Sewage sludge-derived materials as efficient adsorbents for removal of hydrogen sulfide

Sewage sludge-derived materials were used as adsorbents of hydrogen sulfide from moist air. The adsorbent obtained by carbonization at 950 degrees C has a capacity twice of that of coconut-shell-based activated carbon. The capacity of the sludge-derived materials increases with increasing carbonization temperature. It is likelythatduring carbonization at 950 degrees C a mineral-like phase is formed that consists of such catalytically active metals as iron, zinc, and copper. The results obtained demonstrate that the presence of iron oxide significantly increases the capacity of commercial carbon and activated alumina. The sludge-derived adsorbents are efficient for hydrogen sulfide removal until the pore entrances are blocked with sulfur as the product of oxidation reaction. For materials in which the catalytic effect is predominant, hydrogen sulfide is adsorbed until all pores are filled with sulfur. There is also indication that chemisorption plays a significant role in the removal of hydrogen sulfide from moist air.     

The effect of pH on thiosulfate formation in a biotechnological process for the removal of hydrogen sulfide from gas streams

In a biotechnological process for hydrogen sulfide (H2S) removal from gas streams, operating at natronophilic conditions, formation of thiosulfate (S2O3(2-)) is unfavorable, as it leads to a reduced sulfur production. Thiosulfate formation was studied in gas-lift bioreactors, using natronophilic biomass at [Na+] + [K+] = 2 mol L(-1). The results show that at sulfur producing conditions, selectivity for S2O3(2-) formation mainly depends on the equilibrium between free sulfide (HS(-)) and polysulfide (Sx(2-)), which can be controlled via the pH. At pH 8.6, 21% of the total dissolved sulfide is present as Sx(2-) and selectivity for S2O3(2-) formation is 3.9-5.5%. At pH 10, 87% of the total dissolved sulfide is present as Sx(2-) and 20-22% of the supplied H2S is converted to S2O3(2-), independent of the H2S loading rate. Based on results of bioreactor experiments and biomass activity tests, a mechanistic model is proposed to describe the relation between S2O3(2-) formation and pH.     

Inorganic-organic phase arrangement as a factor affecting gas-phase desulfurization on catalytic carbonaceous adsorbents

Dried sewage sludge was physically mixed with waste paper (paper-to-sludge ratios from 25% to 75%). To increase the catalytic activity, from 1% to 6% calcium hydroxide was added to the mixtures. Then the precursors were carbonized at 950 degrees C. The performance of materials as H2S adsorbents was tested using a home-developed dynamic breakthrough test. The samples, before and after the adsorption process, were characterized by adsorption of nitrogen, potentiometric titration, thermal analysis, XRF, and SEM. Differences in the performance were linked to the surface properties. Itwas found that mixing paper with sludge increases the amount of H2S adsorbed/oxidized in comparison with that adsorbed/oxidized by the adsorbents obtained from pure precursors (sludge or waste paper) and the capacity is comparable to those of the best activated carbons existing on the market. Although both sewage sludge and waste paper provide the catalytic centers for hydrogen sulfide oxidation, the dispersion of the catalyst and its location within accessible pores is an important factor. The presence of cellulose in the precursor mixture leads to the formation of a light macroporous char whose particles physically separate the inorganic catalytic phase of the sewage sludge origin, decreasing the density of the adsorbent and thus providing more space for storage of oxidation products. This, along with calcium, contributes to a significant increase in the capacity of the materials as hydrogen sulfide adsorbents. On their surface about 30 wt % H2S can be adsorbed, mainly as elemental sulfur or sulfates. The results demonstrate the importance of the composition and arrangement of inorganic/ organic phases for the removal of hydrogen sulfide. The interesting finding is that although some microporosity is necessary to increase the storage area for oxidation products, the carbonaceous phase does not need to be highly microporous. It is important that it provides space for deposition of sulfur, which is formed on the inorganic-phase catalyst. That space can be in meso- and macropores as shown in the case of char derived from the waste paper.     

Polysulfide reduction using sulfate-reducing bacteria in a photocatalytic hydrogen generation system

A hydrogen generation process using photocatalytic reactions has been proposed. In this process, hydrogen sulfide is a source of hydrogen and is turned into polysulfide. In order to establish the cyclic operation of a photocatalytic hydrogen generation system, it is necessary to convert polysulfide back into hydrogen sulfide with a small energy input. This paper proposes the use of sulfate-reducing bacteria (SRB) for the regeneration of hydrogen sulfide. Batch cultivation of natural source SRB samples were carried out using a culture medium containing polysulfide as the only sulfur compound source. SRB produced hydrogen sulfide from several kinds of polysulfide sources, including a photocatalytic hydrogen generation-produces solution. Production lag phase and production rate of hydrogen sulfide were affected by initial polysulfide concentration. SRB activity was inhibited at high initial polysulfide concentrations. SRB enrichment culture T2, exhibited the highest hydrogen sulfide production rate, and was able to utilize several kinds of organic matter as the electron donor. The results suggest the possibility of using large biomass sources, such as sewage sludge and the raw garbage in a hydrogen generation system. We developed speculative estimates that an SRB based hydrogen generation system is feasible.     

Polysulfide reduction by Clostridium relatives isolated from sulfate-reducing enrichment cultures

Sulfur is almost insoluble in water at ambient temperatures, and therefore polysulfide (S_n²⁻) has been considered as a possible intermediate that is used directly by bacteria in sulfur respiration. Sulfur-reducing reductases have been purified and characterized from a few sulfur reducers. However, polysulfide reduction has only been confirmed in Wolinella succinogenes. In our previous study, the direct production of hydrogen sulfide from polysulfide was confirmed by an enrichment culture obtained from natural samples under sulfate-reducing conditions. The present study attempted to isolate and identify polysulfide-reducing bacteria from the enrichment cultures. Almost all the isolated strains were classified into the genus Clostridium, based on 16S rRNA gene sequence analysis. The isolates, and some closely related strains, were able to reduce polysulfide to hydrogen sulfide. During production of 1 mol of hydrogen sulfide, approximately 2 mol of lactate was converted to acetate. Thus, dissimilatory polysulfide reduction occurred using lactate as an electron donor. The ability to reduce elemental sulfur was also examined with the isolates and the related strains. Although elemental sulfur reducing strains can reduce polysulfides, not all polysulfide-reducing strains can reduce elemental sulfur. These results demonstrate that the conversion of elemental sulfur to polysulfide seems to be important in the reduction process of sulfur.     

Purification and some properties of sulfur reductase from the iron-oxidizing bacterium Thiobacillus ferrooxidans NASF-1

Thiobacillus ferrooxidans strain NASF-1 grown aerobically in an Fe2+ (3%)-medium produces hydrogen sulfide (H2S) from elemental sulfur under anaerobic conditions with argon gas at pH 7.5. Sulfur reductase, which catalyzes the reduction of elemental sulfur (S0) with NAD(P)H as an electron donor to produce hydrogen sulfide (H2S) under anaerobic conditions, was purified 69-fold after 35-65% ammonium sulfate precipitation and Q-Sepharose FF, Phenyl-Toyopearl 650 ML, and Blue Sepharose FF column chromatography, with a specific activity of 57.6 U (mg protein)(-1). The purified enzyme was quite labile under aerobic conditions, but comparatively stable in the presence of sodium hydrosulfite and under anaerobic conditions, especially under hydrogen gas conditions. The purified enzyme showed both sulfur reductase and hydrogenase activities. Both activities had an optimum pH of 9.0. Sulfur reductase has an apparent molecular weight of 120,000 Da, and is composed of three different subunits (M(r) 54,000 Da (alpha), 36,000 Da (beta), and 35,000 Da (gamma)), as estimated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. This is the first report on the purification of sulfur reductase from a mesophilic and obligate chemolithotrophic iron-oxidizing bacterium.     

Processing of arsenopyritic gold concentrates by partial bio-oxidation followed by bioreduction

Gold is commonly liberated from sulfide minerals by chemical and biological oxidation. Although these technologies are successful, they are costly and produce acidic waste streams. Removal of mineral-sulfur to overcome the mineralogical barrier could also be done by bioreduction, producing hydrogen sulfide (H(2)S). To make the sulfur within these minerals available for bioreduction, the use of partial bio-oxidation as a pretreatment to oxidize the sulfides to elemental sulfur was investigated in gas lift loop reactor experiments. Experiments at 35 °C using a refractory concentrate showed that at pH 2 arsenopyrite is preferentially partially oxidized over pyrite and that elemental sulfur can be subsequently converted into H(2)S at pH 5 via bioreduction using H(2) gas. A single partial bio-oxidation/bioreduction treatment increased the gold recovery of the concentrate from 6% to 39%. As elemental sulfur seems to inhibit further oxidation by covering the mineral surface, several treatments may be required to reach a gold recovery >90%. Depending on the number of treatments this method could be an interesting alternative to bio-oxidation.     

Efficient hydrogen sulfide adsorbents obtained by pyrolysis of sewage sludge derived fertilizer modified with spent mineral oil

Terrene, sewage sludge derived granulated fertilizer, was impregnated with spent mineral oil and then pyrolyzed at 600, 800, and 950 degrees C. Materials obtained were characterized from the point of view of the pore structure and surface chemistry. Then the H2S breakthrough capacitywas measured using a lab designed test. The results showed that the new adsorbents over perform by 30% materials obtained by simple thermal treatment of Terrene and by 230% virgin coconut shell based activated carbon. The surface reaction products were evaluated using thermal analysis. On the surface of new adsorbents hydrogen sulfide is oxidized mainly to elemental sulfur which is then deposited within the pore system. The breakthrough occurs when all small pores available to promote catalytic oxidation (caused by the inorganic sludge component) are filled with sulfur. An increase in pyrolysis temperature leads to an improvement in the performance of materials as hydrogen sulfide adsorbents. This is caused likely by changes in an inorganic phase and inorganic/carbonaceous phase interactions during pyrolysis.     

Adsorption of hydrogen sulfide onto activated carbon fibers: effect of pore structure and surface chemistry

To understand the nature of H2S adsorption onto carbon surfaces under dry and anoxic conditions, the effects of carbon pore structure and surface chemistry were studied using activated carbon fibers (ACFs) with different pore structures and surface areas. Surface pretreatments, including oxidation and heattreatment, were conducted before adsorption/desorption tests in a fixed-bed reactor. Raw ACFs with higher surface area showed greater adsorption and retention of sulfur, and heat treatment further enhanced adsorption and retention of sulfur. The retained amount of hydrogen sulfide correlated well with the amount of basic functional groups on the carbon surface, while the desorbed amount reflected the effect of pore structure. Temperature-programmed desorption (TPD) and thermal gravimetric analysis (TGA) showed that the retained sulfurous compounds were strongly bonded to the carbon surface. In addition, surface chemistry of the sorbent might determine the predominant form of adsorbate on the surface.     

Effects of variation of dietary sulfur on movement of sulfur in sheep rumen

Effects of variations in dietary sulfur on rumen sulfur dynamics were studied under steady state conditions. In the first experimental period, three sheep were given 33.3 g of a pelleted diet hourly containing 1.59 g sulfur/kg (low) and in the second period the sulfur content was increased to 3.21 g/kg (high) by the addition of sodium sulfate. The daily sulfur intake was 1.158 g on the low sulfur diet and .545 g of this passed from the rumen in protein, .614 g was calculated to be absorbed from the rumen as sulfide, and .052 g was estimated to be recycled to the rumen. For sheep with daily intakes of 2.317 g sulfur, 1.212 g passed from the rumen in protein, 1.078 g was absorbed from the rumen, and .093 g was estimated to be recycled. It was estimated that 127 and 165 g microbial protein were synthesized/kg organic matter "truly digested" in the rumen for low and high sulfur diets, respectively. A simple model using simultaneous equations was proposed to describe rumen sulfur metabolism.     

脱氮硫杆菌硫转移酶SoxAX的建模及分子对接

硫氧化酶系统(Sulfur oxidizing,Sox)在脱氮硫杆菌(Thiobacillus denitrificans,Td)的硫代谢过程中起着至关重要的作用,其核心为Sox AXYZB,硫化物需先经Sox AX蛋白催化并转移到Sox YZ上才能进行Sox通路后续的硫氧化反应,而目前尚无脱氮硫杆菌Sox AX蛋白结构解析的报道。本文采用反向折叠法构建了Sox AX蛋白的二聚体结构并验证其合理性,并通过分子对接实验探讨Sox AX蛋白模型与硫代硫酸盐、硫化氢和亚硫酸盐等不同底物结合在构型与能量上的差异。结果表明,构建的Sox AX二聚体蛋白结构相对合理,氢键是维持Sox AX二聚体结合的主要作用力,10个短强氢键和1个π键作用力参与维持二聚体结构的稳定,Sox A的Arg160等6个残基及Sox X的Asn15等8个残基对维持二聚体结构有重要作用。分子对接试验显示氢键是维持底物与Sox AX结合的主要作用力,与底物结合的关键氨基酸为Arg210、Cys214和Gln217。在三种底物与酶结合的亲和力中以硫化氢最高、硫代硫酸盐次之、亚硫酸盐最低。     

Municipal sludge-industrial sludge composite desulfurization adsorbents: synergy enhancing the catalytic properties

Mixtures of sewage sludge, waste oil sludge, and metal oil sludge were prepared and carbonized at 950 degrees C in an inert atmosphere. Dynamic adsorption of H2S was measured on the materials obtained, and the breakthrough capacity was calculated. The initial and exhausted adsorbents after the breakthrough tests were characterized using sorption of nitrogen, thermal analysis, and XRF, XRD, and surface pH measurements. Mixing sludges leads to very high capacity adsorbents on which hydrogen sulfide is oxidized to elemental sulfur. Although the micropore volume of the adsorbents obtained is not high, their high volume of mesopores contributes significantly to reactive adsorption and provides space to store the oxidation products. The H2S breakthrough capacity on the new materials reaches 10 wt %. These adsorbents work until all active pores are filled and the catalytic centers are exhausted. The reason for such high capacity is in the formation of catalytically active mineral like phases during pyrolysis in the presence of nitrogen and carbon. This highly dispersed phase provides basicity and catalytic centers for hydrogen sulfide dissociation and its oxidation to sulfur.     

Involvement of Volatile Sulfur Compounds in Ionizing Radiation-induced Off-odor of Fresh Orange Juice

ABSTRACT: The influences of ionizing radiation on volatile sulfur compounds in fresh Valencia orange juice were analyzed using gas chromatography (GC)-pulsed flame photometric detection and sensory evaluation. Methyl sulfide (MS) and methanethiol (MT) were induced most, followed by dimethyl disulfide and dimethyl trisulfide. Carbon disulfide was reduced by irradiation, while hydrogen sulfide was not consistently affected. Sensory evaluation indicated that the odor of irradiated juice differed from the nonirradiated samples at 0.5, 1, 2, or 3 kGy. Addition of the 2 major irradiation-induced sulfur compounds (MS and MT) into fresh juice changed the juice odor, indicating that those 2 compounds were probably involved in the development of irradiation-induced off-odor.     

Kinetics and mechanism of degradation of dichlorvos in aqueous solutions containing reduced sulfur species

Reactions of dichlorvos with five reduced sulfur species (hydrogen sulfide, bisulfide, thiosulfate, thiophenol, and thiophenolate) were examined in well-defined anoxic aqueous solutions to investigate their role in its degradation. Reactions were monitored at varying concentrations of reduced sulfur species over pH range to obtain the second-order reaction rate constants. Experiments at 25 degrees C demonstrated that degradation of dichlorvos promoted by bisufide, thiosulfate, and thiophenolate were of much greater importance than hydrolysis under the experimental conditions in our study. In contrast, hydrogen sulfide and thiophenol were not effective in the degradation of dichlorvos. The activation parameters of the reaction of dichlorvos with bisulfide, thiosulfate, and thiophenolate were also determined from the measured second-order rate constants over a temperature range of 12-50 degrees C. The relative reactivity of the reduced sulfur species decreases in the following order: PhS- > HS- approximately equal to S2O3(2-). When the second-order rate constants at 25 degrees C are multiplied by the environmentally relevant concentration of the reduced sulfur species, predicted half-lives of dichlorvos ranged from hours to days. The results indicated that reduced sulfur species could play a very important role in the chemical fate of dichlorvos in coastal marine environments.     

Sulfide-oxidizing activity and bacterial community structure in a fluidized bed reactor from a zero-discharge mariculture system

In the present work we describe a comprehensive analysis of sulfide oxidation in a fluidized bed reactor (FBR) from an environmentally sustainable, zero-discharge mariculture system. The FBR received oxygen-depleted effluent from a digestion basin (DB) that is responsible for gasification of organic matter and nitrogen. The FBR is a crucial component in this recirculating system because it safeguards the fish from the toxic sulfide produced in the DB. Microscale sulfide oxidation potential and bacterial community composition within FBR biofilms were correlated to biofilter performance by integrating bulk chemical, microsensor (O2, pH, and H2S), and molecular microbial community analyses. The FBR consistently oxidized sulfide during two years of continuous operation, with an estimated average sulfide removal rate of 1.3 g of sulfide-S L(FBR)(-1) d(-1). Maximum sulfide oxidation rates within the FBR biofilms were 0.36 and 0.21 mg of sulfide-S cm(-3) h(-1) in the oxic and anoxic layers, respectively, indicating that both oxygen and nitrate serve as electron acceptors for sulfide oxidation. The estimated anoxic sulfide removal rate, as extrapolated from bench scale, autotrophic, nitrate-amended experiments, was 0.7 g of sulfide-S L(FBR)(-1) d(-1), which is approximately 50% of the total estimated sulfide removal in the FBR. Community composition analyses using denaturing gradient gel electrophoresis (DGGE) of bacterial 16S rRNA gene fragments from FBR samples taken at six-month intervals revealed several sequences that were closely affiliated with sulfide-oxidizing bacteria. These included the denitrifying, sulfide-oxidizing bacteria Thiomicrospira denitrificans, members of the filamentous Thiothrix genus, and sulfide-oxidizing symbionts from the Gammaproteobacteria. In addition, marine Alphaproteobacteria and Bacteroidetes species were present in all of the DGGE profiles examined. DGGE analyses showed significant shifts in the bacterial community composition between profiles over two years of sampling, indicating the presence of a diverse and dynamic microbial community within the functionally stable FBR. The FBR's combined capacity for both oxic and anoxic sulfide oxidation, as indicated by bulk chemical, microsensor, and molecular microbial analyses, gives it significant functional elasticity, which is crucial for proper performance in the dynamic environment of this mariculture system.     

中药材二氧化硫快速定量检测系统的研发及验证

目的 建立一种针对中药材二氧化硫残留特异性强的定量快速检测系统。方法 利用醋酸铅检测微量硫化氢的高敏感性,以硫化铅黑色沉淀的灰度响应值为定量依据,设计醋酸铅检测卡,设计可控制反应条件使硫化铅灰度可线性地反映二氧化硫含量的检测反应器,研发与检测卡配套的可准确检测灰度值的定量检测仪。制备标准灰度卡、绘制检测灰度值与标准溶液浓度关系曲线、考察定量检测系统的精密度、加样回收率、时间稳定性,同时做干扰实验及用本系统与国标方法对同一批次中药材的二氧化硫残留量进行检测比较,评价检测体系的定量检测效果。结果 本检测系统试纸条的灰度值与标准溶液的浓度线性关系良好(R_²=0.99),线性检测范围在0 mg/kg到805 mg/kg之间;对高中低浓度的二氧化硫残留样品多次检测值的相对标准偏差均小于5%,加样回收率达到85%以上,精确性良好;常见的含硫化合物对其没有干扰,系统与2015版药典第三法(离子色谱法)对同一批次的中药材二氧化硫检测结果一致。结论 该检测系统准确性好,稳定可靠,特异性强,操作简便,可用于中药材二氧化硫残留的快速定量检测。     

Green chemistry methods in sulfur dyeing: application of various reducing D-sugars and analysis of the importance of optimum redox potential

The importance of sulfur dyeing of cellulosic fibers, particularly cotton, is realized economically throughout the dyeing industry. At the present time, dyeing with sulfur dyes requires the use of various auxiliaries, many of which have adverse effects on the environment. The most damaging of these is the reducing agent sodium sulfide, required to reduce the dye molecules to a water-soluble leuco form to enable adsorption and diffusion into the fiber. In this study, attempts have been made to replace the sodium sulfide used within the sulfur dyeing process with a variety of environmentally friendly reducing sugars. The redox potential of various hexose and pentose monosaccharides and reducing disaccharides was recorded and compared. Subsequently, cotton was dyed with the world's most important sulfur dye, C. I. Sulfur Black 1, using the reducing sugars under alkaline conditions, and compared to dyeings secured by employing commercial sulfide reducing agents. It was observed that reducing sugars gave comparable, and in many cases superior, color strength and wash fastness results, with respect to the commercial sulfide-based reducing agents, which still account for the vast majority of sulfur dyeing processes and that pose significant environmental concern. Employment of reducing sugars in sulfur dyeing could provide a sustainable, nontoxic, biodegradable, cost-effective alternative to sodium polysulfide and sodium hydrogen sulfide. Comparison of the redox potential of reducing sugars against the color strength of the dyeings secured demonstrated that there was an optimum redox potential of around -650 mV for maximum color strength achieved. The same redox potential also conferred the lowest color loss upon washing. These observations were attributed to reduction of the polymeric dye molecules to an optimum size for fiber affinity and diffusion into the fiber, but which would also confer maximum wash fastness upon oxidation.