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Active microbial sulfur disproportionation in the Mesoproterozoic.

The environmental expression of sulfur compound disproportionation has been placed between 640 and 1050 million years ago (Ma) and linked to increases in atmospheric oxygen. These arguments have their basis in temporal changes in the magnitude of 34S/32S fractionations between sulfate and sulfide. Here, we present a Proterozoic seawater sulfate isotope record that includes the less abundant sulfur isotope 33S. These measurements imply that sulfur compound disproportionation was an active part of the sulfur cycle by 1300 Ma and that progressive Earth surface oxygenation may have characterized the Mesoproterozoic.

Environment↗

Effect of Sulfur-Containing Compounds on Growth of Methanosarcina barkeri in Defined Medium.

Methanosarcina barkeri Fusaro (DSM 804) could grow on methanol in a mineral medium containing cysteine or thiosulfate as the sole sulfur source. Optimum growth occurred at cysteine concentrations of 1 to 2.8 mM and at thiosulfate concentrations of 2.5 to 5 mM. No inhibition of growth was observed even when these concentrations were doubled in the culture medium. Under the optimum cysteine and thiosulfate concentrations, the generation times of the organism were about 8 to 10 and 10 to 12 h, respectively, giving a cell yield of about 0.14 to 0.17 and 0.08 to 0.11 g (dry weight)/g of methanol consumed. The organism metabolized cysteine and thiosulfate during growth, giving rise to sulfide in the culture medium. H(2)S evolution from cysteine and thiosulfate was catalyzed by two enzymes, namely cysteine desulfhydrase and thiosulfate reductase, respectively, as revealed by enzyme assay in the crude cell-free extract of the organism.

Journal Article↗

Tetrathiobacter kashmirensis gen. nov., sp. nov., a novel mesophilic, neutrophilic, tetrathionate-oxidizing, facultatively chemolithotrophic betaproteobacterium isolated from soil from a temperate orchard in Jammu and Kashmir, India.

Twelve chemolithotrophic strains were isolated from temperate orchard soil on reduced sulfur compounds as energy and electron sources and characterized on the basis of their physiological properties and ability to oxidize various reduced sulfur compounds. The new isolates could oxidize tetrathionate as well as thiosulfate, and oxidation of the latter involved conversion of thiosulfate to tetrathionate followed by its accumulation and eventual oxidation to sulfate, manifested in the production of acid. The mesophilic, neutrophilic, Gram-negative and coccoid bacteria had a respiratory metabolism. Physiologically and biochemically, all the strains were more or less similar, differing only in their growth rates and ability to utilize a few carbon compounds as single heterotrophic substrates. 16S rRNA gene sequence analysis was performed with five representative strains, which revealed a high degree of similarity (> or =99%) among them and placed the cluster in the 'Betaproteobacteria'. The strains showed low levels (93.5-95.3 %) of 16S rRNA gene sequence similarity to Pigmentiphaga kullae, Achromobacter xylosoxidans, Pelistega europaea and species belonging to the genera Alcaligenes, Taylorella and Bordetella. The taxonomic coherence of the new isolates was confirmed by DNA-DNA hybridization. On the basis of their uniformly low 16S rRNA gene sequence similarities to species of all the closest genera, unique fatty acid profile, distinct G+C content (54-55.2 mol%) and phenotypic characteristics that include efficient chemolithotrophic utilization of tetrathionate, the organisms were classified in a new genus, Tetrathiobacter gen. nov. In the absence of any significant discriminatory phenotypic or genotypic characteristics, all the new isolates are considered to constitute a single species, for which the name Tetrathiobacter kashmirensis sp. nov. (type strain WT001(T)=LMG 22695(T)=MTCC 7002(T)) is proposed.

Bacterial Typing Techniques↗

Environmental VOSCs--formation and degradation of dimethyl sulfide, methanethiol and related materials.

Volatile organic sulfur compounds (VOSCs) play a major role in the global sulfur cycle. Two components, dimethyl sulfide (DMS) and methanethiol (MT) are formed in large amounts by living systems (e.g. algae, bacteria, plants), particularly in marine environments. A major route to DMS is by action of a lyase enzyme on dimethylsulfoniopropionate (DMSP). DMSP has other roles, for instance as an osmoprotectant and cryoprotectant. Demethiolation of DMSP and other materials leads to MT. A major transport process is release of DMS from the oceans to the atmosphere. Oxidation of DMS in the atmosphere by hydroxyl and nitrate radicals produces many degradation products including CO2, COS, dimethyl sulfoxide, dimethyl sulfone, organic oxyacids of sulfur, and sulfate. These materials also have roles in biotic processes and there are complex metabolic interrelationships between some of them. This review emphasizes the chemical reactions of the organic sulfur cycle. For biotic reactions, details of relevant enzymes are provided when possible.

Atmosphere↗

Deep desulfurization of diesel oil and crude oils by a newly isolated Rhodococcus erythropolis strain.

The soil-isolated strain XP was identified as Rhodococcus erythropolis. R. erythropolis XP could efficiently desulfurize benzonaphthothiophene, a complicated model sulfur compound that exists in crude oil. The desulfurization product of benzonaphthothiophene was identified as alpha-hydroxy-beta-phenyl-naphthalene. Resting cells could desulfurize diesel oil (total organic sulfur, 259 ppm) after hydrodesulfurization. The sulfur content of diesel oil was reduced by 94.5% by using the resting cell biocatalyst for 24 h at 30 degrees C. Biodesulfurization of crude oils was also investigated. After 72 h of treatment at 30 degrees C, 62.3% of the total sulfur content in Fushun crude oil (initial total sulfur content, 3,210 ppm) and 47.2% of that in Sudanese crude oil (initial total sulfur, 1,237 ppm) were removed. Gas chromatography with pulsed-flame photometric detector analysis was used to evaluate the effect of R. erythropolis XP treatment on the sulfur content in Fushun crude oil, and it was shown that most organic sulfur compounds were eliminated after biodesulfurization.

Gasoline↗

Regulation of cystathionine gamma-lyase in Saccharomyces cerevisiae.

Regulation of the two enzymes in reverse trans-sulfuration was investigated in Saccharomyces cerevisiae. In wild-type strains, cystathionine gamma-lyase, but not cystathionine beta-synthase, was depressed nearly 15-fold if cells were starved for both inorganic and organic sulfur compounds. In a met17 strain which is defective of O-acetylserine and O-acetylhomoserine sulfhydrylase, the same enzyme was derepressed if organic sulfur compounds were limited; the repressive effect was in the order of glutathione greater than methionine greater than cysteine. The repressive effect of methionine was not observed, however, in a cys2 cys4 strain which is deficient of serine O-acetyltransferase and cystathionine beta-synthase, indicating that methionine itself is not the effector. The weak repressive effect of cysteine was attributed to inefficient uptake of this amino acid. Our observations indicate that cystathionine gamma-lyase is the target of regulation in reverse trans-sulfuration and that cysteine is very likely to be the effector of this regulation.

Cystathionine gamma-Lyase↗

Genomics, metagenomics and proteomics in biomining microorganisms.

The use of acidophilic, chemolithotrophic microorganisms capable of oxidizing iron and sulfur in industrial processes to recover metals from minerals containing copper, gold and uranium is a well established biotechnology with distinctive advantages over traditional mining. A consortium of different microorganisms participates in the oxidative reactions resulting in the extraction of dissolved metal values from ores. Considerable effort has been spent in the last years to understand the biochemistry of iron and sulfur compounds oxidation, bacteria-mineral interactions (chemotaxis, quorum sensing, adhesion, biofilm formation) and several adaptive responses allowing the microorganisms to survive in a bioleaching environment. All of these are considered key phenomena for understanding the process of biomining. The use of genomics, metagenomics and high throughput proteomics to study the global regulatory responses that the biomining community uses to adapt to their changing environment is just beginning to emerge in the last years. These powerful approaches are reviewed here since they offer the possibility of exciting new findings that will allow analyzing the community as a microbial system, determining the extent to which each of the individual participants contributes to the process, how they evolve in time to keep the conglomerate healthy and therefore efficient during the entire process of bioleaching.

Bacteria↗

Key odor impact compounds in three yeast extract pastes.

Three types of yeast extract pastes from two different suppliers were compared. Compounds responsible for the key odors include 2-methyl-3-furanthiol, 2-methyl-3-methyldithiofuran, methional, 1-octen-3-one, dimethyltrisulphide together with a number of pyrazines, thiophenes, and aliphatic compounds. The three types of yeast extract paste differed in the intensity of their main odors and, in particular, those caused by furans, furanthiols, and heterocyclic sulfur compounds. Not only do pastes from different suppliers differ in terms of odor volatiles, but so do different treatments and batches of yeast extract from one supplier. The results suggest that normal variations in the concentrations of precursors and processing conditions may cause variations in the flavor of the end product.

Chromatography, Gas↗

Microbial fuel cells for sulfide removal.

Thus far, microbial fuel cells (MFCs) have been used to convert carbon-based substrates to electricity. However, sulfur compounds are ubiquitously present in organic waste and wastewater. In this study, a MFC with a hexacyanoferrate cathodic electrolyte was used to convert dissolved sulfide to elemental sulfur. Two types of MFCs were used, a square type closed to the air and a tubular type in which the cathode compartment was open to the air. The square-type MFCs demonstrated a potential-dependent conversion of sulfide to sulfur. In the tubular system, up to 514 mg sulfide L(-1) net anodic compartment (NAC) day(-1) (241 mg L(-1) day(-1) total anodic compartment, TAC) was removed. The sulfide oxidation in the anodic compartment resulted in electricity generation with power outputs up to 101 mW L(-1) NAC (47 W m(-3) TAC). Microbial fuel cells were coupled to an anaerobic upflow anaerobic sludge blanket reactor, providing total removals of up to 98% and 46% of the sulfide and acetate, respectively. The MFCs were capable of simultaneously removing sulfate via sulfide. This demonstrates that digester effluents can be polished by a MFC for both residual carbon and sulfur compounds. The recovery of electrons from sulfides implies a recovery of energy otherwise lost in the methane digester.

Anaerobiosis↗

Synthesis and stable isotope dilution assay of ethanethiol and diethyl disulfide in wine using solid phase microextraction. Effect of aging on their levels in wine.

Ethanethiol and diethyl disulfide (DEDS) most often occurred at levels above their olfactive threshold in wines with nauseous sulfur-linked smells. As ethanethiol is very oxidizable and chemically reactive, a stable isotopic dilution analysis of both ethanethiol and its disulfide in wines using solid phase microextraction and GC-MS was developed. The latter involved the determination of the proportion of DEDS formed by oxidation of the thiol during the analysis conditions, which was obtained by the use of two differently labeled disulfide standards. An original synthesis of labeled ethanethiol standards in conditions minimizing oxidation was developed, and the corresponding labeled diethyl disulfides were obtained from these thiols. This analytical method was used to follow the levels of these sulfur compounds during aging in a young red wine spiked with ethanethiol and added with enological tannins, with or without oxygen addition. The total levels of these two sulfur compounds were shown to decrease steadily after 60 days of aging, up to 83%. The effect of oxygen sped this decrease, but the effect of enological tannins was very slight. Residual ethanethiol was detected in its disulfide form from approximately 36% in the nonoxygenated wines to 69% in the oxygenated samples.

Deuterium↗

Characterization of high-molecular-weight sulfur-containing aromatics in vacuum residues using Fourier transform ion cyclotron resonance mass spectrometry.

Millions of tons of vacuum residues are produced in refineries every year and could be a potentially valuable resource for generating electricity and has possible application as heating and marine fuel. In this work, the polycyclic aromatic sulfur compounds (PASHs) from the aromatic fraction of vacuum residue before and after partial hydrodesulfurization (HDS) were derivatized by methylation to the methylsulfonium salts. Fourier transform ion cyclotron resonance mass spectrometry provided high-resolution data on these high-molecular-weight sulfur compounds. Compounds containing one and two S atoms were found to dominate, with masses up to ca. 900 Da. Classification according to hydrogen deficiency and the number of heteroatoms showed extensive series of homologues for double bond equivalents from 5 to 20. The sulfur-containing aromatics were separated using a palladium(II) complex as a liquid chromatographic phase into two compound groups: one containing compounds with an unconjugated thiophene ring and another with a condensed thiophene ring. This, combined with the mass spectrometry (MS) data, allows for the identification of several parent structures. Partial HDS removed primarily compounds with one S atom, whereas those with two S atoms were largely unaffected.

Journal Article↗

Mixotrophic and Autotrophic Growth of Thiobacillus acidophilus on Glucose and Thiosulfate.

Mixotrophic growth of the facultatively autotrophic acidophile Thiobacillus acidophilus on mixtures of glucose and thiosulfate or tetrathionate was studied in substrate-limited chemostat cultures. Growth yields in mixotrophic cultures were higher than the sum of the heterotrophic and autotrophic growth yields. Pulse experiments with thiosulfate indicated that tetrathionate is an intermediate during thiosulfate oxidation by cell suspensions of T. acidophilus. From mixotrophic growth studies, the energetic value of thiosulfate and tetrathionate redox equivalents was estimated to be 50% of that of redox equivalents derived from glucose oxidation. Ribulose 1,5-bisphosphate carboxylase (RuBPCase) activities in cell extracts and rates of sulfur compound oxidation by cell suspensions increased with increasing thiosulfate/glucose ratios in the influent medium of the mixotrophic cultures. Significant RuBPCase and sulfur compound-oxidizing activities were detected in heterotrophically grown T. acidophilus. Polyhedral inclusion bodies (carboxysomes) could be observed at low frequencies in thin sections of cells grown in heterotrophic, glucose-limited chemostat cultures. Highest RuBPCase activities and carboxysome abundancy were observed in cells from autotrophic, CO(2)-limited chemostat cultures. The maximum growth rate at which thiosulfate was still completely oxidized was increased when glucose was utilized simultaneously. This, together with the fact that even during heterotrophic growth the organism exhibited significant activities of enzymes involved in autotrophic metabolism, indicates that T. acidophilus is well adapted to a mixotrophic lifestyle. In this respect, T. acidophilus may have a competitive advantage over autotrophic acidophiles with respect to the sulfur compound oxidation in environments in which organic compounds are present.

Journal Article↗

Possible mechanism by which allyl sulfides suppress neoplastic cell proliferation.

Both oil- and water-soluble allyl sulfur compounds from garlic have been found to possess antitumorigenic properties. These antitumorigenic properties increase as exposure increases both in vitro and in vivo. Generally, oil-soluble allyl sulfur compounds are more effective antiproliferative agents than their water-soluble counterparts. The ability of these compounds to suppress proliferation is associated with a depression in cell cycle progression and the induction of apoptosis. This depression in cell division coincides with an increase in the percentage of cells blocked in the G(2)/M phase of the cell cycle. A depression in p34(cdc2) kinase may account for this blockage in cell division.

Allyl Compounds↗

The clinical effectiveness of a dentifrice containing triclosan and a copolymer for providing long-term control of breath odor measured chromatographically.

The objective of this double-blind clinical study was to investigate the effectiveness of a commercially available dentifrice containing triclosan and a copolymer (Colgate Total Toothpaste) for controlling long-term, i.e., seven-hour and overnight breath odor. In particular, a comparison was made between the level of control of breath odor provided by the test dentifrice, and that provided by a placebo dentifrice which did not contain triclosan or a copolymer. This study followed a two-treatment, two-period crossover design. Prospective subjects were provided with a supply of a commercially available fluoride dentifrice, which was used for a one-week period prior to the two seven-day treatment periods. During each treatment period, subjects were instructed to brush their teeth twice a day, morning and evening, for sixty seconds with their assigned study dentifrice, using the soft-bristled toothbrush which had been provided. On the morning following the seventh day of each treatment period, subjects reported to the clinical facility for overnight breath odor assessments. Directly following this, subjects brushed their teeth, ate and drank normally, and reported once again to the clinical facility at seven hours post-toothbrushing for another breath odor assessment. Prior to the overnight breath odor assessments, subjects refrained from brushing their teeth, rinsing their mouths or using breath mints, and from eating or drinking anything on the morning of the evaluation. Subjects refrained from the use of tobacco products, and from eating onions, garlic, or strong spices throughout the entire study. Breath odor was instrumentally evaluated by measuring the level of volatile sulfur compounds in the mouth air using a 565 Tracor gas chromatograph equipped with a flame photometric detector. Measurements were taken in duplicate, and then averaged. Levels of volatile sulfur compounds were expressed in nanograms per milliliter (ng/ml) of mouth air. The two dentifrices exhibited statistically significant differences (p < 0.05) with respect to both overnight breath odor and seven-hour post-toothbrushing breath odor. The mean overnight breath odor scores were 9.63 ng/ml for Colgate Total Toothpaste, and 12.64 ng/ml for the placebo dentifrice. For seven-hour breath odor, the mean scores were 5.62 ng/ml for Colgate Total Toothpaste, and 7.10 ng/ml for the placebo dentifrice. Thus, the results of this double-blind clinical study on 19 subjects support the conclusion that Colgate Total Toothpaste provides effective seven-hour and overnight control of breath odor.

Adult↗