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1.
The reactions of thiometon and its ethyl analogue, disulfoton, with reduced sulfur species [e.g., bisulfide (HS-), polysulfide (S(n)2-), thiophenolate (PhS-), and thiosulfate (S2O3(2-))] were examined in well-defined aqueous solutions under anoxic conditions. The role of reduced sulfur species was investigated in the abiotic degradation of thiometon and disulfoton. Experiments at 25 degrees C demonstrated that HS-, S(n)2-, PhS-, and S2O3(2-) promoted the degradation of thiometon to a great extent while only S(n)2- and PhS- showed a small accelerating effect in the degradation of disulfoton. Reactions were monitored at varying concentrations of reduced sulfur species to obtain the second-order rate constants. The reactivity of the reduced sulfur species decreased in the following order: S(n)2- > PhS- > HS- approximately S2O3(2-). Transformation products were confirmed by standards or characterized by gas chromatography mass spectrometry. The results illustrate that multiple pathways occur in the reactions with reduced sulfur species, among which the nucleophilic attack at the alpha-carbon of the alkoxy group was the predominant pathway. Activation parameters of the reaction of thiometon and disulfoton with HS- were also determined from the measured second-order rate constants over a temperature range. DeltaH( not equal) values indicated that the reactivity of thiometon toward HS- was much greater than for disulfoton. Nucleophilic attack at the alkoxy group was more important for thiometon than disulfoton. When the measured second-order rate constants at 25 degrees C are multiplied by [HS-] and Sigma[S(n)2-] reported in saltmarsh porewaters, predicted half-lives show that reduced sulfur species present at environmentally relevant concentrations may present an important sink for thiometon in coastal marine environments.  相似文献   

2.
The reactions of phorate and terbufos with bisulfide (HS-), polysulfide (Sn2-), thiosulfate (S2O32-), and thiophenolate (PhS-) were examined in well-defined aqueous solution under anoxic conditions to investigate their role in the degradations of phorate and terbufos. Reactions were monitored at various concentrations of reduced sulfur species to obtain the second-order rate constants. The reactivity of the reduced sulfur species decreased in the order Sn2- > PhS- > HS- > S2O32-. Hydrolysis products, formaldehyde and diethyl disulfide/di-tert-butyl disulfide, indicated that OH-/H2O attacked the carbon atom between the two sulfur atoms, the so-called thioacetal carbon, which is very reactive due to the presence of the two neighboring sulfur atoms. The reaction of phorate and terbufos with PhS- was investigated to study the transformation products in the reactions with reduced sulfur species. The transformation products demonstrated that the observed increase in rate constants in the reaction with reduced sulfur species compared to hydrolysis could result from the nucleophilic attack of reduced sulfur species at the alpha-carbon of the ethoxy group and at the thioacetal carbon atom. The temperature dependence of measured second-order rate constants of the reaction of phorate and terbufos with HS- over 25-50 degrees C was investigated to explore activation parameters, which are not significantly different for phorate and terbufos. All of the observations may imply similar pathways in the degradation of phorate and terbufos in the presence of reduced sulfur species. Slightly higher hydrolysis rates of terbufos and second-order reaction rate constants for the reactions with sulfur species of terbufos compared with those for phorate are observed, which could be attributed to the slightly different substituents.  相似文献   

3.
The chlorinated fumigants chloropicrin (trichloronitromethane) and 1,3-dichloropropene (1,3-D) are extensively used in agricultural production for the control of soilborne pests. The reaction of these two fumigants with hydrogen sulfide species (H2S and HS-) was examined in well-defined anoxic aqueous solutions. Chloropicrin underwent an extremely rapid redox reaction in the hydrogen sulfide solution. Transformation products indicated reductive dechlorination of chloropicrin by hydrogen sulfide species to produce dichloro- and chloronitromethane. The transformation of chloropicrin in hydrogen sulfide solution significantly increased with increasing pH, indicating that H2S is less reactive toward chloropicrin than HS- is. For both 1,3-D isomers, kinetics and transformation products analysis revealed that the reaction between 1,3-D and hydrogen sulfide species is an S(N)2 nucleophilic substitution process, in which the chlorine at C3 of 1,3-D is substituted by the sulfur nucleophile to form corresponding mercaptans. The 50% disappearance time (DT50) of 1,3-D decreased with increasing hydrogen sulfide species concentration at a constant pH. Transformation of 1,3-D was more rapid at high pH, suggesting that the reactivity of hydrogen sulfide species in the experimental system stems primarily from HS-. Because of the relatively low smell threshold values and potential environmental persistence of organic sulfur products yielded by the reaction of 1,3-D and HS-, the effects of reduced sulfide species should be considered in the development of alternative fumigation practices, especially in the integrated application of sulfur-containing fertilizers.  相似文献   

4.
Fatalities associated with entry into on-farm confined-space manure storage facilities occur each year. The fatalities are due to asphyxiation or poisoning by exposure to high concentrations of hydrogen sulfide, methane, and carbon dioxide. Forced ventilation has been shown to be an effective way to reduce concentrations of noxious gases to levels that are safe for human entry into these storage facilities. Hydrogen sulfide (H2S) was used as an indicator gas to investigate the effectiveness of forced-air ventilation strategies for eliminating the toxic and oxygen-deficient atmosphere in confined-space manure storage facilities. This article focuses on experimental methods for identifying ventilation strategies that effectively reduce toxic gas (i.e., H2S) concentrations in a fan-ventilated confined-space manure tank to the OSHA permissible exposure limit (PEL) (H2S PEL = 10 ppm) and to 25% of the initial gas concentration. Typical H2S concentration reduction curves during forced-air ventilation were identified in the tank as well. Based on the experimental tests conducted in this research, the most promising candidate ventilation strategies were identified for this rectangular confined-space manure tank with solid, fully slotted, and partially slotted covers. In addition, based on the results of experimental tests, a field-based database was developed for future validation of computational fluid dynamics modeling protocols.  相似文献   

5.
Accumulating evidence shows that hydrogen sulfide (H(2)S) plays various physiological roles in plants, such as seed germination, root organogenesis, abiotic stress tolerance, and senescence of cut flowers. However, whether H(2)S participates in the regulation of ripening and senescence in postharvest fruits remains unknown. In the present study, the effect of H(2)S on postharvest shelf life and antioxidant metabolism in strawberry fruits was investigated. Fumigation with H(2)S gas released from the H(2)S donor NaHS prolonged postharvest shelf life of strawberry fruits in a dose-dependent manner. Strawberry fruits fumigated with various concentrations of H(2)S sustained significantly lower rot index, higher fruit firmness, and kept lower respiration intensity and polygalacturonase activities than controls. Further investigation showed that H(2)S treatment maintained higher activities of catalase, guaiacol peroxidase, ascorbate peroxidase, and glutathione reductase and lower activities of lipoxygenase relative to untreated controls. H(2)S also reduced malondialdehyde, hydrogen peroxide, and superoxide anion to levels below control fruits during storage. Moreover, H(2)S treatment maintained higher contents of reducing sugars, soluble proteins, free amino acid, and endogenous H(2)S in fruits. We interpret these data as indicating that H(2)S plays an antioxidative role in prolonging postharvest shelf life of strawberry fruits.  相似文献   

6.
Vanillin was found to be efficient as a deactivator of ferrylmyoglobin with a second-order rate constant of k(2) = 57 ± 1 L mol(-1) s(-1) for reduction to metmyoglobin with ΔH(?) = 58.3 ± 0.3 kJ mol(-1) and ΔS(?) = -14 ± 1 J mol(-1) K(-1) in aqueous pH 7.4 solution at 25 °C. Binding to β-lactoglobulin (βLG) was found to affect the reactivity of vanillin at 25 °C only slightly to k(2) = 48 ± 2 L mol(-1) s(-1) (ΔH(?) = 68.4 ± 0.4 kJ mol(-1) and ΔS(?) = 17 ± 1 J mol(-1) K(-1)) for deactivation of ferrylmyoglobin. Binding of vanillin to βLG was found to have a binding stoichiometry vanillin/βLG > 10 with K(A) = 6 × 10(2) L mol(-1) and an apparent total ΔH° of approximately -38 kJ mol(-1) and ΔS° = -55.4 ± 4 J mol(-1) K(-1) at 25 °C and ΔC(p, obs) = -1.02 kJ mol(-1) K(-1) indicative of increasing ordering in the complex, as determined by isothermal titration microcalorimetry. From tryptophan fluorescence quenching for βLG by vanillin, approximately one vanillin was found to bind to each βLG far stronger with K(A) = 5 × 10(4) L mol(-1) and a ΔH° = -10.2 kJ mol(-1) and ΔS° = 55 J mol(-1) K(-1) at 25 °C. The kinetic entropy/enthalpy compensation effect seen for vanillin reactivity by binding to βLG is concluded to relate to the weakly bound vanillin oriented through hydrogen bonds on the βLG surface with the phenolic group pointing toward the solvent, in effect making both ΔH(?) and ΔS(?) more positive. The more strongly bound vanillin capable of tryptophan quenching in the βLG calyx seems less or nonreactive.  相似文献   

7.
The effects of wine composition and postbottling oxygen exposure on 3-mercaptohexanol (3-MH), hydrogen sulfide (H2S), and methyl mercaptan (MeSH) were investigated. A Sauvignon blanc wine with initial copper concentration of 0.1 mg/L was treated with copper sulfate and/or glutathione (GSH) prior to bottling to give final concentrations of 0.3 and 20 mg/L, respectively. The wines were bottled with a synthetic closure previously stored in either ambient air or nitrogen to study the effect of the oxygen normally present in the closure. Bottled wines were stored for 6 months in either air or nitrogen to study the effect of oxygen ingress through the closure. Copper addition resulted in a rapid initial decrease in 3-MH. During storage, a further decrease of 3-MH was observed, which was lower with GSH addition and lowered oxygen exposure. H2S accumulated largely during the second 3 months of bottle storage, with the highest concentrations attained in the wines treated with GSH and copper. Lower oxygen from and through the closure promoted H2S accumulation. The concentration of MeSH was virtually not affected by the experimental variables at 6 months, although differences were observed after 3 months of storage. The implications for wine quality are discussed.  相似文献   

8.
The emission of gaseous sulfur (S) compounds by plants is related to several factors, such as the plant S status or fungal infection. Hydrogen sulfide (H(2)S) is either released or taken up by the plant depending on the ambient air concentration and the plant demand for S. On the contrary, carbonyl sulfide (COS) is normally taken up by plants. In a greenhouse experiment, the dependence of H(2)S and COS exchange with ambient air on the S status of oilseed rape ( Brassica napus L.) and on fungal infection with Sclerotinia sclerotiorum was investigated. Thiol contents were determined to understand their influence on the exchange of gaseous S compounds. The experiment revealed that H(2)S emissions were closely related to pathogen infections as well as to S nutrition. S fertilization caused a change from H(2)S consumption by S-deficient oilseed rape plants to a H(2)S release of 41 pg g(-1) (dw) min(-1) after the addition of 250 mg of S per pot. Fungal infection caused an even stronger increase of H(2)S emissions with a maximum of 1842 pg g(-1) (dw) min(-1) 2 days after infection. Healthy oilseed rape plants acted as a sink for COS. Fungal infection caused a shift from COS uptake to COS releases. The release of S-containing gases thus seems to be part of the response to fungal infection. The roles the S-containing gases may play in this response are discussed.  相似文献   

9.
Recently a new assay method that can quantify the singlet oxygen absorption capacity (SOAC) of antioxidants was proposed. In the present work, kinetic study of the reaction of singlet oxygen ((1)O(2)) with carotenoids and vegetable extracts has been performed in ethanol/chloroform/D(2)O (50:50:1, v/v/v) solution at 35 °C. Measurements of the second-order rate constants (k(Q)(S)) and the SOAC values were performed for eight kinds of carotenoids and three kinds of vegetable extracts (red paprika, carrot, and tomato). Furthermore, measurements of the concentrations of the carotenoids included in vegetable extracts were performed, using a HPLC technique. From the results, it has been clarified that the total (1)O(2)-quenching activity (that is, the SOAC value) for vegetable extracts may be explained as the sum of the product {Σ k(Q)(Car-i)(S) [Car-i](i)} of the rate constant (k(Q)(Car-i)(S)) and the concentration ([Car (i)]) of carotenoids included in vegetable extracts.  相似文献   

10.
多层生物滤塔去除废气中硫化氢   总被引：3，自引：1，他引：2  
为了解决填料及单层滤塔中压降大、效率低的问题,以单层玉米芯生物滤塔为对照,研究了多层生物滤塔对低浓度H2S气体的净化效果,其适宜的工艺条件和生物降解宏观动力学。结果表明：填料分层填充可提高废气中H2S去除率,当进气浓度低于140 mg/m3时,H2S的去除率90%以上;H2S进气容积负荷、去除率与填料层填充厚度有一定的相关性,负荷低于42.2 g/(m3·d),下层200 mm填料对H2S总去除率的贡献在95%以上;填料含水率为55%～70%,生物滤塔的微生物活性较高,净化效率高;试验条件下,采用Michaelis-Menten模型进行生物降解宏观动力学研究,其中半饱和常数为12.4 mg/m3,污染物最大去除速率为909 g/(m3·d)。试验表明：多层生物滤塔净化效果优于单层,其气流分布更均匀,停留时间延长,压降低,效率高;在适宜的工艺条件下运行3个月,对H2S净化效率均稳定在90%以上,为进一步研究及工程应用提供理论指导。  相似文献   

11.
Sulfur (S) conversions were determined during summer stratification in 1995/96 to assess the extent to which benthic release of phosphorus (P) is influenced by the S cycling in eutrophic, dimictic, sulfate-rich (61.33 ± 10.41 mg SO42- l-1) freshwater Lake Schamützelsee. Hypolimnetic SO42- reduction (4.56 ± 0.73 g (S) m-2 d-1) forming ΣH2S (44.71 ± 17.57 mg ΣH2S m-2 d-1), leading to iron sulfide precipitation (5.62 ± 1.72 mg FeS m-2 d-1) and dissolved iron depletion in the hypolimnion has a major influence on benthic P mobilization and release. The most important inorganic S pool is the CRS (FeS2 + S° + H2S; 15.1 % total S), being 1.3 to 6.6 times higher than the AVS (FeS + H2S) in the uppermost 0 - 8 cm sediment. This diminishes the ability of the sediment to bind P (indicated by 14.6 % loosely bound P (NH4Cl-P) and an exhaustion of the redox-sensitive P (BD-P)), leading to interstitial water P concentrations up to 10.8 mg l-1 and P release rates of 2.64 ± 0.56 mg P m-2 d-1. As a consequence the P content of the lake increased fourfold within 58 days.  相似文献   

12.
Water, Air, & Soil Pollution - The article presents the results of the study of sulfur-containing gases (carbon disulfide, CS2, and dimethyl sulfide, C2H6S) in the air above the sulfide...  相似文献   

13.
Carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) (CBF) is a widely used insecticide. Traditional methods like hydrolysis and direct photolysis cannot remove CBF effectively. In this study, the photodecay of 0.1 mM CBF in UV/H2O2, UV/S2O8(2-), and UV/H2O2/S2O8(2-) and sequential addition of a second oxidant were studied under UV light at 254 nm. The degradations of CBF follow pseudo-first-order decay kinetics. Direct photolysis was slow, but the corresponding degradation rate was increased with the addition of hydrogen peroxide (H2O2) or potassium peroxydisulfate (K2S2O8). In the UV/H2O2 reaction, the optimum reaction rate was 0.9841 min-1 at 10 mM H2O2 (pH 7); however, retardation is observed if H2O2 is overdosed. Such retardation is not observed in the UV/S2O8(2-) system, but a nonlinear increment of removal efficiency is identified. The UV/H2O2/S2O8(2-) process on the other hand shows the best performance in CBF degradation, but it has a less effective mineralization than that of the sole UV/S2O8(2-) reaction.  相似文献   

14.
2-Alkyl-(2H)-thiapyrans and 2-alkylthiophenes have been identified in the volatiles of cooked beef and lamb. The quantities of both groups of compounds were higher in the meat of animals fed lipid supplements high in n-3 polyunsaturated fatty acids. 2-Alkyl-(2H)-thiapyrans were formed when (E,E)-2,4-dienals (C(6)-C(11)) and hydrogen sulfide were heated at 140 degrees C for 30 min. This confirmed their proposed route of formation in cooked meat from lipid-derived aldehydes and hydrogen sulfide; the latter was produced from the degradation of cysteine, via the Maillard reaction. The mass spectra and NMR spectra of these thiapyrans are reported for the first time. Although 2-alkyl-(2H)-thiapyrans were found to have only low odor potency, the reactions by which they are formed may have important implications for meat flavor. These reactions may remove potent aroma compounds and their intermediates from meat, thus modifying the overall aroma profile.  相似文献   

15.
The biofilter system containing tire-derived rubber particle (TDRP) filter media was utilized to treat the odorous gas contaminant, hydrogen sulfide, in consideration of the economic advantage of reusing discarded tire materials and the high potential of TDRP media for biofilm attachment. The pilot-scale system having 0.38 m3 of bed volume operated with synthetic hydrogen sulfide gas on continuous basis from a range of 0.34 to 1.15 m3/min. This bioreactor system achieved over 94% removal efficiency at 20?C90 ppm of inlet H2S concentration while operating in 20?C67 s of empty bed retention time, indicating that overall effective operation was performed at mass loading rates of H2S ranging from 19.6 to 28.5 g H2S/(m3?h). It was apparent by the effectiveness of the system??s performance that this system had the capability to effectively remove hydrogen sulfide with high efficiency over a range of concentrations. A maximum elimination capacity was not found for the biofilter during this study, which tested loading rates between 0 and 30 g H2S/(m3?h).  相似文献   

16.
Metolachlor is one of the most widely used herbicides in the world for controlling weeds. It has been detected in both ground and surface waters in the United States, and there are rising concerns in regard to its health risks and in developing effective treatment processes for its removal from water. Degradation of metolachlor via ultraviolet (UV) photolysis and an UV/hydrogen peroxide advanced oxidation process (AOP) was studied. The quantum yield of metolachlor at 254 nm was found to be 0.302 +/- 0.001 mol E-1 through direct UV photolysis in the range of pH 6-8. The second-order rate constant of the reaction between metolachlor and hydroxyl radical was determined to be 9.07 (+/-0.21) x 10(9) M-1 s-1 by using a competition kinetics model that utilized nitrobenzene as a reference compound. In addition, these parameters were successfully applied in modeling the kinetics of elimination of metolachlor using an UV/H2O2 process in both laboratory and natural waters. The formation of several photolysis byproducts was identified using gas chromatography/mass spectrometry, and a scheme for the metolachlor photodegradation pathway is proposed.  相似文献   

17.
  【目的】  研究通风量对城市污泥堆肥过程中硫素转化和挥发性硫化物释放的影响,为有效控制挥发性含硫恶臭物质,保留污泥堆肥产品中的硫素营养提供理论依据和方法。  【方法】  城市污泥和调理剂 (锯末) 以3∶1 (湿重) 的比例混合后,采用自动好氧堆肥控制装置进行15天的堆肥试验,通过改变鼓风机频率实现不同堆体的通风量调节。设置鼓风机工作频率10、13、16 Hz 3个处理,相应的通风量为2.5、3.0和3.5 L/min。在堆肥的第0、1、2、3、5、7、9、11、13、15天进行堆体内部多点混合采样,进行挥发性硫化物的浓度测定,研究城市污泥不同堆肥阶段硫素的转化特征。  【结果】  相较于低通风量 (10 Hz),高通风量 (16 Hz) 下H2S的峰值浓度下降了约50%,但其累积释放量增加了45.4%;甲硫醚的累积释放量提高了398%,峰值浓度增加了490.8%;CS2的累积释放量下降了57.8%,其峰值浓度下降了77%。堆肥产品中有效硫浓度在低、中、高通风量条件下相较于堆肥前分别上升了19.5%、19.1%、36.1%。  【结论】  城市污泥堆肥过程中,提高通风量可以降低H2S的浓度峰值,但增加了H2S的累积释放量,甲硫醚的峰值浓度和累积释放量均显著增加;提高通风量可以抑制城市污泥堆肥过程中CS2的释放。在低、中、高3种通风量条件下,堆肥产品的有效硫浓度相较于堆肥前都明显升高。高通风处理虽然全量硫的损失最大,但更有利于提高堆肥产品中可直接被植物吸收的有效硫含量。  相似文献   

18.
Studies were conducted to evaluate the cell damage caused by exposing human colon carcinoma cells, Caco-2, to hydrogen peroxide at concentrations varying from 0 to 250 microM for 30 min. Evaluation of cell viability, as measured by trypan blue dye exclusion test, showed that the loss of viability was < 5% at concentrations up to 250 microM hydrogen peroxide. Cell membrane damage and DNA damage as measured by the leakage of lactate dehydrogenase and the comet assay, respectively, were significantly high at concentrations >100 microM hydrogen peroxide compared to those of the control. Antioxidant mechanisms in Caco-2 cells were evaluated by measuring catalase, superoxide dismutase, and glutathione peroxidase activities. Catalase activities remained constant in cells treated with 50-250 microM hydrogen peroxide. Superoxide dismutase activity decreased, whereas glutathione peroxidase activity increased in cells treated with H(2)O(2) concentrations of >50 microM. This study showed that with increasing hydrogen peroxide concentration, cell membrane leakage and DNA damage increased, whereas the three antioxidant enzymes responded differently, as shown by mathematical models.  相似文献   

19.
The main scope of the wide use of organic amendments of various origin and nature in modern agriculture is to increase and/or restore the organic matter content in organically poor or depleted soils in order to maintain and/or increase crop production and reduce soil exposure to degradation, erosion, desertification and pollution. The agronomically efficient and environmentally safe use of any organic amendment requires, however, an adequate control not only of the chemical quality of the humic substance (HS)-like fractions contained, which is an important indicator of the maturity and stability achieved by organic matter in the amendment, but also of the effects that these HS may have on native soil HS. In this review, the most recent results obtained on this topic by the research groups operating in Bari, Italy, and in Madrid, Spain, are discussed comparatively with results recently published by other research groups. Overall, HS-like components of organic amendments are characterized by higher aliphatic character and molecular heterogeneity, lower contents of O, acidic functional groups and organic free radicals, and lower degrees of aromatic ring polycondensation, polymerization and humification than native soil HS. These differences are less evident for composted materials. The composition, structure and functionalities of HS in amended soils may be affected in different ways and at various extents on dependence of the nature, origin and rate of amendment. In general, these properties are intermediate between those of the unamended soil HS and the HS-like fractions in the amendment, but generally resemble more the former than the latter, especially with increasing time after amendment application.  相似文献   

20.
In recent decades, SO4 2- concentrations have increased in groundwater and surface water of freshwater wetlands. For many minerotrophic peatlands, S originating from SO4 2--polluted groundwater and surface water is a more significant source of SO4 2- than the actual atmospheric deposition of S compounds. Lowered groundwater tables in wetlands, as a result of either natural or anthropogenic desiccation, may cause acidification because of concomitant geochemical oxidation processes. The impact of the enhanced availability of reduced S compounds, due to preceding SO4 2- pollution, on these processes was tested in a mesocosm experiment, using soil cores including vegetation from a mesotrophic wet meadow. The soils had been maintained in waterlogged condition for seven months, using two environmentally relevant SO4 2- concentrations (2 and 4 mmol L-1). The groundwater table was reduced in two successive steps: 10 cm below soil surface, and complete desiccation. Control pretreated soils did not show a decrease in soil pH during desiccation, due to adequate buffering by bicarbonate. However, both SO4 2--pretreated groups showed a significant drop in pH (from 6.5 to 4.5) caused by additional sulfide oxidation, leading to high SO4 2- concentrations (10 and 16 mmol L-1, respectively). Cation exchange and acidification-related solubilization processes induced the mobiliztation of base cations and potentially phytotoxic metals like Al. Nutrient concentrations in soil moisture were influenced strongly by SO4 2- pretreatment, showing distinct patterns for P, N and K. Therefore, S polluted groundwater and surface water may severely increase the sensitivity of wetlands to desiccation. The results are discussed in relation to wetland management.  相似文献   

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