Reduced Sulfur Compounds Research Articles

Effect of reduced sulfur group on the formation of CX3R-type disinfection by-products during chlor(am)ination of reduced sulfur compounds

Previous studies have examined the effects of peptide bond and unsaturated bond on the formation of disinfection by-products (DBPs). However, limited information has been available for the impact of reduced sulfur group on the formation of DBPs. This study investigated the formation of carbonaceous and nitrogenous DBPs (C-DBPs and N-DBPs) with a similar structure of ''CX3R'' (X = H, Cl, Br or I, R = functional group), including trihalomethanes, haloacetaldehydes, haloketones, haloacetonitriles, haloacetamides and halonitromethanes, during chlor(am)ination of three reduced sulfur compounds (RSCs), such as N-acetylcysteine, glutathione and glutathiol. Results showed that all DBPs except dichloroacetonitrile (DCAN) continuously increased with increasing Cl2 or NH2Cl doses in this study. The chlor(am)ination of three RSCs with lower disinfectant doses (the molar ratio of disinfectant to precursor ≤5) generated low DBPs compare to non-RSCs. More chloroform was observed in alkaline condition, while weak acidic condition was in favor of DCAN and dichloroacetamide formation. The results of frontier electron density calculation reported that the much higher reactivity for Cl2 and NH2Cl toward reduced sulfur group in RSCs protects other groups, which account for the formation of CX3R-type DBPs. This phenomenon has important environmental implications. When RSCs are present in the water, Cl2 or NH2Cl will reacts preferably with them rather than non-RSCs to form RSO3H as the major products. Hence, the trade-offs of between the products generated upon S-chlorination, which account for the formation RSO3H, and alkyl halogenation and N-chlorination, which account for the formation of CX3R-type DBPs, influence the formation of CX3R-type DBPs.

Principal component analysis of summertime ground site measurements in the Athabasca oil sands with a focus on analytically unresolved intermediate-volatility organic compounds

Abstract. In this paper, measurements of air pollutants made at a ground site near Fort McKay in the Athabasca oil sands region as part of a multi-platform campaign in the summer of 2013 are presented. The observations included measurements of selected volatile organic compounds (VOCs) by a gas chromatograph–ion trap mass spectrometer (GC-ITMS). This instrument observed a large, analytically unresolved hydrocarbon peak (with a retention index between 1100 and 1700) associated with intermediate-volatility organic compounds (IVOCs). However, the activities or processes that contribute to the release of these IVOCs in the oil sands region remain unclear. Principal component analysis (PCA) with varimax rotation was applied to elucidate major source types impacting the sampling site in the summer of 2013. The analysis included 28 variables, including concentrations of total odd nitrogen (NOy), carbon dioxide (CO2), methane (CH4), ammonia (NH3), carbon monoxide (CO), sulfur dioxide (SO2), total reduced-sulfur compounds (TRSs), speciated monoterpenes (including α- and β-pinene and limonene), particle volume calculated from measured size distributions of particles less than 10 and 1 µm in diameter (PM10−1 and PM1), particle-surface-bound polycyclic aromatic hydrocarbons (pPAHs), and aerosol mass spectrometer composition measurements, including refractory black carbon (rBC) and organic aerosol components. The PCA was complemented by bivariate polar plots showing the joint wind speed and direction dependence of air pollutant concentrations to illustrate the spatial distribution of sources in the area. Using the 95 % cumulative percentage of variance criterion, 10 components were identified and categorized by source type. These included emissions by wet tailing ponds, vegetation, open pit mining operations, upgrader facilities, and surface dust. Three components correlated with IVOCs, with the largest associated with surface mining and likely caused by the unearthing and processing of raw bitumen.

Unknown Widespread Iron- and Sulfur-Oxidizing Bacteria beneath the East Antarctic Ice Sheet

Comparative analysis of the Vostok ice core (Central East Antarctica; one horizon, three boreholes) and D10 ice core (shoreline nearby the French Dumont d’Urville station) has reliably revealed three phylotypes (species) of aerobic iron-oxidizing betaproteobacteria of the family Gallionellaceae (closely related at the genus level to Sideroxydans lithotrophicus and Ferriphaselus amnicola), one of which has been detected from both the Vostok (borehole 5G-3) and D10 cores. In addition, the phylotype related to sulfur-oxidizing bacteria Tumebacillus sp. has been detected from both the Vostok (borehole 5G-2) and D10 cores. The both ice cores are almost equal in age, about 20 000 years; however, they differ in origin: the ice from Dumont d’Urville is atmospheric, while that from Vostok is a lake ice. The ice samples greatly vary in the storage time before treatment in the laboratory (from 0.5 to 40 years) and in intervals between treatments (from 1 to 5 years). The drilling sites are more than 1000 km apart. No evident hydrological links (the transfer of water beneath the ice sheet) between the Lake Vostok and Dumont D’Urville station have been found. This coincidence can be explained by the fact that minerals from the bedrock under the glacier, containing ferrous iron and reduced sulfur compounds, as well as physical and chemical conditions in both sites, liquid fresh water at a temperature near the freezing point, are similar. These and other assumptions are considered in the present article.

Genetic variability in Acidithiobacillus spp. – a working horse of environmental biotechnologies

AbstractThe genus Acidithiobacillus comprises 7 species of Gram-negative obligatory acidophilic chemolithotrophic bacteria that derive energy mainly from the oxidation of reduced sulphur compounds. Four of the species also catalyse the dissimilatory oxidation of ferrous iron while three (A. thiooxidans, A. albertensis, and A. caldus) do not. Bacteria from the genus Acidithiobacillus are often associated with mineral biotechnologies (biomining) and acid mine drainage. While acceleration of mineral solubilisation is a positive aspect in environmental biotechnologies, it is undesirable in acid mine drainage with strong negative ecological impact and there is profound interest in genetics and genomics of these bacteria. Representatives of Acidithiobacillus genus occur world-wide, however there are limited data on Acidithiobacillus spp. variability from Slovakia. In our work the variability of Acidithiobacillus spp., from Slovakia was analysed and the presence of A ferrooxidans was detected. In addition, for the first time we report here on the occurrence of A. albertensis as well. Comparative analyses confirmed pronounced genetic and genomic diversity within the genus, especially within A. ferrooxidans and A. thioxidans complexes. Based on data presented, several Acidithiobacillus species could be considered as a complex species and the description of several new species is very probable in the near future.

Abnormally High δ34S Values of Edifices at the Mid-Atlantic Ridge: The Closed System Effect at the Sulfide Generation Zone

The S isotope composition of single sulfide grains was studied taking into account the sequence of their formation in samples from the sulfide structures of hydrothermal fields confined to the Mid-Atlantic Ridge. The ranges of δ34S values obtained for the structures of the Logachev, Krasnov, and Rainbow fields are the following (‰): from +3.9 to +6, from +7.1 to +9.8, and from +2.1 to +8.4, respectively. Sulfides of later generations within each of these fields are regularly enriched in the 34S isotope relative to sulfides of earlier generations. Here, the S isotope composition does not depend on the composition and structure of the mineral. The data obtained show that in the sulfide generation zone, where seawater sulfate reduction takes place, the system is closed relatively to fluid. This leads to an increase in δ34S values of reduced sulfur compounds in the hydrothermal fluid and to sulfides being crystallized.

Coupled Carbon, Sulfur, and Nitrogen Cycles Mediated by Microorganisms in the Water Column of a Shallow-Water Hydrothermal Ecosystem.

Shallow-water hydrothermal vent ecosystems are distinctly different from deep-sea vents, as other than geothermal, sunlight is one of their primary sources of energy, so their resulting microbial communities differ to some extent. Yet compared with deep-sea systems, less is known about the active microbial community in shallow-water ecosystems. Thus, we studied the community compositions, their metabolic pathways, and possible coupling of microbially driven biogeochemical cycles in a shallow-water hydrothermal vent system off Kueishantao Islet, Taiwan, using high-throughput 16S rRNA sequences and metatranscriptome analyses. Gammaproteobacteria and Epsilonbacteraeota were the major active bacterial groups in the 16S rRNA libraries and the metatranscriptomes, and involved in the carbon, sulfur, and nitrogen metabolic pathways. As core players, Thiomicrospira, Thiomicrorhabdus, Thiothrix, Sulfurovum, and Arcobacter derived energy from the oxidation of reduced sulfur compounds and fixed dissolved inorganic carbon (DIC) by the Calvin-Benson-Bassham (CBB) or reverse tricarboxylic acid cycles. Sox-dependent and reverse sulfate reduction were the main pathways of energy generation, and probably coupled to denitrification by providing electrons to nitrate and nitrite. Sulfur-reducing Nautiliaceae members, accounting for a small proportion in the community, obtained energy by the oxidation of hydrogen, which also supplies metabolic energy for some sulfur-oxidizing bacteria. In addition, ammonia and nitrite oxidation is another type of energy generation in this hydrothermal system, with marker gene sequences belonging to Thaumarchaeota/Crenarchaeota and Nitrospina, respectively, and ammonia and nitrite oxidation was likely coupled to denitrification by providing substrate for nitrate and nitrite reduction to nitric oxide. Moreover, unlike the deep-sea systems, cyanobacteria may also actively participate in major metabolic pathways. This study helps us to better understand biogeochemical processes mediated by microorganisms and possible coupling of the carbon, sulfur, and nitrogen cycles in these unique ecosystems.

Sulfate Metabolism in C4 Flaveria Species Is Controlled by the Root and Connected to Serine Biosynthesis.

The evolution of C4 photosynthesis led to an increase in carbon assimilation rates and plant growth compared to C3 photosynthetic plants. This enhanced plant growth, in turn, affects the requirement for soil-derived mineral nutrients. However, mineral plant nutrition has scarcely been considered in connection with C4 photosynthesis. Sulfur is crucial for plant growth and development, and preliminary studies in the genus Flaveria suggested metabolic differences in sulfate assimilation along the C4 evolutionary trajectory. Here, we show that in controlled conditions, foliar accumulation of the reduced sulfur compounds Cys and glutathione (GSH) increased with progressing establishment of the C4 photosynthetic cycle in different Flaveria species. An enhanced demand for reduced sulfur in C4 Flaveria species is reflected in high rates of [35S]sulfate incorporation into GSH upon sulfate deprivation and increased GSH turnover as a reaction to the inhibition of GSH synthesis. Expression analyses indicate that the γ-glutamyl cycle is crucial for the recycling of GSH in C4 species. Sulfate reduction and GSH synthesis seems to be preferentially localized in the roots of C4 species, which might be linked to its colocalization with the phosphorylated pathway of Ser biosynthesis. Interspecies grafting experiments of F. robusta (C3) and F. bidentis (C4) revealed that the root system primarily controls sulfate acquisition, GSH synthesis, and sulfate and metabolite allocation in C3 and C4 plants. This study thus shows that evolution of C4 photosynthesis resulted in a wide range of adaptations of sulfur metabolism and points out the need for broader studies on importance of mineral nutrition for C4 plants.

Biological oxidation of sulfur compounds in artificially degraded wood

Marine and lacustrine archaeological waterlogged wood encounters serious problems after excavation due to the accumulation of sulfur and iron compounds during burial. Exposure of these compounds to oxygen results in precipitation of salts and acidification, which can lead to serious structural damage, and ultimately the loss of important cultural heritage. In this study, we evaluated the capacity of the bacterium Thiobacillus denitrificans to transform sulfur compounds commonly found in waterlogged wooden objects, to more readily extractable compounds thereby eliminating the threat of degradation. Oak samples, impregnated with a solution containing iron(II) and sulfides, were used to assess the efficiency of the bacterial treatment. The model wood samples were characterized before and after treatment using different techniques such as ESEM-EDS, micro-Raman spectroscopy, XRD and Sy-XRF mapping. Before treatment, mackinawite (FeS) and mineral sulfur (α-S8) were detected in the impregnated wood. After treatment with T. denitrificans, even though some mineral sulfur remained in the samples, the predominant phase corresponded to oxidized sulfur. This demonstrates that T. denitrificans was able to use the reduced sulfur compounds present in the wood samples as an energy source, thereby producing more soluble oxidized sulfur compounds. In addition, non-invasive techniques such as Fourier transform infrared (FTIR) spectroscopy, were carried out to assess the consequences of the biological treatment on the wood structure. No negative effect on the wood was detected after the treatment in comparison with the reference-impregnated wood. This study demonstrates the feasibility of a biotechnological procedure for the preventive extraction of sulfur species from archaeological waterlogged wood.

Thiosulfate- and hydrogen-driven autotrophic denitrification by a microbial consortium enriched from groundwater of an oligotrophic limestone aquifer.

Despite its potentially high relevance for nitrate removal in freshwater environments limited in organic carbon, chemolithoautotrophic denitrification has rarely been studied in oligotrophic groundwater. Using thiosulfate and H2 as electron donors, we established a chemolithoautotrophic enrichment culture from groundwater of a carbonate-rock aquifer to get more insight into the metabolic repertoire, substrate turnover, and transcriptional activity of subsurface denitrifying consortia. The enriched consortium was dominated by representatives of the genus Thiobacillus along with denitrifiers related to Sulfuritalea hydrogenivorans, Sulfuricella denitrificans, Dechloromonas sp. and Hydrogenophaga sp., representing the consortium's capacity to use multiple inorganic electron donors. Microcosm experiments coupled with Raman gas spectroscopy demonstrated complete denitrification driven by reduced sulfur compounds and hydrogen without formation of N2O. The initial nitrate/thiosulfate ratio had a strong effect on nosZ transcriptional activity and on N2 formation, suggesting similar patterns of the regulation of gene expression as in heterotrophic denitrifiers. Sequence analysis targeting nirS and nosZ transcripts identified Thiobacillus denitrificans-related organisms as the dominant active nirS-type denitrifiers in the consortium. An additional assessment of the nirS-type denitrifier community in the groundwaterclearly confirmed the potential for sulfur- and hydrogen-dependent chemolithoautotrophic denitrification as important metabolic feature widely spread among subsurface denitrifiers at the Hainich Critical Zone Exploratory.

A preconcentration method based on a new sorbent for the measurement of selected reduced sulfur compounds at ppb level in ambient air

Odour annoyance forms the main source of environmental stress in residents living nearby industrial or agricultural fields. However, despite a relative simplicity of odour measurement at the emission source, odour measurement in the field is a quite more complicated task. Because of their low odour threshold and offensive odour, this study focuses on 6 reduced sulfur compounds (RSCs): methylmercaptan (MM), ethylmercaptan (EM), dimethylsulfide (DMS), isopropylmercaptan (IPM), tertbutylmercatpan (TBM), diethylsulfide (DES). Because of their very low concentrations in ambient air (few ppb), a preconcentration step is usually required. The literature points Tenax TA® as the more suitable sorbent for sulfur compounds adsorption but shows also an important impact of humidity and storage parameters inducing an underestimation of sulfur ambient air concentrations. So only qualitative or semi-quantitative data results are obtained with Tenax TA® samplings of targeted compounds. To guarantee quantitative concentration data, a new sampling device, using a S-Sorbent Tube450 combined with an optimal drying device, was performed and optimized sampling and analysis parameters were determined. The assessment of uncertainties attests of quantitative measurements for 5 of the 6 RSCs (EM, DMS, IPM, TBM, DES) with relative expanded uncertainties less than 33% considering that samples were stored properly in freeze during 7 days. Only semi-quantitative measurements could be considered for MM with a global uncertainty estimated to 48%, storage contributing for a half.

Optofluidic Single-Cell Genome Amplification of Sub-micron Bacteria in the Ocean Subsurface.

Optofluidic single-cell genome amplification was used to obtain genome sequences from sub-micron cells collected from the euphotic and mesopelagic zones of the northwestern Sargasso Sea. Plankton cells were visually selected and manually sorted with an optical trap, yielding 20 partial genome sequences representing seven bacterial phyla. Two organisms, E01-9C-26 (Gammaproteobacteria), represented by four single cell genomes, and Opi.OSU.00C, an uncharacterized Verrucomicrobia, were the first of their types retrieved by single cell genome sequencing and were studied in detail. Metagenomic data showed that E01-9C-26 is found throughout the dark ocean, while Opi.OSU.00C was observed to bloom transiently in the nutrient-depleted euphotic zone of the late spring and early summer. The E01-9C-26 genomes had an estimated size of 4.76–5.05 Mbps, and contained “O” and “W”-type monooxygenase genes related to methane and ammonium monooxygenases that were previously reported from ocean metagenomes. Metabolic reconstruction indicated E01-9C-26 are likely versatile methylotrophs capable of scavenging C1 compounds, methylated compounds, reduced sulfur compounds, and a wide range of amines, including D-amino acids. The genome sequences identified E01-9C-26 as a source of “O” and “W”-type monooxygenase genes related to methane and ammonium monooxygenases that were previously reported from ocean metagenomes, but are of unknown function. In contrast, Opi.OSU.00C genomes encode genes for catabolizing carbohydrate compounds normally associated with eukaryotic phytoplankton. This exploration of optofluidics showed that it was effective for retrieving diverse single-cell bacterioplankton genomes and has potential advantages in microbiology applications that require working with small sample volumes or targeting cells by their morphology.

Activation strategies of metal-organic frameworks for the sorption of reduced sulfur compounds

In order to investigate the possible options to improve the pore properties of metal-organic frameworks (MOFs), the sorptive capacity of MOF-199 was assessed based on the two contrasting activation approaches (i.e., ‘chemical (C)’ and ‘thermal (T)’ activation) against four reduced sulfur (S) compounds (RSCs: H2S, CH3SH, (CH3)2S (DMS), and CH3SSCH3 (DMDS)). In order to represent the pristine (C1) and chemically activated forms of MOF-199 (C2), the pores were filled by N,N′-dimethylformamide (DMF) (i.e., as synthesized) and dichloromethane (CH2Cl2), respectively. For comparative purpose, these samples were further subject to thermal treatment (150 °C under 100 mL min−1) and named as T1 and T2, respectively. The combined effects of chemical/thermal activation were found to be most effective to enhance the sorption capacity of MOF-199. (Note that such advantage was not evident when treated by chemical activation only.) Overall, the relative ordering of sorption capacities between four different types of MOF-199, when tested against diverse S compounds, was found to be DMDS > CH3SH > H2S > DMS. The mechanism for such sorption patterns was ascribed to two major competing interactions: a) S-Cu for lighter S and b) –CH3 group (in S compound) and aromatic ring (in MOF ligand) for heavier S. This synergetic effect was also confirmed by both theoretically (density functional theory (DFT)) and experimentally (Fourier Transform Infrared (FTIR) spectroscopy analysis). As such, MOF-199 prepared through both chemical and thermal treatments was identified as an efficient sorbent to capture S compounds even in ambient conditions.

The Oxidative Metabolism of Fossil Hydrocarbons and Sulfide Minerals by the Lithobiontic Microbial Community Inhabiting Deep Subterrestrial Kupferschiefer Black Shale.

Black shales are one of the largest reservoirs of fossil organic carbon and inorganic reduced sulfur on Earth. It is assumed that microorganisms play an important role in the transformations of these sedimentary rocks and contribute to the return of organic carbon and inorganic sulfur to the global geochemical cycles. An outcrop of deep subterrestrial ~256-million-year-old Kupferschiefer black shale was studied to define the metabolic processes of the deep biosphere important in transformations of organic carbon and inorganic reduced sulfur compounds. This outcrop was created during mining activity 12 years ago and since then it has been exposed to the activity of oxygen and microorganisms. The microbial processes were described based on metagenome and metaproteome studies as well as on the geochemistry of the rock. The microorganisms inhabiting the subterrestrial black shale were dominated by bacterial genera such as Pseudomonas, Limnobacter, Yonghaparkia, Thiobacillus, Bradyrhizobium, and Sulfuricaulis. This study on black shale was the first to detect archaea and fungi, represented by Nitrososphaera and Aspergillus genera, respectively. The enzymatic oxidation of fossil aliphatic and aromatic hydrocarbons was mediated mostly by chemoorganotrophic bacteria, but also by archaea and fungi. The dissimilative enzymatic oxidation of primary reduced sulfur compounds was performed by chemolithotrophic bacteria. The geochemical consequences of microbial activity were the oxidation and dehydrogenation of kerogen, as well as oxidation of sulfide minerals.

Alternate approaches for assessing impacts of oil sands development on air quality: A case study using the First Nation Community of Fort McKay

ABSTRACTPrevious analyses of continuously measured compounds in Fort McKay, an indigenous community in the Athabasca Oil Sands, have detected increasing concentrations of nitrogen dioxide (NO2) and total hydrocarbons (THC), but not of sulfur dioxide (SO2), ozone (O3), total reduced sulfur compounds (TRS), or particulate matter (aerodynamic diameter <2.5 μm; PM2.5). Yet the community frequently experiences odors, dust, and reduced air quality. The authors used Fort McKay’s continuously monitored air quality data (1998–2014) as a case study to assess techniques for air quality analysis that make no assumptions regarding type of change. Linear trend analysis detected increasing concentrations of higher percentiles of NO2, nitric oxide (NO), and nitrogen oxides (NOx), and THC. However, comparisons of all compounds between an early industrial expansion period (1998–2001) and current day (2011–2014) show that concentrations of NO2, SO2, THC, TRS, and PM2.5 have significantly increased, whereas concentrations of O3 are significantly lower. An assessment of the frequency and duration of periods when concentrations of each compound were above a variety of thresholds indicated that the frequency of air quality events is increasing for NO2 and THC. Assessment of change over time with odds ratios of the 25th, 50th, 75th, and 90th percentile concentrations for each compound compared with an estimate of natural background variability showed that concentrations of TRS, SO2, and THC are dynamic, higher than background, and changes are nonlinear and nonmonotonic. An assessment of concentrations as a function of wind direction showed a clear and generally increasing influence of industry on air quality. This work shows that evaluating air quality without assumptions of linearity reveals dynamic changes in air quality in Fort McKay, and that it is increasingly being affected by oil sands operations.Implications: Understanding the nature and types of air quality changes occurring in a community or region is essential for the development of appropriate air quality management policies. Time-series trending of air quality data is a common tool for assessing air quality changes and is often used to assess the effectiveness of current emission management programs. The use of this tool, in the context of oil sands development, has significant limitations, and alternate air quality change analysis approaches need to be applied to ensure that the impact of this development on air quality is fully understood so that appropriate emission management actions can be taken.

Microbial Community Composition and Rates of the Methane Cycle Microbial Processes in the Upper Sediments of the Yamal Sector of the Southwestern Kara Sea

Geochemical, biogeochemical, and molecular genetic investigation of the upper (0–5 cm) bottom sediments of the Yamal sector of the Kara Sea was carried out. The Yamal sector is well-protected from the massive inflow of river water. The sediments were oxidized at the surface and weakly reduced in the 3−5-cm layer. Corg content varied from 0.1 to 1.3%, while the level of dissolved СН4 was 1.9 to 20.3 μmol L–1. The isotopic composition of organic matter (OM) carbon, δ13Corg, varied from–27.5 to–22.2‰ (–25.4‰ on average). The share of terrigenous OM was 13.3 to 72.2% (48.9% on average). The rate of methane production, methane oxidation, and sulfate reduction varied from 0.8 to 9.0 (2.7 on average) nmol СН4 dm–3 day–1, from 9.9 to 103 (31.6 on average) nmol СН4 dm–3 day–1, and from 0.49 to 2.2 (1.1 on average) μmol S dm–3 day–1, respectively. High-throughput sequencing of the amplicons of the 16S rRNA genes was used to reveal the physiological groups of microorganisms responsible for the processes of methane production and oxidation, sulfate reduction, and oxidation of reduced sulfur compounds. Members of the phylum Woesearchaeota were predominant among archaea. Methanogenic archaea belonged to the families Methanobacteriaceae, Methanococcaceae, and Methanosarcinaceae (Euryarchaeota). Methanotrophs of the family Methylococcaceae were revealed among the Gammaproteobacteria, with their share in the sediments ~1%. In the class Deltaproteobacteria (15.4%), three orders of sulfate reducers were predominant: Desulfobacterales, Desulfovibrionales, and Desulfuromonadales. Oxidation of reduced sulfur compounds was carried out by chemolithoautotrophic bacteria of the genera Sulfurovum, Sulfurimonas, and Arcobacter of the class Epsilonproteobacteria (1.1% of the total microbial number).

Factors affecting the adsorption of gaseous environmental odors by activated carbon: A critical review

ABSTRACTActivated carbon has a long history of application to abate gaseous environmental odors; however, design and operating decisions are primarily based on empirical relations and pilot testing, with limited use of fundamental mechanistic knowledge. To support improved abatement outcomes, environmental odorant adsorption was reviewed. While influenced by a range of adsorbate and adsorbent properties and process operating conditions, information about their impacts is often limited or unavailable. Current research has focused on volatile sulfur compounds, with lesser focus on volatile organic compounds and volatile nitrogen compounds. Even within volatile sulfur compounds, most work has focused on hydrogen sulfide and the full range of reduced sulfur compounds (important environmental odorants) remain to be studied. The current narrow window of knowledge does not reflect the complexity of environmental odorants and is limiting development and systematic application of this technology. It has been demonstrated that single component adsorbent characterization does not reflect the adsorption of the complex mixture of odorants and non-odorous compounds that make up environmental odor emissions. Studies to explore adsorption competition in multi-compound systems and develop methods/guidance to account for this in abatement system selection and design are required to achieve cost effective and reliable outcomes.

Application of Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) and 33S Isotope Labeling for Monitoring Sulfur Processes in Livestock Waste.

Reduced sulfur compounds emitted from livestock production cause odor nuisance for local residents. The microbial processes responsible for this are not well described in swine manure and a method for monitoring the biological processes is necessary to develop strategic abatement technologies. In this study, Proton-Transfer-Reaction Mass Spectrometry and isotope-labeled sulfate were combined and applied to elucidate the sulfur processes in swine manure with high time resolution. We successfully monitored reduction of isotope 33S labeled sulfate into corresponding 33S hydrogen sulfide and found that some of the 33S hydrogen sulfide was further methylated into 33S methanethiol. The isotope patterns in reduced sulfur compounds together with usage of inhibitors enabled us to calculate a sulfate reduction rate of 1.03 ± 0.18 mM/day equivalent to 76.9 ± 3.0% of total hydrogen sulfide emissions. Cysteine degradation constituted 20.2 ± 2.7% of the total hydrogen sulfide produced and the remaining hydrogen sulfide came from demethylation of methanethiol and dimethyl sulfide. Another source to methanethiol, besides hydrogen sulfide methylation, was methionine degradation, which contributed with 78.3 ± 2.5% of the methanethiol production, whereas the remaining 21.7 ± 2.5% came from hydrogen sulfide methylation. This study suggests, therefore, that emissions of odorous sulfur compounds from swine manure can be reduced by inhibiting methionine degradation and sulfate reduction.

Metagenomic Signatures of Microbial Communities in Deep-Sea Hydrothermal Sediments of Azores Vent Fields.

The organisms inhabiting the deep-seafloor are known to play a crucial role in global biogeochemical cycles. Chemolithoautotrophic prokaryotes, which produce biomass from single carbon molecules, constitute the primary source of nutrition for the higher organisms, being critical for the sustainability of food webs and overall life in the deep-sea hydrothermal ecosystems. The present study investigates the metabolic profiles of chemolithoautotrophs inhabiting the sediments of Menez Gwen and Rainbow deep-sea vent fields, in the Mid-Atlantic Ridge. Differences in the microbial community structure might be reflecting the distinct depth, geology, and distance from vent of the studied sediments. A metagenomic sequencing approach was conducted to characterize the microbiome of the deep-sea hydrothermal sediments and the relevant metabolic pathways used by microbes. Both Menez Gwen and Rainbow metagenomes contained a significant number of genes involved in carbon fixation, revealing the largely autotrophic communities thriving in both sites. Carbon fixation at Menez Gwen site was predicted to occur mainly via the reductive tricarboxylic acid cycle, likely reflecting the dominance of sulfur-oxidizing Epsilonproteobacteria at this site, while different autotrophic pathways were identified at Rainbow site, in particular the Calvin-Benson-Bassham cycle. Chemolithotrophy appeared to be primarily driven by the oxidation of reduced sulfur compounds, whether through the SOX-dependent pathway at Menez Gwen site or through reverse sulfate reduction at Rainbow site. Other energy-yielding processes, such as methane, nitrite, or ammonia oxidation, were also detected but presumably contributing less to chemolithoautotrophy. This work furthers our knowledge of the microbial ecology of deep-sea hydrothermal sediments and represents an important repository of novel genes with potential biotechnological interest.

Differential RNA Sequencing Implicates Sulfide as the Master Regulator of S0 Metabolism in Chlorobaculum tepidum and Other Green Sulfur Bacteria.

The green sulfur bacteria (Chlorobiaceae) are anaerobes that use electrons from reduced sulfur compounds (sulfide, S0, and thiosulfate) as electron donors for photoautotrophic growth. Chlorobaculum tepidum, the model system for the Chlorobiaceae, both produces and consumes extracellular S0 globules depending on the availability of sulfide in the environment. These physiological changes imply significant changes in gene regulation, which has been observed when sulfide is added to Cba. tepidum growing on thiosulfate. However, the underlying mechanisms driving these gene expression changes, i.e., the specific regulators and promoter elements involved, have not yet been defined. Here, differential RNA sequencing (dRNA-seq) was used to globally identify transcript start sites (TSS) that were present during growth on sulfide, biogenic S0, and thiosulfate as sole electron donors. TSS positions were used in combination with RNA-seq data from cultures growing on these same electron donors to identify both basal promoter elements and motifs associated with electron donor-dependent transcriptional regulation. These motifs were conserved across homologous Chlorobiaceae promoters. Two lines of evidence suggest that sulfide-mediated repression is the dominant regulatory mode in Cba. tepidum First, motifs associated with genes regulated by sulfide overlap key basal promoter elements. Second, deletion of the Cba. tepidum1277 (CT1277) gene, encoding a putative regulatory protein, leads to constitutive overexpression of the sulfide:quinone oxidoreductase CT1087 in the absence of sulfide. The results suggest that sulfide is the master regulator of sulfur metabolism in Cba. tepidum and the Chlorobiaceae Finally, the identification of basal promoter elements with differing strengths will further the development of synthetic biology in Cba. tepidum and perhaps other ChlorobiaceaeIMPORTANCE Elemental sulfur is a key intermediate in biogeochemical sulfur cycling. The photoautotrophic green sulfur bacterium Chlorobaculum tepidum either produces or consumes elemental sulfur depending on the availability of sulfide in the environment. Our results reveal transcriptional dynamics of Chlorobaculum tepidum on elemental sulfur and increase our understanding of the mechanisms of transcriptional regulation governing growth on different reduced sulfur compounds. This report identifies genes and sequence motifs that likely play significant roles in the production and consumption of elemental sulfur. Beyond this focused impact, this report paves the way for the development of synthetic biology in Chlorobaculum tepidum and other Chlorobiaceae by providing a comprehensive identification of promoter elements for control of gene expression, a key element of strain engineering.

Bone char effects on soil: sequential fractionations and XANES spectroscopy

Abstract. The acceptability of novel bone char fertilizers depends on their P release, but reactions at bone char surfaces and impacts on soil P speciation are insufficiently known. By using sequential fractionation and synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy we investigated whether and how the chemical composition of bone char particles has been altered in soil and has consequently affected the P speciation of amended soils. Therefore, two different kinds of bone char particles (BC produced by the pyrolysis of degreased animal bone chips at 800 °C and BCplus, a BC enriched with reduced sulfur compounds) were manually separated from the soil at the end of two different experiments: incubation leaching and ryegrass cultivation. Sequential P fractionation of amended soils showed P enrichment in all fractions compared to the control. The most P increase between all treatments significantly occurred in the NaOH–P and resin-P fractions in response to BCplus application in both incubation-leaching and ryegrass cultivation experiments. This increase in the readily available P fraction in BCplus-treated soils was confirmed by linear combination fitting (LCF) analysis on P K-edge XANES spectra of BC particles and amended soils. The proportion of Ca hydroxyapatite decreased, whereas the proportion of CaHPO4 increased in BCplus particles after amended soils had been incubated and leached and cropped by ryegrass. Based on P XANES speciation as determined by LCF analysis, the proportion of inorganic Ca(H2PO4)2 increased in amended soils after BCplus application. These results indicate that soil amendment with BCplus particles leads to elevated P concentration and maintains more soluble P species than BC particles even after 230 days of ryegrass cultivation.