavoltine, Na6K2Fe2+Fe3+6(SO4)12O2·18H2O, and voltaite, K2Fe2+5Fe3+3Al(SO4)12 18H2O. The investigated specimens were formed at the burning coal dump Anna I (Alsdorf, Germany) due to alteration processes connected with the subsurface thermal activity. It is found that all three minerals display complex Raman spectra with an extensive proliferation of bands attributed to the sulfate vibrational modes. Both clairite and metavoltine show extraordinary strong Raman bands in the low‐wavenumber region, which can be attributed to the FeO stretching modes. Clairite and metavoltine show a very similar spectral shape; it can be concluded that both minerals can exhibit a similar crystal structure. In comparison, voltaite represents a different structural type; therefore, a distinct Raman spectrum is observed. [ABSTRACT FROM AUTHOR]

Essential and fixed oils have been researched as alternatives to chemical acaricides. The activity of volatile compounds from essential oils (1,8‐cineole, citral and eugenol) at 1.0% (w/v) and fixed oil (castor oil) at 0.3% (w/v) dissolved in 2.0% (v/v) dimethyl sulfoxide (DMSO) + 0.2% (w/v) Tween 80® was assessed against Rhipicephalus microplus using immersion tests. 1,8‐cineole (29.0%) and castor oil (30.2%) had the highest reproductive inhibition rate. A second experiment was performed to verify the effect of the 1,8‐cineole (10.0% w/v) and, or castor oil (0.3% w/v) on tick reproduction using different solubilizing agents. The highest reproductive inhibition was observed for the combination of 1,8‐cineole/castor oil (94.1%) and 1,8‐cineole in 2.0% (w/v) sodium lauryl ether sulphate (SLES) (92.8%). A third experiment showed morphological changes in R. microplus oocytes at different stages of development, as well as in pedicel cells. The most intense effects were observed when ticks were immersed in the formulation containing 1,8‐cineole (10.0% w/v) and castor oil (0.3% w/v) dissolved in 2% (w/v) SLES. These findings highlight the potential of this formulation as an alternative for managing cattle ticks as their cytotoxic effects can reduce R. microplus reproductive success. [ABSTRACT FROM AUTHOR]

Sulfated metabolites have been shown to have potential as long‐term markers of anabolic–androgenic steroid (AAS) abuse. In 2019, the compatibility of gas chromatography–mass spectrometry (GC–MS) with non‐hydrolysed sulfated steroids was demonstrated, and this approach allowed the incorporation of these compounds in a broad GC–MS initial testing procedure at a later stage. However, research is needed to identify which are beneficial. In this study, a search for new long‐term metabolites of two popular AAS, metenolone and drostanolone, was undertaken through two excretion studies each. The excretion samples were analysed using GC–chemical ionization–triple quadrupole MS (GC–CI–MS/MS) after the application of three separate sample preparation methodologies (i.e. hydrolysis with Escherichia coli–derived β‐glucuronidase, Helix pomatia–derived β‐glucuronidase/arylsulfatase and non‐hydrolysed sulfated steroids). For metenolone, a non‐hydrolysed sulfated metabolite, 1β‐methyl‐5α‐androstan‐17‐one‐3ζ‐sulfate, was documented for the first time to provide the longest detection time of up to 17 days. This metabolite increased the detection time by nearly a factor of 2 in comparison with the currently monitored markers for metenolone in a routine doping control initial testing procedure. In the second excretion study, it prolonged the detection window by 25%. In the case of drostanolone, the non‐hydrolysed sulfated metabolite with the longest detection time was the sulfated analogue of the main drostanolone metabolite (3α‐hydroxy‐2α‐methyl‐5α‐androstan‐17‐one) with a detection time of up to 24 days. However, the currently monitored main drostanolone metabolite in routine doping control, after hydrolysis of the glucuronide with E.coli, remained superior in detection time (i.e. up to 29 days). [ABSTRACT FROM AUTHOR]

Sulfate minerals are rare in the Archean rock record and largely restricted to the occurrence of barite (BaSO4). The origin of this barite remains controversially debated. The mass‐independent fractionation of sulfur isotopes in these and other Archean sedimentary rocks suggests that photolysis of volcanic aerosols in an oxygen‐poor atmosphere played an important role in their formation. Here, we report on the multiple sulfur isotopic composition of sedimentary anhydrite in the ca. 3.22 Ga Moodies Group of the Barberton Greenstone Belt, southern Africa. Anhydrite occurs, together with barite and pyrite, in regionally traceable beds that formed in fluvial settings. Variable abundances of barite versus anhydrite reflect changes in sulfate enrichment by evaporitic concentration across orders of magnitude in an arid, nearshore terrestrial environment, periodically replenished by influxes of seawater. The multiple S‐isotope compositions of anhydrite and pyrite are consistent with microbial sulfate reduction. S‐isotope signatures in barite suggest an additional oxidative sulfate source probably derived from continental weathering of sulfide possibly enhanced by microbial sulfur oxidation. Although depositional environments of Moodies sulfate minerals differ strongly from marine barite deposits, their sulfur isotopic composition is similar and most likely reflects a primary isotopic signature. The data indicate that a constant input of small portions of oxidized sulfur from the continents into the ocean may have contributed to the observed long‐term increase in Δ33Ssulfate values through the Paleoarchean. [ABSTRACT FROM AUTHOR]

The São Domingos area (Corte do Pinto, Portugal) represents a large sulfide ore deposit in the Iberian Pyrite Belt that was mined primarily for copper and sulfur in the past. Currently, the deserted mine and mine wastes are the reason for the production of acid mining drainage releasing potentially harmful elements. Because metastable secondary sulfates may temporary sink toxic pollutants, the in situ monitoring of their distribution is required. In this work, we tested a handheld Raman spectrometer equipped with a 532 nm laser excitation for this task. Twelve selected samples of complex composition were analyzed directly in the field using the handheld Raman spectrometer. For comparison, the collected samples were additionally analyzed through laboratory‐based Raman spectroscopy and X‐ray diffraction. Based on the in situ measurements, rozenite, melanterite, coquimbite, jarosite, metavoltine, chalcanthite, bonattite, antlerite, halotrichite‐group minerals, gypsum, and sulfur were detected. The results show that handheld Raman spectrometer is comparable with other laboratory techniques and such handheld systems can be deployed successfully for monitoring of sulfate distribution directly on site. [ABSTRACT FROM AUTHOR]

This study was carried out to investigate the potential therapeutic effect of galangin, a promising active principle of honeybee propolis, in dextran sulphate sodium (DSS)–induced colitis in mice. We explored the possible underlying mechanisms for galangin action and the therapeutic benefit of adding galangin to the standard therapy sulphasalazine. A galangin dose of 40 mg/kg was selected based on a preliminary dose‐selection study for investigation in a 4‐week cyclical model of DSS‐induced colitis. Mice received 3% DSS in their drinking water during the first and third weeks and were administered the treatments (40 mg/kg galangin, 100 mg/kg sulphasalazine and a combination of 20 mg/kg galangin and 50 mg/kg sulphasalazine) daily starting from the second week. Galangin significantly ameliorated DSS‐induced histopathological alterations and tissue injury, down‐regulated Toll‐like receptor 4 expression, suppressed NF‐κB p65 activation, lowered inflammatory cytokine levels and demonstrated antioxidant effects. The combination of galangin and sulphasalazine at half doses yielded comparable results to either drug alone at full dose. This study highlights galangin as a promising therapy for colitis management. [ABSTRACT FROM AUTHOR]

Background: This study evaluated the efficacy, safety, and acceptability of a new ferrous sulfate oral solution (Tardyferon® 20 mg/mL) in young children with mild or moderate iron deficiency anemia (IDA). Methods: This was a multicenter, national, single‐arm, open‐label study. Children aged 6–53 months presenting with mild or moderate IDA (i.e., blood hemoglobin (Hb) ranging from 7.0 to 10.9 g/dL and serum ferritin <12 ng/mL) were eligible for inclusion. The ferrous sulfate heptahydrate solution (2 mg/kg/day) was administered orally for 3 months. If normalization of either Hb or ferritin was not achieved at month 3 the treatment was continued for another 3 months. Results: Of the 100 children screened, 21 aged 6–17 months were included and received the study treatment, and 19 were analyzed for hematologic outcomes at month 3. Only one patient continued treatment for the additional 3 months. At month 3, mean ± SD Hb and ferritin levels were 12.0 ± 0.7 g/dL and 31.5 ± 19.4 ng/mL, respectively. Hemoglobin and ferritin levels were normalized in 95% (18/19) and 84% (16/19) of the patients, respectively. Treatment compliance and levels of satisfaction of both the parents and the investigators were high. Overall, 33.3% of patients (7/21) experienced at least one adverse event. Only one patient (4.8%) experienced a drug‐related adverse event (upper abdominal pain). Conclusions: A 2 mg/kg daily dose of the new oral ferrous sulfate heptahydrate solution provides substantial therapeutic benefit with high levels of tolerability in young children who have mild or moderate IDA. [ABSTRACT FROM AUTHOR]

Oral squamous cell carcinoma (OSCC) is a very aggressive malignancy, and 50% of patients who receive curative treatment die from the disease or related complications within 5 years. Epigallocatechin‐3‐gallate (EGCG) is the most abundant bioactive ingredient of tea polyphenols in green tea and has anticancer properties. Here, we evaluated the preclinical efficacy of EGCG combined with vincristine sulfate (VCR) on the growth, angiogenic activity and vascular endothelial growth factor (VEGF) expression in xenograft nude mice inoculated with KBV200 cells. Compared with VCR alone, the combined use of EGCG and VCR strongly inhibited tumour growth and angiogenesis (P < 0.01). VEGF mRNA and protein levels were lower in the KBV200 xenograft group treated with the combined regime (P < 0.01) than those in the VCR alone group. EGCG sensitises multidrug‐resistant OSCC to VCR, and this may occur through the inhibition of angiogenesis via VEGF down‐regulation. [ABSTRACT FROM AUTHOR]

Crystals of a new uranyl sulfate (C2N4H8S2)[UO2(SO4)2]·0.3H2O (1) templated by a relatively rare bis‐isothiouronium cation, were formed upon evaporation of aqueous solutions containing uranyl acetate, thiourea, and excess sulfuric acid. The new compound is orthorhombic, P212121, a = 6.928(2) Å, b = 13.398(3) Å, c = 15.225(3) Å, Z = 2. Its crystal structure is comprised of [UO2(SO4)2] moieties linked by hydrogen bonds formed between the template cations and terminal oxygen atoms of the sulfate tetrahedra. The C2N4H8S22+ template is most likely formed in situ during a redox reaction between uranyl cation and thiourea in a strongly acidic medium, with UO22+ partially reduced to U4+. [ABSTRACT FROM AUTHOR]

Summary: Chemotrophic microorganisms gain energy for cellular functions by catalyzing oxidation–reduction (redox) reactions that are out of equilibrium. Calculations of the Gibbs energy (ΔGr) can identify whether a reaction is thermodynamically favourable and quantify the accompanying energy yield at the temperature, pressure and chemical composition in the system of interest. Based on carefully calculated values of ΔGr, we predict a novel microbial metabolism – sulfur comproportionation (3H2S + SO42− + 2H+⇌ 4S0 + 4H2O). We show that at elevated concentrations of sulfide and sulfate in acidic environments over a broad temperature range, this putative metabolism can be exergonic (ΔGr<0), yielding ~30–50 kJ mol−1. We suggest that this may be sufficient energy to support a chemolithotrophic metabolism currently missing from the literature. Other versions of this metabolism, comproportionation to thiosulfate (H2S + SO42−⇌S2O32− + H2O) and to sulfite (H2S + 3SO42−⇌ 4SO32− + 2H+), are only moderately exergonic or endergonic even at ideal geochemical conditions. Natural and impacted environments, including sulfidic karst systems, shallow‐sea hydrothermal vents, sites of acid mine drainage, and acid–sulfate crater lakes, may be ideal hunting grounds for finding microbial sulfur comproportionators. [ABSTRACT FROM AUTHOR]

Exposure to vanadium has been associated with deleterious effects on the central nervous system in animals and humans. Although vanadium‐derived pro‐oxidant species were reported to be involved in vanadium‐mediated neurotoxicity, the ability of this metal to induce oxidative stress markers in glial cells remains to be elucidated. In this study, we investigated the cytotoxicity and the generation of reactive oxygen species (ROS) and nitric oxide (NO) by mouse primary astrocytes after treatment with vanadyl sulfate (VOSO4) at concentrations of 20, 50, 100, 200, and 500 μM. The resazurin assay revealed that treatment with VOSO4 for 24 and 48 h at concentrations of 50 and 100 μM, respectively, or higher substantially induced astrocytic cytotoxicity. Intracellular ROS increased after 6‐h exposure to the lowest concentration tested (20 μM VOSO4) and tended to intensify after 24‐ and 48‐h treatments reaching significant values for 20 and 500 μM VOSO4. In turn, NO production in the examined cells was elevated after exposure to all concentrations at the 6‐, 24‐, and 48‐h incubation periods. Our study demonstrated the ability of VOSO4 to induce H2O2 generation in cell‐free DMEM/F12 medium. The H2O2 levels were in the micromolar range (up to 5 μM) and were detected mostly during the first few minutes after VOSO4 addition, suggesting that the generated H2O2 could not induce toxic effects on the cells. Taken together, these results show VOSO4 induced cytotoxicity in primary astrocyte cells, which may have resulted from vanadyl‐stimulated intracellular ROS and NO generation in these cells. The regression analysis for the levels of H2O2 produced by VOSO4 in the culture medium showed that 86% and 85% of the variation in the concentration of H2O2 (measured after the 0‐ and 5‐min incubation with VOSO4, respectively) was determined by vanadium. [ABSTRACT FROM AUTHOR]

Organosulfates (OSs), a key component of secondary organic aerosols (SOA), account for up to one third of organic matter in the atmosphere. However, high molecular weight (HMW, 500–800 Da) OSs in ambient aerosols are poorly characterized at a molecular level, due to experimental difficulties. With Fourier transform‐ion cyclotron resonance mass spectrometry (FT‐ICRMS), we are able to identify more than 8,000 OSs in wintertime aerosols in Beijing. We found that both the number and signal magnitudes of HMW OSs with low H/C and O/C ratios and degrees of unsaturation were greatly enhanced during hazy days, indicating that most HMW OSs were freshly formed during stagnant air pollution episodes. They are most likely to be the oxidation products of semivolatility to low‐volatility precursors (e.g., polycyclic aromatic hydrocarbons and fatty acids) and have showed a strong influence of anthropogenic emissions. The molecular corridor analysis suggests that the high abundance of HMW aromatic‐like and aliphatic OSs considerably decreases the volatility of organic aerosols in the urban atmosphere. Key Points: Large numbers of high molecular weight organosulfates with low volatility are produced in urban aerosols with increased air pollutionNumerous aliphatic‐ and aromatic‐like OSs are potentially generated from anthropogenic precursors affected by urban emissionsThe high abundance of high molecular weight OSs decreases the volatility of urban organic aerosols [ABSTRACT FROM AUTHOR]

Summary: Sulfur‐oxidizing Sulfurimonas spp. are widespread in sediments, hydrothermal vent fields, aquifers and subsurface environments such as oil reservoirs where they play an important role in the sulfur cycle. We determined the genome sequence of the oil field isolate Sulfurimonas sp. strain CVO and compared its gene expression during nitrate‐dependent sulfide oxidation to the coastal sediment isolate Sulfurimonas denitrificans. Formation of elemental sulfur (S0) and high expression of sulfide quinone oxidoreductase (SQR) genes indicates that sulfide oxidation in both strains is mediated by SQR. Subsequent oxidation of S0 was achieved by the sulfur oxidation enzyme complex (SOX). In the coastal S. denitrificans, the genes are arranged and expressed as two clusters: soxXY1Z1AB and soxCDY2Z2H, and sulfate was the sole metabolic end product. By contrast, the oil field strain CVO has only the soxCDY2Z2H cluster and not soxXY1Z1AB. Despite the absence of the soxXY1Z1AB cluster, strain CVO oxidized S0 to thiosulfate and sulfate, demonstrating that soxCDY2Z2H genes alone are sufficient for S0 oxidation in Sulfurimonas spp. and that thiosulfate is an additional metabolic end product. Screening of publicly available metagenomes revealed that Sulfurimonas spp. with only the soxCDY2Z2H cluster are widespread suggesting this mechanism of thiosulfate formation is environmentally significant. [ABSTRACT FROM AUTHOR]

Silicate mercapto Duolite composite (SMDC) and activated Duolite A 101 D (AD) were prepared, characterized, and tested for uranium removal from sulfate solution using batch experiment technique. The capability of newly adsorbents for sorption of uranium was estimated and optimized under different controlling variables, including the impact of uranium initial concentration, pH of the medium, equilibrium time, temperatures, dose and interfering ions. Testing of different adsorbents for adsorption isotherms revealed that the achieved experimental data were fitting well with the Langmuir isotherm model with 68.02 mg·g–1 and 208.33 mg·g–1 as theoretical capacity for AD and SMDC, respectively. Thermodynamic parameters have been resulted in negative values for ΔH and ΔS indicating an exothermic and decreased randomness behavior for uranium(VI) adsorption, while negative values of ΔG indicate spontaneous uranium adsorption. The kinetics studies showed that the adsorption process was controlled expressed by pseudo‐second order model. Finally, the optimized factors have been applied for uranium(VI) recovery from Gattar leach liquor producing a uranium concentrate (Na2U2O7) with uranium concentration of 70 % and purity of 93.33 %. [ABSTRACT FROM AUTHOR]

Devils Lake is a terminal lake located in northeast North Dakota. Because of its glacial origin and accumulated salts from evaporation, the lake has a high concentration of sulfate compared to the surrounding water bodies. From 1993 to 2011, Devils Lake water levels rose by ~10 m, which flooded surrounding communities and increased the chance of an overspill to the Sheyenne River. To control the flooding, the State of North Dakota constructed two outlets to pump the lake water to the river. However, the pumped water has raised concerns about of water quality degradation and potential flooding risk of the Sheyenne River. To investigate these perceived impacts, a Soil and Water Assessment Tool (SWAT) model was developed for the Sheyenne River and it was linked to a coupled SWAT and CE‐QUAL‐W2 model that was developed for Devils Lake in a previous study. While the current outlet schedule has attempted to maintain the total river discharge within the confines of a two‐year flood (36 m3/s), our simulation from 2012 to 2018 revealed that the diversion increased the Sheyenne River sulfate concentration from an average of 125 to >750 mg/L. Furthermore, a conceptual optimization model was developed with a goal of better preserving the water quality of the Sheyenne River while effectively mitigating the flooding of Devils Lake. The optimal solution provides a "win–win" outlet management that maintains the efficiency of the outlets while reducing the Sheyenne River sulfate concentration to ≤600 mg/L. Research Impact Statement: The operation of the Devils Lake outlets can be optimized to reduce the impact on sulfate concentration of the Sheyenne River. [ABSTRACT FROM AUTHOR]

The noncentrosymmetric structure is one prerequisite of a nonlinear optical (NLO) material. Here, a sulfate Cs2Ca2(SO4)3 with a noncentrosymmetric structure was synthesized by high‐temperature solid‐state reaction, and its crystals were grown by spontaneous crystallization. Single‐crystal X‐ray diffraction indicates that Cs2Ca2(SO4)3 features a three‐dimensional framework constituted by corner‐sharing CaO6 octahedra and SO4 tetrahedra. Optical characterizations suggest that Cs2Ca2(SO4)3 is transparent down to 200 nm and exhibits a moderate second‐order NLO response of about 0.6 × KH2PO4. Electronic band structure calculations were performed to elucidate the optical origin. Furthermore, the title compound has good thermal stability of up to about 1000 K, which is greatly higher than those of NLO sulfates reported recently. This work may shed useful light on the development of new NLO sulfates with high thermal stability. [ABSTRACT FROM AUTHOR]

The noncentrosymmetric structure is one prerequisite of a nonlinear optical (NLO) material. Here, a sulfate Cs2Ca2(SO4)3 with a noncentrosymmetric structure was synthesized by high‐temperature solid‐state reaction, and its crystals were grown by spontaneous crystallization. Single‐crystal X‐ray diffraction indicates that Cs2Ca2(SO4)3 features a three‐dimensional framework constituted by corner‐sharing CaO6 octahedra and SO4 tetrahedra. Optical characterizations suggest that Cs2Ca2(SO4)3 is transparent down to 200 nm and exhibits a moderate second‐order NLO response of about 0.6 × KH2PO4. Electronic band structure calculations were performed to elucidate the optical origin. Furthermore, the title compound has good thermal stability of up to about 1000 K, which is greatly higher than those of NLO sulfates reported recently. This work may shed useful light on the development of new NLO sulfates with high thermal stability. [ABSTRACT FROM AUTHOR]

The Asian Tropopause Aerosol Layer (ATAL) represents an accumulation of aerosol in the upper troposphere and lower stratosphere associated with the Asian Summer Monsoon. Here we simulate the ATAL for summer 2013 with the GEOS‐Chem chemical transport model and explore the likely composition of ATAL aerosols and the relative contributions of regional anthropogenic sources versus those from farther afield. The model indicates significant contributions from organic aerosol, nitrate, sulfate, and ammonium aerosol, with regional anthropogenic precursor sources dominant. The model underestimates aerosol backscatter in the ATAL during summer 2013, compared with Cloud‐Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) satellite instrument. Tests of a more physically based treatment of wet scavenging of SO2 in convective updrafts raise sulfate, eliminating the low bias with respect to CALIPSO backscatter in the ATAL, but lead to an unacceptable high bias of sulfate compared with in situ observations from aircraft over the United States. Source apportionment of the model results indicate the dominance of regional anthropogenic emissions from China and the Indian subcontinent to aerosol concentrations in the ATAL; ~60% of sulfate in the ATAL region in August 2013 is attributable to anthropogenic sources of SO2 from China (~30%) and from the Indian subcontinent (~30%), twice as much as in previously published estimates. Nitrate aerosol is found to be a dominant component of aerosol composition on the southern flank of the Asian Summer Monsoon anticyclone. Lightning sources of NOx are found to make a significant (10–15%) contribution to nitrate in the ATAL for the case studied. Key Points: Regional anthropogenic emissions from China and India dominate aerosol concentrations in the ATAL, in contrast with previous estimatesGEOS‐Chem underestimates aerosol backscatter in the ATAL during summer 2013, compared with CALIPSO satellite instrumentA more physically based treatment of wet scavenging of SO2 in convective updraft is tested in GEOS‐Chem [ABSTRACT FROM AUTHOR]

Summary: Arabidopsis thaliana contains 13 fibrillins (FBNs), which are all localized to chloroplasts. FBN1 and FBN2 are involved in photoprotection of photosystem II, and FBN4 and FBN5 are thought to be involved in plastoquinone transport and biosynthesis, respectively. The functions of the other FBNs remain largely unknown.To gain insight into the function of FBN6, we performed coexpression and Western analyses, conducted fluorescence and transmission electron microscopy, stained reactive oxygen species (ROS), measured photosynthetic parameters and glutathione levels, and applied transcriptomics and metabolomics.Using coexpression analyses, FBN6 was identified as a photosynthesis‐associated gene. FBN6 is localized to thylakoid and envelope membranes, and its knockout results in stunted plants. The delayed‐growth phenotype cannot be attributed to altered basic photosynthesis parameters or a reduced CO2 assimilation rate. Under moderate light stress, primary leaves of fbn6 plants begin to bleach and contain enlarged plastoglobules. RNA sequencing and metabolomics analyses point to an alteration in sulfate reduction in fbn6. Indeed, glutathione content is higher in fbn6, which in turn confers cadmium tolerance of fbn6 seedlings.We conclude that loss of FBN6 leads to perturbation of ROS homeostasis. FBN6 enables plants to cope with moderate light stress and affects cadmium tolerance. [ABSTRACT FROM AUTHOR]

Luminol is chemically sufficiently stable to be diprotonated at high proton concentrations as provided by concentrated sulfuric acid. The luminol dication (5‐ammonium‐2‐hydro‐1,4‐phthalzinediol) sulfate was isolated as macroscopic single crystals and its structure was determined and refined from single‐crystal X‐ray data collected at 173 K [cell parameters: a = 8.3994(17) Å, b = 6.9985(14) Å, c = 17.486(4) Å, β = 90.85(3)°, V = 1027.8(4) Å3, space group P21/c]. The structure is comprised of layers stacked along the b axis. Intralayer interactions are accomplished by strong hydrogen bonds of three luminol dications to one central [SO4]2– ion. Interlayer interactions are formed by weak hydrogen bonds of one luminol dication to two [SO4]2– ions in the adjacent layers, respectively, and alternating sandwich and parallel‐displaced π‐π‐stacking of the 1‐hydropyridazine‐3,6‐diol moieties of luminol dications in adjacent layers, respectively. [ABSTRACT FROM AUTHOR]

Prion‐like transcellular spreading of tau in Alzheimer's Disease (AD) is mediated by tau binding to cell surface heparan sulfate (HS). However, the structural determinants for tau–HS interaction are not well understood. Microarray and SPR assays of structurally defined HS oligosaccharides show that a rare 3‐O‐sulfation (3‐O‐S) of HS significantly enhances tau binding. In Hs3st1−/− (HS 3‐O‐sulfotransferase‐1 knockout) cells, reduced 3‐O‐S levels of HS diminished both cell surface binding and internalization of tau. In a cell culture, the addition of a 3‐O‐S HS 12‐mer reduced both tau cell surface binding and cellular uptake. NMR titrations mapped 3‐O‐S binding sites to the microtubule binding repeat 2 (R2) and proline‐rich region 2 (PRR2) of tau. Tau is only the seventh protein currently known to recognize HS 3‐O‐sulfation. Our work demonstrates that this rare 3‐O‐sulfation enhances tau–HS binding and likely the transcellular spread of tau, providing a novel target for disease‐modifying treatment of AD and other tauopathies. [ABSTRACT FROM AUTHOR]

Background and Aim: PBK‐1701TC is a novel sulfate tablet‐based that contains 320 mg of simethicone and delivers 90% of the salt and water delivered by oral sulfate solution (OSS) preparation. This study evaluated the efficacy, safety, and tolerability of PBK‐1701TC compared with OSS in bowel preparation for colonoscopy. Methods: This randomized, multicenter, phase 3 non‐inferiority trial included adults aged 19 years or older with a body mass index of 19–30 kg/m2 undergoing colonoscopy at five university hospitals in Korea. The primary efficacy endpoint was successful bowel‐cleansing rate, defined as Harefield Cleansing Scale grade A or B as evaluated by blinded central readers. Secondary endpoints included the presence of residual air bubbles. Adverse events and laboratory evaluations were monitored to assess safety. Tolerability was assessed via participant interview. Results: Overall, 235 participants were randomized, and 224 were included in the per‐protocol analysis (PBK, 112; OSS, 112). Successful bowel cleansing was achieved for 95.5% (107/112) in the PBK group, which was non‐inferior to the OSS group (98.2%, 110/112) with a difference of −2.7% (one sided 97.5% confidence limit, −8.1%). The participants in the PBK group had fewer intraluminal bubbles (0.9% vs 81.3%, P < 0.001) and reported a lower incidence of nausea and vomiting, with better acceptance, taste, and willingness to repeat the regimen than those in the OSS group (all P < 0.05). Conclusion: The novel sulfate tablet, PBK‐1701TC, was non‐inferior to OSS with respect to bowel‐cleansing efficacy and exhibited better safety and tolerability in adults undergoing colonoscopy. [ABSTRACT FROM AUTHOR]

Studies on α‐nickel sulfate hexahydrate (NSH) crystals grown under different conditions are undertaken to investigate how changes in growth conditions affect crystal properties and whether or not there is any modification of the average crystal structure due to changes in crystallization conditions. Thermogravimetric and microhardness studies were carried out on the crystals grown from two different aqueous solutions, one of them containing an excess of sulfuric acid. Raman spectra were recorded and a single‐crystal neutron diffraction investigation was conducted on both crystals. A detailed comparison between the two crystal structures and their Raman spectra showed that, although the two crystal structures are very similar, there are slight differences, such as the change in unit‐cell volume, differences in the ionic structure, particularly of the sulfate ions, and changes in the hydrogen‐bonding network. During solution crystal growth of a salt like NSH, varying the ionic environment around the solute ions influences the interionic interactions between them. Hence it is suggested that the above‐mentioned structural differences result from a fine‐tuning of the interionic interaction between the cations and anions of NSH in the solution phase. This difference is finally carried over to the crystalline phase. The resulting small crystal structure differences are enough to produce measurable changes in the thermal stability and fragility of the crystals. These differences in crystal properties can be explained on the basis of the observed structural differences between the two crystals grown under different conditions. [ABSTRACT FROM AUTHOR]

Late Palaeozoic‐age strata from the Capitan Reef in west Texas show facies‐dependent heterogeneity in the sulphur isotopic composition of carbonate‐associated sulphate, which is trace sulphate incorporated into carbonate minerals that is often used to reconstruct the sulphur isotopic composition of ancient seawater. However, diagenetic pore fluid processes may influence the sulphur isotopic composition of carbonate‐associated sulphate. These processes variously modify the sulphur isotopic composition of incorporated sulphate from syndepositional seawater in shelf crest, outer shelf, shelf margin and slope depositional settings. This study used a new multicollector inductively‐coupled plasma mass spectrometry technique to determine the sulphur isotopic composition of samples of individual depositional and diagenetic textures. Carbonate rocks representing peritidal facies in the Yates and Tansill formations preserve the sulphur isotopic composition of Guadalupian seawater sulphate despite alteration of the carbon and oxygen isotopic compositions by meteoric and dolomitizing diagenetic processes. However, sulphur isotopic data indicate that limestones deposited in reef and slope facies in the Capitan and Bell Canyon formations largely incorporate sulphate from anoxic marine‐phreatic pore fluids isotopically modified from seawater by microbial sulphate reduction, despite generally preserving the carbon and oxygen isotopic compositions of Permian seawater. Some early and all late meteoric calcite cements have carbonate‐associated sulphate with a sulphur isotopic composition distinct from that of Permian seawater. Detailed petrographic and sedimentary context for carbonate‐associated sulphate analyses will allow for improved reconstructions of ancient seawater composition and diagenetic conditions in ancient carbonate platforms. The results of this study indicate that carbonate rocks that diagenetically stabilize in high‐energy environments without pore fluid sulphate gradients can provide a robust archive of ancient seawater's sulphur isotopic composition. [ABSTRACT FROM AUTHOR]

Sulfate cancrinite (SO4‐CAN) Na8[AlSiO4]6(SO4)(H2O)n (2.6 < n < 3.2) was synthesized under hydrothermal conditions at 200 °C and 48 hours. Three different Si‐Al sources were inserted: (a) kaolinite (K), (b) a gel of sodium‐waterglass and sodium aluminate (G), and (c) an oxide mixture of cristobalite and corundum (CK). The products were characterized by X‐ray powder diffraction (XRD), 29Si and 27Al MAS NMR spectroscopy, scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDXS) and BET surface area analysis as well as simultaneous thermoanalysis (TG‐DTA). Mostly nanocrystals of platelet habit and dimensions smaller than 100 nm (beside a very few larger crystals) were observed from K. In contrast the gel (G) yielded to cancrinites with typical rod‐like morphology and dimensions of 100 × 500 nm. Large prismatic cancrinites up to 5 μm width and 10 μm length were observed from the oxide mixture CK. Furthermore the transition kinetics of the cancrinites into nosean was investigated at a temperature of 1000 °C under open conditions. This process was already complete after 1 hour for the nanocrystals from K but needed 10 hours for the nanocrystals from G and the microcrystals from CK. The relations between the individual Si‐Al source and the crystal properties like size, habit, and thermal transition kinetics were discussed. [ABSTRACT FROM AUTHOR]

The extent of fractionation of sulfur isotopes by sulfate‐reducing microbes is dictated by genomic and environmental factors. A greater understanding of species‐specific fractionations may better inform interpretation of sulfur isotopes preserved in the rock record. To examine whether gene diversity influences net isotopic fractionation in situ, we assessed environmental chemistry, sulfate reduction rates, diversity of putative sulfur‐metabolizing organisms by 16S rRNA and dissimilatory sulfite reductase (dsrB) gene amplicon sequencing, and net fractionation of sulfur isotopes along a sediment transect of a hypersaline Arctic spring. In situ sulfate reduction rates yielded minimum cell‐specific sulfate reduction rates < 0.3 × 10−15 moles cell−1 day−1. Neither 16S rRNA nor dsrB diversity indices correlated with relatively constant (38‰–45‰) net isotope fractionation (ε34Ssulfide‐sulfate). Measured ε34S values could be reproduced in a mechanistic fractionation model if 1%–2% of the microbial community (10%–60% of Deltaproteobacteria) were engaged in sulfate respiration, indicating heterogeneous respiratory activity within sulfate‐reducing populations. This model indicated enzymatic kinetic diversity of Apr was more likely to correlate with sulfur fractionation than DsrB. We propose that, above a threshold Shannon diversity value of 0.8 for dsrB, the influence of the specific composition of the microbial community responsible for generating an isotope signal is overprinted by the control exerted by environmental variables on microbial physiology. [ABSTRACT FROM AUTHOR]

Nearly 70 years ago, it was shown that the reaction between equimolar amounts of SO3 and N2O5 results in dinitronium disulfate (NO2)2S2O7 rather than monosulfate (NO2)2SO4. Because SO3 can dimerize, it was believed for long that this feature is the main cause of the formation of nitronium disulfate. Then, it was discovered that the reaction of NOSO3Cl with N2O5 results in dinitronium disulfate, and (NO2)2SO4 was suggested as an intermediate. The development of Raman spectroscopy made it possible for us to solve the fundamental problem of the existence of an elusive dinitro sulfate. The inevitability of dinitro sulfate formation was demonstrated by the transformations of nitronium sulfates (NO2)2S2O7, NO2HSO4, and (NO2)[CF3C(O)OSO3], and the Raman spectroscopy technique has shown the presence of the compound in the solid reaction products. In order to establish the structure of solid dinitro sulfate, quantum chemical calculations of the nitro ester form (O2NOSO3NO2) and of the [OSO3NO2]− anion were performed, but the conclusions about the diionic structure [NO2]+2[SO4]2− were made only due to the synthesis of the related nitronium sulfates K (NO2)SO4 and K (NO2)S2O7 whose Raman spectra were compared with that of dinitro sulfate. The decomposition pathways of all these unstable molecules were established. Reactions of nitronium disulfates, (NO2)2S2O7 or (NO2)[CF3C(O)OS2O6], with CF3COOH showed that, unlike HNO3, the organic acid does not destroy the sulfate chains but can substitute terminal groups including nitronium ion. So the chemistry of nitronium monosulfates was studied for the first time, and the existence of an unstable dinitronium sulfate was proved using Raman spectroscopy. [ABSTRACT FROM AUTHOR]

In the luminous ostracod Cypridina (presently Vargula) hilgendorfii, Cypridina luciferyl sulfate (3‐enol sulfate of Cypridina luciferin) is converted to Cypridina luciferin by a sulfotransferase with 3′‐phosphoadenosine‐5′‐phosphate (PAP) as a sulfate acceptor. The resultant Cypridina luciferin is used for the luciferase–luciferin reaction of Cypridina to emit blue light. The luminescence stimulation with major organic cofactors was examined using the crude extracts of Cypridina specimens, and we found that the addition of coenzyme A (CoA) to the crude extracts significantly stimulated luminescence intensity. Further, the light‐emitting source in the crude extracts stimulated with CoA was identified as Cypridina luciferyl sulfate, and we demonstrated that CoA could act as a sulfate acceptor from Cypridina luciferyl sulfate. In addition, the sulfate group of Cypridina luciferyl sulfate was also transferred to adenosine 5′‐monophosphate (5′‐AMP) and adenosine 3′‐monophosphate (3′‐AMP) by a sulfotransferase. The sulfated products corresponding to CoA, 5′‐AMP and 3′‐AMP were identified using mass spectrometry. This is the first report that CoA can act as a sulfate acceptor in a sulfotransferase reaction. [ABSTRACT FROM AUTHOR]

Two organic–inorganic hybrid layered materials, namely poly[(μ‐1,4‐diaminobenzene‐κ2N:N′)[μ3‐sulfato(VI)‐κ4O:O′:O′′,O′′′]manganese], [Mn(SO4)(C6H8N2)]n, 1, and poly[(μ‐1,4‐diaminobenzene‐κ2N:N′)[μ3‐sulfato(VI)‐κ4O:O′:O′′,O′′′]copper], [Cu(SO4)(C6H8N2)]n, 2, have been synthesized using 1,4‐phenylenediamine (PPD) as an organic template and component (linker). Both materials form three‐dimensional frameworks. The crystal structures were determined using data from powder X‐ray diffraction measurements. The purity and morphology of the compounds were studied by elemental analyses and SEM investigations, and their thermal stabilities were determined by thermogravimetric and nonambient powder X‐ray diffraction measurements, which indicated that 1 is stable up to 537 K and 2 is stable up to 437 K. [ABSTRACT FROM AUTHOR]

Steroid detection and identification remain key issues in toxicology, drug testing, medical diagnostics, food safety control, and doping control. In this study, we evaluate the capabilities and usefulness of analyzing non‐hydrolyzed sulfated steroids with gas chromatography−mass spectrometry (GC–MS) instead of the conventionally applied liquid chromatography−mass spectrometry (LC–MS) approach. Sulfates of 31 steroids were synthesized and their MS and chromatographic behavior studied by chemical ionization−GC−triple quadrupole MS (CI−GC‐TQMS) and low energy−electron ionization−GC−quadrupole time‐of‐flight−MS (LE−EI−GC−QTOF−MS). The collected data shows that the sulfate group is cleaved off in the injection port of the GC–MS, forming two isomers. In CI, the dominant species (ie, [MH – H2SO4]+ or [MH – H4S2O8]+ for bis‐sulfates) is very abundant due to the limited amount of fragmentation, making it an ideal precursor ion for MS/MS. In LE−EI, [M – H2SO4].+ and/or [M – H2SO4 – CH3].+ are the dominant species in most cases. Based on the common GC–MS behavior of non‐hydrolyzed sulfated steroids, two applications were evaluated and compared with the conventionally applied LC–MS approach; (a) discovery of (new) sulfated steroid metabolites of mesterolone and (b) expanding anabolic androgenic steroid abuse detection windows. GC–MS and LC–MS analysis of non‐hydrolyzed sulfated steroids offered comparable sensitivities, superseding these of GC–MS after hydrolysis. For non‐hydrolyzed sulfated steroids, GC–MS offers a higher structural elucidating power and a more straightforward inclusion in screening methods than LC–MS. [ABSTRACT FROM AUTHOR]

This paper investigated the influence of compressive fatigue on the sulfate resistance of slag (0, 20, 50, and 70%) contained concrete under steam curing. After 10,000 cycles loading of 0.5, 0.6, and 0.7 stress level, the concrete was exposed to 5% Na2SO4 for 540 days. The compressive strength, relative dynamic modulus of elasticity (RDME) and SO42− contents were tested after sulfate immersion. Results showed that the standard‐cured fatigued concrete had less strength reduction than the steam‐cured fatigued concrete during sulfate attack. The steam‐cured fatigued concrete containing 20% slag suffered the largest strength reduction, followed by the concrete containing 50, 70, and 0% slag. Compressive fatigue at high stress level (0.7) accelerated the sulfate deterioration of PC standard‐cured concrete, while the effect of low stress level (0.5) was minor. The RDME was not a sensitive indicator to access the sulfate resistance of concrete at the beginning of immersion. Compressive fatigue distinctly promoted the sulfate diffusion; the effective SO42− diffusion coefficient was increased when damage occurred in slag concrete. Besides, based on the fatigue damage, an experimental model of the sulfate deterioration of fatigued concrete was proposed. [ABSTRACT FROM AUTHOR]

In this study, mechanical, visual, and microstructure changes of geopolymer concrete exposed to sulfate and salt effects were investigated. Elazığ ferrochrome slag (EFS) and blast furnace slag (BFS)‐based geopolymer concretes which completed curing time were immersed in 5% sodium sulfate (Na2SO4), magnesium sulfate (MgSO4), sodium chloride (NaCl), and magnesium chloride (MgCl2) solutions for 12 weeks. The compressive strength values, ultrasonic pulse velocities, visual inspections, weight, and length changes of the samples were determined in this investigation. In addition, scanning electron microscopy was performed for the microstructure analysis of the samples removed from the solutions. Sulfate solutions had a more negative effect on the samples than salt solutions. As the EFS ratio in the mixture increases, the loss rate in the strength of the samples exposed to sulfate and salt solutions decreased. While samples exposed to sodium chloride, sodium sulfate, and magnesium sulfate solutions occurred weight gain, samples exposed to magnesium chloride occurred weight loss. The samples in salt solutions shrank, while the samples in sulfate solutions expanded. No deterioration occurred on the surfaces of the samples exposed to the solutions for 12 weeks. [ABSTRACT FROM AUTHOR]

Keywords: lanthanide; inorganic network; CO2 adsorption; structural transformation; magnetic propertiesThis study shows how pH and reaction temperatures can change the structure of antiferromagnetic rare earth sulfate‐based inorganic networks. Thermal dehydration and coordination geometry and dimensionality alterations cause irreversible structural transformations in the compounds, affecting CO2 sorption (DOI: 10.1002/zaac.202300161)...By Suwadee Jiajaroen; Songwuit Chanthee; Winya Dungkaew; Filip Kielar; Mongkol Sukwattanasinitt; Shinya Hayami and Kittipong ChainokReported by Author; Author; Author; Author; Author; Author; Author [Extracted from the article]

Microbial sulfur cycling in marine sediments often occurs in environments characterized by transient chemical gradients that affect both the availability of nutrients and the activity of microbes. High turnover rates of intermediate valence sulfur compounds and the intermittent availability of oxygen in these systems greatly impact the activity of sulfur‐oxidizing micro‐organisms in particular. In this study, the thiosulfate‐oxidizing hydrothermal vent bacterium Thiomicrospira thermophila strain EPR85 was grown in continuous culture at a range of dissolved oxygen concentrations (0.04–1.9 mM) and high pressure (5–10 MPa) in medium buffered at pH 8. Thiosulfate oxidation under these conditions produced tetrathionate, sulfate, and elemental sulfur, in contrast to previous closed‐system experiments at ambient pressure during which thiosulfate was quantitatively oxidized to sulfate. The maximum observed specific growth rate at 5 MPa pressure under unlimited O2 was 0.25 hr−1. This is comparable to the μmax (0.28 hr−1) observed at low pH (<6) at ambient pressure when T. thermophila produces the same mix of sulfur species. The half‐saturation constant for O2 (KO2) estimated from this study was 0.2 mM (at a cell density of 105 cells/ml) and was robust at all pressures tested (0.4–10 MPa), consistent with piezotolerant behavior of this strain. The cell‐specific KO2 was determined to be 1.5 pmol O2/cell. The concentrations of products formed were correlated with oxygen availability, with tetrathionate production in excess of sulfate production at all pressure conditions tested. This study provides evidence for transient sulfur storage during times when substrate concentration exceeds cell‐specific KO2 and subsequent consumption when oxygen dropped below that threshold. These results may be common among sulfur oxidizers in a variety of environments (e.g., deep marine sediments to photosynthetic microbial mats). [ABSTRACT FROM AUTHOR]

The brownmillerite, also known as tetracalcium aluminoferrite (C4AF), represents a solid solution series of Ca2(AlyFe(2–y))O5 (0 ≥ y ≤ 1.33), which is one of the most important components in ordinary Portland cement. The hydration of brownmillerite in the presence of gypsum attracts massive attentions, but the hydration mechanism remains controversial nowadays. In particular, the influence of Al/Fe ratio on brownmillerite hydration with gypsum is obscure and out of favor. This paper studies the hydration characteristics of a binary system containing brownmillerite and gypsum with variables including two Al/Fe ratios and gypsum contents in an attempt to interpret the retarding mechanism of sulfate ions. When the molar ratio of brownmillerite to gypsum is 1.0, the hydration process of Ca2(Al1.3Fe0.7)O5 shows five distinct stages in the conductivity test, while only two stages are observed in the case of Ca2(Al1.0Fe1.0)O5. A decrease of Al/Fe ratio in brownmillerite leads to severe stagnation of the hydration process. When the molar ratio of Ca2(Al1.0Fe1.0)O5 to gypsum is increased to 2.7, the hydration is able to proceed and also displays five stages similar to Ca2(Al1.3Fe0.7)O5. An adsorption layer of sulfate ions on the surface of brownmillerite contributes to the postponement of brownmillerite hydration. In addition, the concentration of aluminum in the solution is the key to break this adsorption layer and dominate the hydration proceeding of brownmillerite. [ABSTRACT FROM AUTHOR]

The chemical and stable isotopic compositions (δ34SSO4 and δ18OSO4) of Xijiang River water in southwest China, were measured to determine the extent of rock weathering and associated CO2 consumption rates, and to assess the contamination sources of river water. The SO42− concentration in the river water was in the range of 0.05 to 0.96 mmol L−1 (mean value = 0.32 mmol L−1) and was characterized by δ34SSO4 values ranging from −9.1 to 5.1‰ (mean value = −2.1‰) and δ18OSO4 values ranging from −0.4 to 10.8‰ (mean value = 5.0‰). The δ34SSO4 and δ18OSO4 values ranged from high to low from the upper reaches to the lower reaches in all the river water samples. The results indicate that the oxidation of sulfide and anthropogenic inputs are the dominant processes affecting SO42− sources and S cycling of the Xijiang River during high‐discharge conditions, which are controlled by regional hydrological processes that are affected by natural processes and anthropogenic inputs Core Ideas: The dual isotopes (δ34SSO4 and δ18OSO4) of sulfate indicated S sources.The weathering rates of carbonate and silicate were calculated.The relative contributions of various sources are identified. [ABSTRACT FROM AUTHOR]

Condition deterioration of the concrete, especially in corrosive environments, is one of the most common imperfection and disadvantages of reinforced concrete structures. Sulfates' main damages are expansion and loss of strength. Geopolymers are one of the newest structural materials that have been widely developed in recent years for use in sustainable designs. Geopolymers are environmentally friendly and considered as green materials since they are effective in sustainable and eco‐friendly material design concept. One of the most important matters in the sustainability of structural materials is their resistance against sulfates. So far, the durability of perlite‐based geopolymers against sulfates and acids has not been investigated. In this research, the fineness influence, curing conditions, duration of maintaining in the sulfate environment at different weight percentage in solution (i.e., 2.5, 5, 7.5, and 10%) have been investigated. Compressive strength and microstructure changes of geopolymer samples have been assessed in this research. As a result, optimum increase in perlite fineness causes increase in compressive strength and durability of samples against sulfate attack. Also, samples that have been cured by autoclave method have better mechanical properties and better durability. It is hoped that by filling these deficiencies and gaps, a positive step can be taken to accelerate attempts for finding a suitable replacement for ordinary Portland cement. [ABSTRACT FROM AUTHOR]

The introduction of alternative markers to the steroid profile can be an effective approach to improving the screening capabilities for the detection of testosterone (T) misuse. In this work, endogenous steroid sulfates were evaluated as potential markers to detect intramuscular (IM) T administration. Fourteen sulfate metabolites were quantified using mixed‐mode solid‐phase extraction and analysis by liquid chromatography–tandem mass spectrometry (LC–MS/MS). Urine samples after a single IM injection (100 mg) of T cypionate to six Caucasian and six Asian healthy male volunteers were analyzed. Principal component analysis (PCA) was used to characterize the sample cohort and to obtain the most useful markers for discrimination between pre‐ and post‐administration samples. For Caucasian volunteers, a separation between pre‐ and post‐administration samples was observed in PCA, whereas for Asian volunteers no separation was obtained. Seventeen ratios between sulfate metabolites were selected and further considered. Detection times (DTs) of each marker were evaluated using individual thresholds for each volunteer. The best results were obtained using ratios involving T and epitestosterone (E) sulfates in the denominator. The best marker was the ratio androsterone sulfate/testosterone sulfate (A‐S/T‐S) which prolonged the DT 1.2–2.1 times in respect to those obtained using T/E ratio in all Caucasian volunteers and 1.3–1.5 times in two Asian volunteers. Other ratios between A‐S or etiocholanolone sulfate and E‐S, and sulfates of etiocholanolone, dehydroandrosterone or epiandrosterone, and T‐S were also found adequate. These ratios improve the DT after IM T administration and their incorporation to complement the current steroid profile is recommended. [ABSTRACT FROM AUTHOR]

Nowadays, several techniques have been utilized to remove sulfate from industrial sewage. The method using ZrO(OH)2 to adsorb sulfate is highly efficient and environmentally friendly, however, nano‐powdered ZrO(OH)2 is hard to be recycled owing to its great loss in the adsorption process, which brings enormous difficulties to industrial applications. In this research, to prevent adsorbents from losing, Y‐zeolite was modified with zirconium, including the incorporation of zirconium as heteroatoms into zeolite frameworks and ion‐exchange of Zr4+ into the cages of zeolite, and then used as carrier to load ZrO(OH)2 to fabricate adsorbent via the stepwise impregnation treatment. The as‐prepared supported adsorbent ZrO(OH)2/Y‐zeolite has a high SO42− adsorption capacity, a strong adsorption selectivity to SO42− and good adsorption‐regeneration circulation performances. The saturated SO42− adsorption capacity of 284.22 mg/g can be obtained under the following adsorption conditions: SO42− concentration of 10 g/L, the pH value of 1.5, the temperature of 25 °C. After five adsorption‐regeneration circulations, its adsorption capacity has decreased only about 10%. The adsorption‐ desorption of sulfate over ZrO(OH)2/Y‐zeolite adsorbent proceeds according to the ion‐exchange mechanism between sulfate and the surface hydroxyl groups. [ABSTRACT FROM AUTHOR]

The preparation and structural characterization of an original Th peroxo sulfate dihydrate, crystallizing at room temperature in the form of stable 1D polymeric microfibres is described. A combination of laboratory and synchrotron techniques allowed solution of the structure of the Th(O2)(SO4)(H2O)2 compound, which crystallizes in a new structure type in the space group Pna21 of the orthorhombic crystal system. Particularly, the peroxide ligand coordinates to the Th cations in an unusual μ3‐η2:η2:η2 bridging mode, forming an infinite 1D chain decorated with sulfato ligands exhibiting simultaneously monodentate and bidentate coordination modes. [ABSTRACT FROM AUTHOR]

More than 2,000 analyses of beryllium‐10 (10Be) and sulfate concentrations were performed at a nominal subannual resolution on an ice core covering the last millennium as well as on records from three sites in Antarctica (Dome C, South Pole, and Vostok) to better understand the increase in 10Be deposition during stratospheric volcanic eruptions. A significant increase in 10Be concentration is observed in 14 of the 26 volcanic events studied. The slope and intercept of the linear regression between 10Be and sulfate concentrations provide different and complementary information. Slope is an indicator of the efficiency of the draining of 10Be atoms by volcanic aerosols depending on the amount of SO2 released and the altitude it reaches in the stratosphere. Intercept gives an image of the 10Be production in the stratospheric reservoir, ultimately depending on solar modulation. The Samalas event (1257 CE) stands out from the others as the biggest eruption of the last millennium with the lowest positive slope of all the events. We hypothetize that the persistence of volcanic aerosols in the stratosphere after the Samalas eruption has drained the stratospheric 10Be reservoir for a decade, meaning that solar reconstructions based on 10Be should be considered with caution during this period. The slope of the linear regression between 10Be and sulfate concentrations can also be used to correct the 10Be snow/ice signal of the volcanic disturbance. Key Points: Beryllium‐10 deposition on polar ice sheets is influenced by stratospheric volcanic eruptionsThe biggest volcanic eruption of the last millennium, the Samalas (1257 CE), probably drained out the polar stratospheric 10Be reservoir over a decadeSolar reconstructions based on 10Be ice core records must take into account volcanic disturbance [ABSTRACT FROM AUTHOR]

Cooling crystallization was successfully carried out in a batch cooling crystallizer from impure acidic solutions to recover nickel as nickel sulfate salt with three different cooling rates. The compositions of the solutions included impurities of sodium, magnesium, chloride, and sulfuric acid to mimic industrial nickel electrowinning process solutions. The results show that NiSO4.6H2O mainly crystallized, and its solubility and purity decreased with the increase in the mass ratio of chloride to sulfate. Cooling rates did not have a significant influence on crystal purity; however, it did affect the filter cake moisture; lower moisture can be obtained with a lower cooling rate. The sequence of impurity removal efficiency from high to low was Cl >Na > Mg. [ABSTRACT FROM AUTHOR]

At a service station closed in 1993, groundwater contained benzene that persisted above the cleanup goal of 1 mg/L in zones depleted of background sulfate. The benzene and other petroleum hydrocarbons (PHCs) were present as much as 36 feet (11 m) below the water table and therefore remediation of a thick saturated zone interval was required. Microcosms using site sediments demonstrated that anaerobic benzene biodegradation occurred only if sulfate was added, suggesting sulfate addition as a remediation approach. Twenty‐four boreholes (9.1″ diameter and 56′ deep) were drilled around four monitoring wells, in which benzene concentrations exceeded 1 mg/L. The boreholes were backfilled with a mixture of gravel and 15,000 pounds of gypsum (which releases sulfate as it dissolves) to create "Permeable Filled Borings" (PFBs). Concurrently, nine high pressure injections (HPIs) of gypsum slurry were conducted in other site locations (312 pounds of gypsum total). PFBs were expected to release sulfate for up to 20 years, whereas HPIs were expected to produce a short‐lived plume of sulfate. Concentrations of benzene and sulfate in groundwater were monitored over a 3‐year period in six monitoring wells. In two wells near PFBs, benzene concentrations dropped below the cleanup goal by two to three orders of magnitude; in one well, sulfate concentrations exceeded 500 mg/L for the most recent 18 months. Benzene concentrations in two other PFB monitoring wells declined by a factor of 2 to 4, but remained above 1 mg/L, presumably due to high‐dissolved PHC concentrations and possibly greater residual PHC mass in adjacent sediments, and therefore greater sulfate demand. However, hydrogen and sulfur isotopic enrichment in benzene and sulfate, respectively, confirmed biodegradation of benzene and stimulation of sulfate‐reducing conditions. Thus, it is hypothesized that the PHC mass in adjacent sediments will decline over time, as will dissolved PHC concentrations, and eventually benzene concentrations will decrease below the cleanup goal. Benzene in two HPI monitoring wells was below the cleanup goal for all but one sampling event before HPIs were conducted and remained below the cleanup goal after HPIs; there was no stimulation of sulfate‐reducing conditions. It is concluded that sulfate released from PFBs contributed to declining benzene concentrations. [ABSTRACT FROM AUTHOR]

Ancient stratigraphy on Isidis Basin's western margin records the history of water on early Mars. Noachian units are overlain by layered, basaltic composition sedimentary rocks that are enriched in polyhydrated sulfates and capped by more resistant units. The layered sulfates—uniquely exposed at northeast Syrtis Major—comprise a sedimentary sequence up to 600 m thick that has undergone a multistage history of deposition, alteration, and erosion. Siliciclastic sediments enriched in polyhydrated sulfates are bedded at meter scale and were deposited on slopes up to 10°, embaying and thinning against preexisting Noachian highlands around the Isidis Basin rim. The layered sulfates were modified by volume loss fracturing during diagenesis. Resultant fractures hosted channelized flow and jarosite mineral precipitation to form resistant ridges upon erosion. The structural form of the layered sulfates is consistent with packages of sediment fallen from either atmospheric or aqueous suspension; coupling with substantial diagenetic volume loss may favor deepwater basin sedimentation. After formation, the layered sulfates were capped by a "smooth capping unit" and then eroded to form paleovalleys. Hesperian Syrtis Major lavas were channelized by this paleotopography, capping it in some places and filling it in others. Later fluvial features and phyllosilicate‐bearing lacustrine deposits, sharing a regional base level of ∼−2,300 m, were superimposed on the sulfate‐lava stratigraphy. The layered sulfates suggest surface bodies of water and active groundwater upwelling during the Noachian‐Hesperian transition. The northeast Syrtis Major stratigraphy records at least four distinct phases of surface and subsurface aqueous activity spanning from late Noachian to early Amazonian time. Key Points: The eroded stratigraphy at Northeast Syrtis Major includes meter‐scale‐layered, sulfate‐enriched sedimentary basin deposits up to 600 m thickLayer dips <10° and topographic high embayment are consistent with deepwater deposition; volume loss fractures indicate diagenetic dewateringStrata also including Syrtis Major lavas and fluvio‐deltaic phyllosilicates record three fluvio‐lacustrine episodes into the early Amazonian [ABSTRACT FROM AUTHOR]

Two ionic carbon nitride type compounds containing the ammelinium cation, ammelinium sulfate cyanuric acid (6C3N5H6O+·3SO4 2-·12/3C3N3H3O3·H2O) (1) and ammelinium sulfate monohydrate (2C3N5H6O+·SO4 2-·H2O) (2) were synthesized through hydrolysis of melam (C6N11H9) in diluted sulfuric acid. 1 crystallizes in hexagonal space group P63 (no. 173) with lattice parameters of a = 14.642(3), c = 13.113(4), and Z = 2. The structure is comprised of protonated ammelinium ions and neutral cyanuric acid molecules, which form a layered structure, as well as sulfate ions that span through these layers. 2 crystallizes in the triclinic space group P1¯ with lattice parameters of a = 7.404(3), b = 9.673(4), c = 10.040(4), α = 91.098(15), β = 109.884(10), γ = 92.567(13), and Z = 2. As for 1, the ammelinium rings form layers with the sulfate ions located in between. In both structures, no extended hydrogen bond networks between the respective triazine-based molecules are formed. Instead, single molecules or small building blocks occur isolated and interact primarily with sulfate anions. Compound 1, which was obtained phase pure, was further investigated by FTIR spectroscopy, solid-state NMR spectroscopy and powder X-ray diffractometry. [ABSTRACT FROM AUTHOR]

Non‐icy material on the surface of Jupiter's moon Europa is hypothesized to have originated from its subsurface ocean and thus provide a record of ocean composition and habitability. The nature of this material is debated, but observations suggest that it comprises hydrated sulfate and chloride salts. Analogue spectroscopic studies have previously focused on single‐phase salts under controlled laboratory conditions. We investigated natural salts from perennially cold (<0 °C) hypersaline springs and characterized their reflectance properties at 100, 253, and 293 K. Despite similar major ion chemistry, these springs form mineralogically diverse deposits, which when measured at 100 K closely match reflectance spectra from Europa. In the most sulfate‐rich samples, we find that spectral features predicted from laboratory salts are obscured. Our data are consistent with sulfate‐dominated europan non‐icy material and further show that the emplacement of endogenic sulfates on Europa's surface would not preclude a chloride‐dominated ocean. Plain Language Summary: Europa, a moon of Jupiter, has become a priority target in the search for life off the Earth, due to the presence of a liquid water ocean under its icy shell. Salts on the moon's surface might originate from this ocean and therefore offer a way of studying the ocean without requiring direct access. Our knowledge of these salts comes from comparing spacecraft measurements to pure salts produced in laboratories. We have studied natural salts from hypersaline springs in the Canadian Arctic as an alternative, complementary approach. Measuring samples from these deposits at europan surface temperatures, several unexpected properties were observed, including the absence of spectral details predicted by previous laboratory studies. This challenges some of the estimates of europan surface composition. Natural analogues such as these will form part of an integrative approach to understanding data from upcoming missions, such as the National Aeronautics and Space Administration's (NASA) Europa Clipper and the European Space Agency's JUpiter ICy moons Explorer. Key Points: Low‐temperature hydrated salts from the Canadian Arctic provide geochemical and spectral analogues for europan surface materialQualitatively different deposits can form from fluids with similar major ion chemistryEndogenic sulfates on Europa would not rule out a chloride‐dominated ocean [ABSTRACT FROM AUTHOR]

Lots of concrete structures are located in marine environment, the durability damage of these structures is often the result of the interaction of load, environment, and other factors. In this paper, tests for the stress–strain relation of concrete under the coupled effects of sustained loading, sulfate attack and dry‐wet cycle were conducted. Then, based on the damage stress–strain relation model of concrete under sulfate attack, a calculation method for the stress–strain relation of concrete under the action of sulfate attack and dry‐wet cycle was proposed. Meanwhile, by taking into account the effect of creep on the stress–strain relation of concrete, a time‐dependent stress–strain relation model of concrete was presented. Numerical simulations by the time‐dependent stress–strain relation model demonstrate that the calculated results agree well with the experimental data. Furthermore, the rationality and applicability of the time‐dependent stress–strain relation model were also discussed. [ABSTRACT FROM AUTHOR]