Total Sulfide Research Articles

Remediation of Sulfides in Produced Waters of the Oil and Gas Industry Using Hydrogen Peroxide

Produced waters are often treated in open lagoons where hydrogen sulfide (H2S) can off gas, posing a risk to human health and the environment. The aim of this study was to optimize a treatment process using hydrogen peroxide (H2O2) to oxidize H2S while minimizing off gassing. Samples of produced water from West Texas and laboratory-prepared waters utilizing sodium sulfide (Na2S) or biogenic polysulfides were oxidized with H2O2 alone or in combination with copper or iron catalysts, sodium hydroxide (NaOH), or a commercial sulfide oxidizer, HydroPower Green™. Sulfur speciation was measured using Hach test kits for sulfide/sulfate/sulfite and Dräger tubes for headspace H2S. HydroPower Green™ (HPG) helped to reduce H2S in the headspace of water samples; some of this was pH related as NaOH also worked, but not as well as HPG. The dose of peroxide necessary to oxidize sulfides to sulfate is a function of the oxidation-reduction potential (Eh) of the water and total sulfide concentration as well as pH; approximately a 1–4:1 ratio of peroxide to sulfide concentration was needed to oxidize sulfidic waters of pH 7–10 with half-lives under 30 min. Both copper and iron catalysts reduce H2O2 demand and the half-life of H2S. Peracetic acid (PAA) and copper (II) sulfate pentahydrate (CuSO4, 5H2O) were explored as biocides for controlling sulfate-reducing bacteria (SRBs) that produce H2S. An AquaSnap (Hygenia) test kit was employed to monitor relative microbial activity in a wetland porewater containing H2S. Microbial regrowth occurred after a few days using the highest dose of PAA; these results showed that PAA was being used by bacteria as a carbon source even after the initial substantial reduction in the microbial activity. CuSO4, 5H2O at a dose of 1 ppm prevented microbial regrowth. The recommended treatment process from this research is determined by jar testing with H2O2, a base for pH control, a biocide, and possibly a metal catalyst or other co-oxidants in order to achieve oxidation of sulfides without H2S release or the precipitation of metal carbonates or oxides.

Water Quality Assessment of Lake Maninjau After the Mass Fish Kill Event

A mass fish kill is often occurring in Lake Maninjau. A lack of oxygen has reportedly resulted in numerous fish kills, including the recent lake Maninjau condition. Deoxygenation of lake water is a natural phenomenon that often occurs after heavy rain events and low sunlight intensity. Additionally, during the strong wind for a long period, the decrease in oxygen could be chemically triggered by the diffusion of sulfide from the bottom layer of the water column. Furthermore, this study examines water quality parameters after the mass fish mortality occurred across locations in Lake Maninjau. Field surveys were conducted by measuring physiochemical parameters and total sulfide at the Fifteen sampling points (five points in the middle and ten points around the lake) from November 26 to December 2, 2022. They were measured directly using the Horriba©U 52 water quality checker (WQC), DO meter YSI ProDO© International and the HACH spectrophotometer DR3900 method. The results show that the average DO levels at each observation point were close to 0 mg/L while the average sulfide level on the surface was 9.5 micro g/L. The average Oxidation Reduction Potential (ORP) of -79.26 mV indicates that the lake is in a reduced state and signifies that much of the dead and decaying material in the water would be slowly broken down and decomposed. Low ORP values indicate that the compound in the water is available in reduced form, which is more toxic. Our diel DO measurement show that sunlight intensity was effective in increasing oxygen concentration in the lake.

Crystal Chemistry, Thermal and Radiation-Induced Conversions and Indicatory Significance of S-Bearing Groups in Balliranoite

Crystal-chemical features of a sulfide-bearing variety of the cancrinite-group mineral balliranoite from the Tuluyskoe lapis lazuli deposit, Baikal Lake area, Siberia, Russia, have been investigated using a multimethodic approach based on infrared (IR), Raman, and electron spin resonance (ESR), as well as ultraviolet, visible and near infrared (UV–Vis–near IR) absorption spectroscopy methods, luminescence spectroscopy, electron microprobe analysis, selective sorption of CO2 and H2O from annealing products, and single-crystal X-ray structure analysis. Holotype balliranoite and its sulfate analogue, davyne, were studied for comparison. The crystal-chemical formula of the studied sample from Tultuyskoe is Na5.4K0.1Ca2.4(Si6Al6O24)Cl2[(CO3)0.7(SO4)0.18S*0.95Cl0.1(H2O)0.16], where the content of the wide zeolite channel is given in square brackets; S* is total sulfide sulfur occurring as disordered S2●−, cis- and trans-S4, S52−, minor S3●−, and HS− groups. The presence of S52− and HS− groups, the absence of CO2 molecules, and the association with pyrrhotite and Fe-free pargasite indicate that the studied sample crystallized under highly reducing, low-temperature conditions, unlike holotype balliranoite whose formation was related to the Somma-Vesuvius volcanic complex, Italy. Irradiation of balliranoite from Tultuyskoe with X-rays results in the transformations of polysulfide groups other than S3●− into S3●− in accordance with the scheme: S52− → S2●− + S3●−; 3S2●− → 2S3●− + e−; S4 + S2●− + e− → 2S3●−; S4 + S2●− + e− → 2S3●−; S4 + S52− + e− → 3S3●− (e− = electron).

Research on the distribution of S species in the pressure oxidation leaching process of SrS solution

Strontium compounds apply extensively in a variety of domains. Commonly, strontium compounds are made by carbonization of SrS solution. H2S is readily generated in this process. To avoid H2S byproducing, a novel strategy for the pressure oxidation leaching process of SrS solution was used. The overoxidation of sulfides was restrained, and a higher separation efficiency of Sr and S was obtained, which was beneficial for synthesizing other strontium compounds. The effects of the oxidation pH environment, reaction temperature, initial total sulfide concentration and reaction time on the conversion ratio of S species were investigated. The results showed that S0 was preferably generated in a near-neutral, low-temperature and low initial total sulfide concentration oxidation environment. The optimum oxidation conditions were summarized experimentally: 48 mL/L HCl (pH = 7.11), 25 °C reaction temperature, 8.2 g/L initial total sulfide concentration and 60 min reaction time. The optimum conversion ratios were obtained under optimum oxidation conditions as follows: χsulfide 2.3%, χH2S 0.5%, χS0 81.5%, χinter 10.0% and χS - Sr 5.7%. SrCl2 crystal was recovered finally from the leachate. At last, the pressure oxidation mechanism of SrS was discussed.

Characterization of microbiomic and geochemical compositions across the photosynthetic fringe.

Hot spring outflow channels provide geochemical gradients that are reflected in microbial community compositions. In many hot spring outflows, there is a distinct visual demarcation as the community transitions from predominantly chemotrophs to having visible pigments from phototrophs. It has been hypothesized that this transition to phototrophy, known as the photosynthetic fringe, is a result of the pH, temperature, and/or sulfide concentration gradients in the hot spring outflows. Here, we explicitly evaluated the predictive capability of geochemistry in determining the location of the photosynthetic fringe in hot spring outflows. A total of 46 samples were taken from 12 hot spring outflows in Yellowstone National Park that spanned pH values from 1.9 to 9.0 and temperatures from 28.9 to 92.2°C. Sampling locations were selected to be equidistant in geochemical space above and below the photosynthetic fringe based on linear discriminant analysis. Although pH, temperature, and total sulfide concentrations have all previously been cited as determining factors for microbial community composition, total sulfide did not correlate with microbial community composition with statistical significance in non-metric multidimensional scaling. In contrast, pH, temperature, ammonia, dissolved organic carbon, dissolved inorganic carbon, and dissolved oxygen did correlate with the microbial community composition with statistical significance. Additionally, there was observed statistical significance between beta diversity and the relative position to the photosynthetic fringe with sites above the photosynthetic fringe being significantly different from those at or below the photosynthetic fringe according to canonical correspondence analysis. However, in combination, the geochemical parameters considered in this study only accounted for 35% of the variation in microbial community composition determined by redundancy analysis. In co-occurrence network analyses, each clique correlated with either pH and/or temperature, whereas sulfide concentrations only correlated with individual nodes. These results indicate that there is a complex interplay between geochemical variables and the position of the photosynthetic fringe that cannot be fully explained by statistical correlations with the individual geochemical variables included in this study.

Sulfide Removal by Catalitic Oxidation From Rayon Waste

Catalytic oxidation of spent sulfidic caustic consist of SH- ion or NaHS compound by H 2 O2 in neutral or acidic solution to elemental sulphur may provide a convenient and economical method for the control of sulphide wastes and their associated odors at pulp, paper and textile industry. Oxidation of sulfide in rayon waste by hydrogen peroxide was investigated in the presence of ferric sulfate catalyst. Kinetic equations and activation energies of H 2 O2 and SH- ion to total sulphur and sulphate in rayon waste for catalytic oxidation reaction were calculated based on the experimental results. For the removal of sulfide from sulfide solution the most common process involves its catalytic oxidation to a more benign form sulfate. The rate of sulfidic catalytic oxidation was found higher at lower initial sulphide concentration and the rate of sulphide catalytic oxidation was found directly proportional to loading and hydrogen peroxide addition. Optimum total sulphide concentration was achieved when sulphide solutions in the presence of H 2 O 2 in the ratios SH-/H 2 O 2 1:4.2. The potential user of H 2 O 2 determine the optimal conditions for control of odor, corrosion and waste treatment cost due to sulfide consisting of sulphur ion, sulphate ion, etc. The catalytic oxidation of sulphides into sulphates by H 2 O 2 may be applied directly to aqueous wastes containing these odorants

P380 Changes in faecal microbiome and metabolome are more pronounced in Crohn’s disease patients who adhered to the CD-TREAT diet and responded by calprotectin.

Abstract Background Treatment with the CD-TREAT solid food diet improves disease activity indices, faecal calprotectin (FCAL) levels and quality of life in adults and children with active Crohn’s disease (CD); particularly in patients who adhere to the diet. Here we describe changes in faecal microbiome parameters during therapy with CD-TREAT and explore these changes against adherence. Methods Children and adult patients with active CD completed an 8-week treatment with CD-TREAT. The levels of FCAL, pH, total sulphide (colorimetry), short chain fatty acids (SCFA), branched chain fatty acids (BCFA) (gas chromatography), total bacterial load (qPCR for total 16S rRNA gene copy number/g) were measured in baseline faecal samples and at four and eight weeks of CD-TREAT. Liquid chromatography mass spectrometry (LC-MS) faecal metabolomics and 16s rRNA sequencing of the faecal microbiome were performed at the same timepoints. Since CD-TREAT is gluten-free, detection of the gluten immunogenic peptide (GIP) in faeces was used as an objective biomarker of treatment adherence. Data are presented as median (IQR). Results Forty patients [17 children, age: 14.0 (11.3-15.1) years; 23 adults, age: 33.9 (27.8-45.9) years] participated. Eighteen (45%) patients had detectable GIP in at least one of the two follow-up timepoints, suggesting incomplete adherence; the remaining 22 (55%) patients had undetectable GIP throughout the treatment course. Baseline FCAL levels decreased significantly in the group of patients with undetectable GIP [mg/kg, baseline: 1,190 (3,611-129); 8 weeks: 534 (92-1,230), p<0.05] but not in patients with detectable GIP [mg/kg, baseline: 599 (328-1,857); 8 weeks: 702 (278-1,496)]. During CD-TREAT, the concentration of faecal acetate, propionate, butyrate, total sulphide, total microbial load and faecal pH significantly changed in those with undetectable GIP but were less pronounced where GIP was detectable (Figure 1). Shannon diversity and richness significantly increased at both genus and OTU level, the abundance of several taxa changed, and LC-MS faecal metabolome shifted during CD-TREAT, but only in those with undetectable GIP (Figures 2 & 3). Conclusion We have identified that full adherence with CD-TREAT only occurs in ~55% of recipients, however a significant reduction in calprotectin is seen in those who adhere, and this is associated with microbial and metabolic changes which parallel those seen in successful exclusive enteral nutrition.

Simultaneous reductıon of nitrate and perchlorate by sulfide-based denitrification process

In this study, sulfide-based denitrification was used for the first time for perchlorate reduction. Perchlorates (CIO4-) are the salts obtained from perchloric acid and are widely used in missile and rocket systems as well as in the automotive industry, fireworks production and some pharmaceutical industries (in the treatment of hyperthyroidism). Perchlorate prevents the iodine uptake of the thyroid gland and inhibits the production of thyroid hormones (triiodothyronine-T3 and thyroxine-T4). Autotrophic reduction methods are gaining popularity in the removal of perchlorate, which is often found together with nitrate in water. In this study, sulfide produced in an ethanol-based sulfidogenic reactor was used for simultaneous reduction of nitrate, nitrite and perchlorate. The study was conducted with batch reactors in 196 hours with varying concentrations of nitrate, nitrite and perchlorate in the presence of 30 mg/L total sulfide. The study showed that the perchlorate removal rate was gradually reduced in reactors containing 10 mg/L nitrite, 10 mg/L nitrate and 20 mg/L nitrite and 20 mg/L nitrate, respectively. The control group reactors revealed that sulfide is used as an electron donor and the process is biological. It was observed that sulfide, a dissolved inorganic sulfur compound, can reduce perchlorate in the presence of nitrate and/or nitrite, and the reduction rate is largely dependent on the presence of nitrate and nitrite.

Slyudyankaite, Na28Ca4(Si24Al24O96)(SO4)6(S6)1/3(CO2)·2H2O, a new sodalite-group mineral from the Malo-Bystrinskoe lazurite deposit, Baikal Lake area, Russia

Abstract The new sodalite-group mineral species slyudyankaite, ideally Na28Ca4(Si24Al24O96) (SO4)6(S6)1/3(CO2)·2H2O, was discovered in altered lazurite-bearing metasomatic rock at the Malo-Bystrinskoe gem lazurite deposit, Baikal Lake area, eastern Siberia, Russia. The associated minerals are diopside, calcite, fluorapatite, phlogopite, lazurite, and pyrite. Slyudyankaite forms green to pale blue isolated anhedral equant grains up to 0.5 cm across and their aggregates. The streak is white and the luster is vitreous. Slyudyankaite is brittle, with a Mohs hardness of 5½. Cleavage and parting are not observed. Density measured by flotation in heavy liquids is equal to 2.46(2) g·cm–3. Density, calculated using the empirical formula and unit-cell volume refined from single-crystal XRD data, is 2.454 g·cm–3. Slyudyankaite was characterized using the IR, Raman, ESR, near infrared (NIR), visible (Vis), and ultraviolet (UV) absorption, XPS and photoluminescence spectroscopy methods. The chemical composition is (wt%, electron microprobe, H2O and CO2 determined by selective sorption of ignition products, CO2 confirmed by quantitative IR spectroscopic method, sulfate sulfur determined by wet chemical analysis): Na2O 19.28, K2O 0.12, CaO 5.13, Al2O3 27.01, SiO2 33.25, SO3 10.94, S 1.75, Cl 0.10, CO2 1.42, H2O 0.90, –O≡(Cl,HS) –0.03, total 99.87. The empirical formula is Na27.57Ca4.05 K0.11(Si24.52Al23.48O96)(SO4)6.06S2.420Cl0.12(CO2)1.43·2.21H2O where S2.420 is the total sulfide sulfur, mainly occurring as neutral S6 and subordinate S4 molecules, according to the structural data. XPS spectroscopy confirms the presence of sulfide sulfur in neutral form. The crystal structure was determined using single-crystal X-ray diffraction data and refined to R = 0.0428. Slyudyankaite is triclinic, space group P1, a = 9.0523(4) Å, b = 12.8806(6) Å, c = 25.681(1) Å, α = 89.988(2)°, β = 90.052(1)°, γ = 90.221(1)°, V = 2994.4(2) Å3, Z = 1. Slyudyankaite contains two kinds of sodalite cages occurring in the structure in a ratio of 3:1. Cages of the first kind are completely occupied by SO42− anions and extra-framework cations, whereas cages of the second type contain only neutral molecules (S6, CO2, H2O, and minor S4). The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 6.45 (11) (004, 112, 020), 3.716 (100) (204, 220, 116, 132), 2.878 (12) (136, 028, 044), 2.625 (23) (208, 240), 2.431 (6) (209), 2.275 (6) (048), 2.143 (12) (0.0.12, 336), 1.784 (7) (444, 1.1.14, 356, 172).

Environmental desulfurization of mine tailings using froth flotation: The case of Amaruq Mine (Nunavut, Canada)

This research examined the the desulfurization of tailings from the Amaruq mine at a laboratory scale using froth flotation. Optimization of the flotation process was carried out by testing the conventional potassium amyl-xanthate collector (PAX) and three alternative collectors from the mercaptobenzothiazole (MBT) and dithiophosphate (DTP) families. The main goal was to assess the efficiency of the desulfurization process as a sustainable tailings management approach to prevent contaminated mine drainage generation. Mineralogical characterization of the Amaruq tailings using automated scanning microscopy (QEMSCAN®) revealed that the total sulfide and carbonate contents were about 8 wt% and 3 wt%, respectively; 63.39 % of the sulfur occurred as pyrrhotite, 30.17 % as pyrite, 3.63 % as gersdorffite, and 2.61 % as arsenopyrite. To compare the collector flotation yields, response surface methodology (RSM) was used for statistical design, analysis, and modelling of froth flotation experiments using three key-parameters: pH, activator (CuSO4) dosage, and collector dosage. Four quadratic mathematical models were developed for each collector to calculate sulfide recovery. Variance analysis (ANOVA) revealed that the factors that most affected sulfide recovery were collector type/dosage and pH. Process optimization yielded a maximum sulfide recovery of 96.73 % using 300 g/t PAX and 300 g/t CuSO4 at pH 11. A similar recovery of 95.83 % was achieved using an MBT-MTP based collector under the same conditions. The maximum recovery obtained using MTP and MTP-DTP based collectors while operating at optimal conditions (alkaline pH and maximum collector dosage at 350 g/t) was 88.65 %. The desulfurization process succeeded in decreasing the sulfur content in the tailings to<0.11 wt%. The final tailings were not acid-forming, as confirmed by the acid-base accounting (ABA) and net acid generation (NAG) static tests, compared to the highly acid-forming feed samples. Kinetic testing on the benign desulfurized tailings was also performed to predict and validate their acid generating potential, as well as their contaminant release rates (particularly As, Ni, Cu, Fe, and Zn). The Amaruq desulfurized material did not present any significant risk of contaminated mine drainage generation, and the leached contaminants did not exceed the criteria set by Quebec provincial legislation.

Effects of operational variations of micro-oxygenation and pH shock on the competition between methane production and sulfate reduction in a UASB reactor

To investigate the effect of oxygen, pH shock, and H2S inhibition on the competition between sulfate-reducing bacteria (SRB) and methane-producing archaea (MPA), a UASB reactor treating wastewater containing sulfate, ethanol and acetate was operated for 360 days. With micro-oxygenation performed at a flow rate of 100 mL/min in the upper part of the up-flow anaerobic sludge blanket (UASB) reactor, the sulfate removal and total sulfide concentration increased to 68.6% and 500 mg S/L, while the methane production rate slightly reduced from 2.5 to 2.1 L/L/d. However, methane production was still the main reaction in the reactor. The pH shock and high H2S concentration finally changed the competition results between SRB and MPA. Sulfate reduction was not affected while methane production was completely inhibited at H2S concentration more than 200 mg/L. Complete sulfate reduction (99.0%) was maintained over the long term with a stable organic COD removal (70.4%). The experimental results proved that in the complete sulfate-reducing stage, ethanol was mainly utilized by incomplete-oxidizing SRB for sulfate reduction.

ANALYSIS OF FLOWRATE, SULFATE, AND TOTAL SULFUR PATTERN IN WASTEWATER INLET TANKS FOR HS MANAGEMENT

Hydrogen sulfide (H2S) is a major source of concrete corrosion in a wastewater treatment plant (WWTP) that causes significant financial losses. Variations in the flow rate and composition of incoming wastewater has significant impact on H2S generation. During anaerobic conditions, sulfur present in excreta and sulfate from rainfall become the source of electron acceptors for the conversion of sulfate to sulfide in wastewater. Sulfide, in turn, is converted to H2S and later to sulfuric acid which leads to concrete corrosion. Flowrate directly relates to the amount of wastewater entering the plant. Hence understanding flow rate pattern will help to analyze H2S generation. Flow rate and H2S concentrations were recorded every two-hours for four days in a wastewater treatment plant. Wastewater samples of 50ml were collected at each sampling event coinciding the recording intervals. Samples were analyzed for sulphate and sulfide concentrations using HACH© kits. Total sulfur was calculated from the collected data. The correlations were analyzed using Minitab©. It was found out that average flow rate was negatively related to average H2S concentration. H2S concentration is higher during night when the flow rate is lower, which is a result of greater resident time. Flowrate changes in a cyclic manner throughout the day. During night, sulfate and total sulfur concentrations are higher, H2S concentration is maximum during this time. It is contrariwise during the day. Sulfate and total sulfide follow a pattern that is similar to that of flowrate. Analyzing these parameters is a critical step in successfully modelling H2S generation.

ANALYSIS OF FLOWRATE, SULFATE, AND TOTAL SULFUR PATTERN IN WASTEWATER INLET TANKS FOR HS MANAGEMENT

Hydrogen sulfide (H2S) is a major source of concrete corrosion in a wastewater treatment plant (WWTP) that causes significant financial losses. Variations in the flow rate and composition of incoming wastewater has significant impact on H2S generation. During anaerobic conditions, sulfur present in excreta and sulfate from rainfall become the source of electron acceptors for the conversion of sulfate to sulfide in wastewater. Sulfide, in turn, is converted to H2S and later to sulfuric acid which leads to concrete corrosion. Flowrate directly relates to the amount of wastewater entering the plant. Hence understanding flow rate pattern will help to analyze H2S generation. Flow rate and H2S concentrations were recorded every two-hours for four days in a wastewater treatment plant. Wastewater samples of 50ml were collected at each sampling event coinciding the recording intervals. Samples were analyzed for sulphate and sulfide concentrations using HACH© kits. Total sulfur was calculated from the collected data. The correlations were analyzed using Minitab©. It was found out that average flow rate was negatively related to average H2S concentration. H2S concentration is higher during night when the flow rate is lower, which is a result of greater resident time. Flowrate changes in a cyclic manner throughout the day. During night, sulfate and total sulfur concentrations are higher, H2S concentration is maximum during this time. It is contrariwise during the day. Sulfate and total sulfide follow a pattern that is similar to that of flowrate. Analyzing these parameters is a critical step in successfully modelling H2S generation.

DNA- and RNA-based bacterial communities and geochemical zonation under changing sediment porewater dynamics on the Aldabra Atoll

The remote Aldabra Atoll, Seychelles, provides the rare opportunity to study bacterial communities in pristine carbonate sediments across an entire biome. The four sampled sites cover sand with high porewater exchange, bioturbated silt and mud with intermediate exchange, as well as a seasonally and episodically desiccated landlocked pool. As sediments harbour dead cells and environmental DNA alongside live cells, we used bacterial 16S rRNA gene and transcript analysis to distinguish between past and present inhabitants. Previously described laminated sediments mirroring past conditions in the Cerin, France could not be retrieved. Thus, the aim was adjusted to determine whether bacterial community composition and diversity follow typical geochemical zonation patterns at different locations of the atoll. Our data confirm previous observations that diversity decreases with depth. In the lagoon, the bacterial community composition changed from Pseudomonas dominating in the sand to diverse mixed surface and sulphate reduction zones in the anaerobic mud with strongly negative Eh. The latter correlated with high total alkalinity, ammonia, and total sulphide, alongside a decrease in SO42−/Cl− and high relative abundances of sulphate reducing (Halo-) Desulfovibrio, sulphur oxidizing Arcobacteraceae, photo(hetero)troph Cyanobacteria, Alphaproteobacteria, and fermenting Propionigenium. In contrast to expectations, deeper mud and pool sediments harboured high abundances of Halomonas or Alphaproteobacteria alongside high C/N and increased salinity. We believe that this atypical community shift may be driven by a change in the complexity of available organic matter.

Sulfide Ore Formation of the Kalatongke Ni-Cu Deposit as Illustrated by Sulfide Textures

Abstract The Kalatongke magmatic Ni-Cu deposit features high Ni-Cu grades compared with other Ni-Cu deposits in the Central Asian orogenic belt. The sulfides, mainly hosted by olivine norite and gabbronorite, are characterized by high Cu/Ni ratios. There is wide variety of textural relationships in the mineralized rocks, including globular, sulfide matrix, emulsion, disseminated, net-textured, and semimassive to massive textures. Quantitative textural measurements reveal that more than 65 vol % of the total sulfide volume in disseminated ore (defined as containing 4–10 vol % sulfide) and more than 90 vol % of the total sulfide volume in net-textured ore (typically 16 vol % sulfide) are hosted in few interconnected networks with equivalent sphere diameters (ESDs) larger than 6 mm. This illustrates that sulfide coalescence is a critical process. The remaining sulfide blebs define two groups of log-linear particle size distribution (PSD), i.e., a finer group (ESD of 0.080–&amp;lt;0.529 mm) and a coarser group (ESD of 0.529–4.084 mm). The PSD of the finer group differs slightly among different types of mineralization. The origin of this group of sulfides is attributed to sulfide nucleation simultaneously with crystallization of the olivine-orthopyroxene-plagioclase phases from the ore-forming magma in the current magma chamber. The PSD of the coarser group from net-textured ores is parallel to that from the disseminated ore but has lower intercept values. Modeling results show that aggregation of ~40–70% sulfide blebs of different grain size from the disseminated ore into the networks can generate the coarser group sulfide PSD of net-textured ore. In addition, monosulfide solution (MSS, pyrrhotite component)-enriched sulfide globules are commonly located close to sulfide matrix ore breccias and emulsion-textured ores, rimming the net-textured and massive orebodies. These globules are different from the sulfide component that was in equilibrium with the mafic magma, suggesting they were formed by mechanical remobilization of a cumulus MSS-enriched component from a previously segregated and partially crystallized sulfide pool. These observations, combined with the ubiquitous chilled margin xenoliths in the high-grade ores, suggest that the Kalatongke deposit was the result of voluminous magma flow through the current location accompanied by sulfide reworking and percolation. All these textural characteristics could be explained by emplacement within a laterally propagating bladed dike. Moreover, the deformation recorded in the emulsion-textured and massive ores suggests the fault system remains active during magma solidification, driving downward migration of sulfide from the sulfide pool at magmatic temperature to form vein-type massive ore. We suggest that the Kalatongke deposit formed by magma pulses injecting into the current location and that the tectonic movement remains active during the solidification of the intrusion. The syntectonic emplacement model, which may be a common feature in the Central Asian orogenic belt Ni-Cu deposits, indicates that the fault systems beneath the intrusion are of great exploration interest for high-grade ores.

Sulfur mass balance and speciation in the water cap during early-stage development in the first pilot pit lake in the Alberta Oil Sands

Environmental context Base Mine Lake (BML) is a demonstration pilot pit lake for long term oil sands tailings reclamation in Alberta, Canada. This study quantified BML water cap sulfur mass balance and speciation to help understand potential risks to oxygen levels during its early-stage development. Results provide important insights for the adaptive management of water-capped oil sands tailings reclamation. Rationale Sulfur cycling is crucial to the persistence of oxygen in the water cap of Base Mine Lake (BML), the first demonstration oil sands pit lake for water capped tailings technology (WCTT) in Alberta, Canada. Methodology Here, we report on the first investigation of sulfur mass balance and sulfur speciation (SO4 2−, SO3 2−, S2O3 2−, S0 and ƩH2S) over seasonal, annual and spatial scales in BML. Results and discussion High aqueous total sulfur concentration (1.7–2 mM), dominated by sulfate (&gt;75%), decreased over the study period (2015–2021), due to the consolidation of fluid fine tailings (FFT) and operational pump-in and pump-out activities. Expanded BML water cap S biogeochemical cycling occurred after a 2016 alum amendment. Late summer hypolimnetic anoxia emerged post-alum (2017–2021), coincident with detectable total sulfide (ƩH2S) and elemental sulfur (S0) concentrations and expanded sulfur-reducing bacteria activity in anoxic bottom waters. Post spring turnover resuspended FFT and particle settling rates also likely increased post-alum, supported by the observed migration of epilimnetic highest sulfite concentration (pre-alum) to metalimnetic waters (post-alum). These sulfide containing particles are likely the primary reduced S substrate for spring–summer sulfur-oxidising bacteria activity, as winter aqueous reactive S species (ƩH2S, S0, S2O3 2 − and SO3 2−) were non-detectable across years. Concentrations of reactive S species reached up to 200 µM, posing risks to BML O2 levels (maximum 300–350 µM). Results of this study establish the interactive effects of physical and biogeochemical processes, as well as operational activities in emergent S risks to water cap oxygen levels, a key criterion for success of this reclamation tailings technology.

Morphological, biochemical, molecular marker, gas chromatography-tandem mass spectrometer analysis of garlic (Allium sativum L.) landraces in the rain shadow high hills of Kerala, India

Background: In Kerala, dry hill agro ecological zone is famous for the commercial cultivation of hill garlic. Vattavada and Kanthalloor panchayaths in Devikulam block of Idukki district, India, are famous for the cultivation of hill garlic. The traditional land races a being cultivated by Muthuva tribes has role in traditional home remedies and fetches better price in market Therefore, we investigated local landraces of garlic (MLPD garlic, MPD garlic, and SGPR garlic) along with two released varieties (Ooty 1 garlic, Yamuna safed 3-garlic) for their chemical composition, bulb morphological traits, and diversity at molecular level. Materials and Methods: Morphological characterization, biochemical parameters analysis, molecular marker analysis using simple sequence repeats, and gas chromatography-tandem mass spectrometer (GC-MS) analysis were performed for five different genotypes of garlic. Results: Significant difference was observed in morphological characterization, biochemical parameters analysis of five different genotypes of garlic. Molecular marker anlalysis results indicated DNA level variation in traditional garlic genotypes and found these garlic having high storability at field level and used in traditional folk medicines preparations. GC-MS analysis results showed MLPD garlic as having 10 total number of active constituents. MPD garlic as having 14 total number of active constituents. SGPR garlic as having six total number of active constituents. Ooty 1 garlic as having 13 total number of active constituents and Yamuna safed 3 garlic having 7 total number of active constituents. Conclusion: This study showed the uniqueness of MLPD garlic and SGPR garlic used in traditional home remedies with high storability at the field level with the presence of high percent of total sulphides and a significant variation at the molecular level.

Simultaneous control of sulfide and methane in sewers achieved by a physical approach targeting dominant active zone in sediments

Sewer sediments not only induce sewer blockages, but also contributes to significant sulfide and methane productions in gravity sewer systems. Chemical control of sulfide and methane production is extremely expensive. This study aims to propose a novel physical control approach—intermittent surface sediment flushing to synchronously address sediment-induced multiple issues. The proposed approach was established investigating the suppression and recovery characteristics of sulfidogenic and methanogenic activities of sediments including the in-situ activity analysis by using the diffusive gradients in thin films (DGT). The results showed that ∼70% of total sulfide and methane production in sediments was contributed by surface sediments (0–1.5 cm), which could be easily flushed away by a low shear stress (<0.1 N/m2). Surface sediment flushing resulted in an immediate reduction in sulfidogenic and methanogenic activities, which both required about one week to recover to 50% of the maximum. These novel insights hopefully provide a feasible approach, i.e., intermittent surface sediment flushing, to effectively reduce sulfide and methane production in sewers. Compared with chemical dosing methods, the proposed approach, which has no chemical input, greatly reduces operating cost and environment impact. Moreover, intermittent surface flushing is expected to keep sediment thickness within a certain range to alleviate sewer blockage.

Abstract 14458: Plasma Gasotransmitter Levels in Atrial Fibrillation

Introduction: Atrial fibrillation (AF) is associated with oxidative stress. Hydrogen sulfide and nitric oxide (NOx) are gasotransmitters involved in cardiovascular redox homeostasis. Free sulfide is increased in the plasma of human patients with atrial fibrillation. Although nitric oxide synthase expression and polymorphism has been studied in atrial fibrillation, NOx levels have not been measured in AF patients Hypothesis: AF is associated with altered NOx levels, and sulfide: nitrite ratio. Methods: Free NOx, total NOx, and nitrotyrosine levels were measured in patients without AF (n = 65), paroxysmal AF (PAF, n = 26) and persistent AF (n = 25) and compared between groups. Previously published sulfide levels from these patients were used to calculate free sulfide: total NOx ratio. Clinical characteristics of these patients were compared. Student’s t-test and nominal logistic regression were used for statistical analysis. Results: The patients without AF were younger but comparable to AF patients with regard to race, sex, diabetes, sleep apnea, and smoking history. Patients with AF were more likely to have hypertension (82% versus 54% non-AF patients, p = 0.002) and heart failure (47% versus 25% of non-AF, p = 0.02). On the other hand, non-AF patients were more likely to have coronary artery disease and/or peripheral arterial disease (43% versus 17% in patients with AF, p = 0.005). Compared to non-AF patients, AF patients had significantly lower total NOx (212 vs 268nM, p=0.005), free NOx (192 vs 237nM, p=0.039), and total sulfide: total NOx ratio (0.028 vs 0.020, p&lt;0.01). Compared to PAF patients, persistent AF patients had further significant reduction in total NOx (177 vs 243nM, p=0.04). At 3-month follow up, free NOx levels increased from baseline in patients who underwent successful conversion to normal sinus rhythm (n=11, p=0.048). Levels of oxidative stress marker, nitrotyrosine, trended higher in patients with AF compared to non-AF patients (1.10 vs 1.01 p=0.08). Multivariable logistic regression showed that total NOx was associated with AF independent of age, sex, race, HTN, DM and heart failure (OR per 10nM decrease in NOx= 1.04, CI=1.001-1.094, p=0.0471*) Conclusion: Reduced NOx levels and increased free sulfide to NOx ratio are associated with AF.

Redox-controlled chalcophile element geochemistry of the Polaris Alaskan-type mafic-ultramafic complex, British Columbia, Canada

ABSTRACT The Early Jurassic Polaris Alaskan-type intrusion in the Quesnel accreted arc terrane of the North American Cordillera is a zoned, mafic-ultramafic intrusive body that contains two main styles of magmatic mineralization of petrologic and potential economic significance: (1) chromitite-associated platinum group element (PGE) mineralization hosted by dunite (±wehrlite); and (2) sulfide-associated Cu-PGE-Au mineralization hosted by olivine (±magnetite) clinopyroxenite, hornblendite, and gabbro-diorite. Dunite-hosted PGE mineralization is spatially associated with thin discontinuous layers and schlieren of chromitite and chromitiferous dunite and is characterized by marked enrichments in iridium-subgroup PGE (IPGE) relative to palladium-subgroup PGE (PPGE). Discrete grains of platinum group minerals (PGM) are exceedingly rare, and the bulk of the PGE are inferred to reside in solid solution within chromite±olivine. The absence of Pt-Fe alloys in dunite of the Polaris intrusion is atypical, as Pt-enrichment of dunite-hosted chromitite is widely regarded as a characteristic feature of Alaskan-type intrusions. This discrepancy appears to be consistent with the strong positive dependence of Pt solubility on the oxidation state of sulfide-undersaturated magmas. Through comparison with experimentally determined PGE solubilities, we infer that the earliest (highest temperature) olivine-chromite cumulates of the Polaris intrusion crystallized from a strongly oxidized ultramafic parental magma with an estimated log f(O2) &amp;gt; FMQ+2. Parental magmas with oxygen fugacities more typical of volcanic arc settings [log f(O2) ∼ FMQ to ∼ FMQ+2] are, in turn, considered more favorable for co-precipitation of Pt-Fe alloys with olivine and chromite. More evolved clinopyroxene- and hornblende-rich cumulates of the Polaris intrusion contain low abundances of disseminated magmatic sulfides, consisting of pyrrhotite and chalcopyrite with minor pentlandite, pyrite, and rare bornite (≤12 wt.% total sulfides), which occur interstitially or as polyphase inclusions in silicates and oxides. The sulfide-bearing rocks are characterized by strong primitive mantle-normalized depletions in IPGE and enrichments in Cu-PPGE-Au, patterns that resemble those of other Alaskan-type intrusions and primitive arc lavas. The absolute abundances and sulfur-normalized whole-rock concentrations (Ci/S, serving as proxy for sulfide metal tenor) of chalcophile elements, including Cu/S, in sulfide-bearing rocks are highest in olivine clinopyroxenite. Sulfide saturation in the relatively evolved magmas of the Polaris intrusion, and Alaskan-type intrusions in general, appears to be intimately tied to the appearance of magnetite. Fractional crystallization of magnetite during the formation of olivine clinopyroxenite at Polaris resulted in reduction of the residual magma to log f(O2) ≤ FMQ+2, leading to segregation of an immiscible sulfide melt with high Cu/Fe and Cu/S, and high PGE and Au tenors. Continued fractionation resulted in sulfide melts that were progressively more depleted in precious and base chalcophile metals. The two styles of PGE mineralization in the Polaris Alaskan-type intrusion are interpreted to reflect the evolution of strongly oxidized, hydrous ultramafic parental magma(s) through intrinsic magmatic fractionation processes that potentially promote sulfide saturation in the absence of wallrock assimilation.