Fulvic Acid-Sulfide Ion Competition for Mercury Ion Binding in the Florida Everglades

Negatively charged functional groups of fulvic acid compete with inorganic sulfide ion for mercury ion binding. This competition is evaluated here by using a discrete site-electrostatic model to calculate mercury solution speciation in the presence of fulvic acid. Model calculatedspecies distributions are used to estimate a mercury-fulvicacid apparent binding constant to quantify fulvic acid and sulfide ion competition for dissolved inorganic mercury (Hg(II)) ion binding. Speciation calculations done with PHREEQC,modified to use the estimated mercury-fulvic acid apparent binding constant, suggest that mercury-fulvic acid and mercury-sulfide complex concentrations are equivalent for very low sulfide ion concentrations (about 10^-11 M) in Everglades' surface water. Where measurable total sulfide concentration (about 10^-7 M or greater) is present inEverglades' surface water, mercury-sulfide complexes shoulddominate dissolved inorganic mercury solution speciation. Inthe absence of sulfide ion (for example, in oxygenated Everglades' surface water), fulvic acid binding should dominateEverglades' dissolved inorganic mercury speciation.     

Dechlorination of chloropicrin and 1,3-dichloropropene by hydrogen sulfide species: redox and nucleophilic substitution reactions

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.     

Gas chromatographic identification of sulfur gases in soil atmospheres

Simple gas Chromatographic methods for identification of sulfur gases in soil atmospheres are described. They involve the use of a flame photometric detector fitted with a sulfur filter and of Teflon columns packed with Chromosorb T and Deactigel. The methods permit identification of 13 volatile sulfur compounds (sulfur dioxide, hydrogen Sulfide, carbon disulfide, carbonyl sulfide, sulfur hexafluoride, methyl mercaptan, ethyl mercaptan, n-butyl mercaptan, dimethyl sulfide, ethyl methyl sulfide, diethyl sulfide, dimethyl disulfide, and diethyl disulfide) in air containing trace (nanogram) amounts of these compounds, and they are not subject to interference by various gases known to be evolved from soils under aerobic or anaerobic conditions. The Deactigel column is not required if the gas mixture analyzed does not contain hydrogen sulfide or carbonyl sulfide.     

Effects of Low-Level Aqueous Hydrogen Sulfide and Other Sulfur Species on Lettuce (Lactuca sativa) Seed Germination

Low concentrations of aqueous hydrogen sulfide (H₂S) can stimulate growth of some crops. However, it is not clear whether H₂S provides crops with only sulfur and whether other sulfur compounds have similar beneficial effects. Therefore, impacts of solutions of sodium sulfate (Na₂SO₄), sodium sulfite (Na₂SO₃), sodium sulfide (Na₂S), ferrous sulfide (FeS), and H₂S at 0.01–1 mM were assessed on 5-day lettuce seed germination. Results showed that 0.01 mM H₂S solution significantly increased lettuce shoot elongation by 40 percent (to 43.6 mm from 31.0 mm in the control), whereas 0.1 mM increased elongation by 24 percent to 38.5 mm. Only a slight 10 percent increase was observed in 0.1 mM Na₂SO₄, suggesting that ameliorative impact of H₂S on plant growth was not a result of providing sulfur nutrient. Other sulfur solutions, however, inhibited lettuce germination and elongation to varying extents, hinting that H₂S might work as a signal molecule in regulating plant cellular activities.     

Garlic allyl sulfides display differential modulation of rat cytochrome P450 2B1 and the placental form glutathione S-transferase in various organs

To investigate whether the regulation of garlic allyl sulfides on biotransformation enzyme expression is tissue-specific, the expression of cytochrome P450 2B1 (CYP 2B1) and the placental form of glutathione S-transferase (PGST) in liver, lung, and intestine, which are the three major organs responsible for drug metabolism, was examined. Rats were orally administrated 0.5 or 2 mmol/kg BW diallyl sulfide (DAS) or 0.5 mmol/kg BW diallyl disulfide (DADS) or diallyl trisulfide (DATS) three times per week for 6 weeks. The final body weights and the body weight ratio of liver and lung were not changed by any of these three allyl sulfide treatments as compared to the control rats. An 11- and 12-fold increase of 7-pentoxyresorufin O-dealkylase (PROD) activities was noted in rats treated with 0.5 or 2 mmol/mg BW DAS, respectively, as compared with the controls (P < 0.05). In contrast, DADS and DATS significantly increased hepatic PGST activity toward ethacrynic acid by 30 and 40%, respectively, as compared with the control rats (P < 0.05). An increase in PGST activity was only noted at 2 mmol/kg BW DAS group (P < 0.05). In addition, similar increases in PGST activity due to DADS and DATS were also noted in lung and jejunum tissue (P < 0.05). Immunoblot assay shows that the changes in CYP 2B1 and PGST proteins due to the three garlic allyl sulfide treatments on liver, lung, and jejunum were consistent with those observed for PROD and PGST activities. Northern blot further revealed that the DADS and DATS increased PGST mRNA levels in both liver (2.9- and 3.0-fold, respectively) and lung (4.1- and 2.6-fold, respectively) and DAS dose-dependently increased CYP 2B1 mRNA levels in the liver. Garlic allyl sulfides differentially induced CYP 2B1 and PGST expression, and this up-regulation of these two biotransformation enzymes is tissue-specific.     

Characterization of the most odor-active compounds of Iberian ham headspace

Gas chromatography-olfactometry (GC-O) based on detection frequency (DF) was used to characterize the most odor-active compounds from the headspace of Iberian ham. Twenty-eight odorants were identified by GC-O on two capillary columns, including aldehydes (11), sulfur-containing compounds (7), ketones (5), nitrogen-containing compounds (2), esters (2), and an alcohol. Among them, the highest odor potencies (DF values) were found for 2-methyl-3-furanthiol, 2-heptanone, 3-methylbutanal, methanethiol, hexanal, hydrogen sulfide, 1-penten-3-one, 2-methylpropanal, ethyl 2-methylbutyrate, and (E)-2-hexenal. Nine of the 28 most odor-active compounds were identified for the first time as aroma components of dry-cured ham, including hydrogen sulfide, 1-penten-3-one, (Z)-3-hexenal, 1-octen-3-one, and the meaty-smelling compounds 2-methyl-3-furanthiol, 2-furfurylthiol, 3-mercapto-2-pentanone, 2-acetyl-1-pyrroline, and 2-propionyl-1-pyrroline.     

牛粪好氧发酵挥发性物质排放特征及恶臭物质分析

不同原料好氧发酵产生的臭气物质组分和浓度存在差异。以牛粪和玉米秸秆为原料研究好氧发酵过程挥发性有机物（Volatile Organic Compound，VOCs）的产排特征及主要致臭物质，开展牛粪好氧发酵试验，采用气相色谱-质谱法分析测定发酵升温期、高温期、降温期及腐熟期等不同发酵阶段的VOCs组分和浓度，硼酸溶液吸收，盐酸滴定法测定NH3，便携式检测器（Tion NH3-H2S 300 G）测定H2S，3点比较式臭袋法测定不同发酵阶段臭气浓度。结果表明，牛粪好氧发酵过程中共检出31种VOCs，其中含硫化合物42种，醇类1种，酯类1种，酮类1种，卤代烃4种，苯系物9种，烷烃类8种，烯烃3种；在好氧发酵高温期臭气浓度最高为724（无量纲），VOCs产生与排放主要在高温期。基于恶臭污染排放标准和恶臭物质气味活度值，并结合各物质检出率、GS-MS图谱及相关性分析，发现NH3、H2S、甲硫醚是牛粪好氧发酵过程的主要致臭物质；其次芳香族化合物对臭气浓度贡献也相对较大，应进行重点监测与控制。该研究可为牛粪好氧发酵过程臭气物质减控提供理论支撑。     

Development of a Biofilter with Tire-Derived Rubber Particle Media for Hydrogen Sulfide Odor Removal

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).     

Sulfide Production by Sulfate Reducing Bacteria with Lactate as Feed in an Upflow Anaerobic Fixed Film Reactor

The sulfate reducing bacteria (SRB) have the capability of reducing sulfate (SO4-2) under anaerobic conditions into sulfide (S-2) which can precipitate metals as metal sulfides. The optimum conditions for sulfide production by SRB utilizing lactate, in an upflow anaerobic fixed film reactor (UAFFR) were not previously established. The main objective of this research was to investigate these conditions for the growth of SRB to ensure the highest sulfide production under consistent behaviour of the system. Substrate containing lactate as the organic carbon source along with sulfate, nitrogen and phosphorus as the required nutrients was used as a feed to the UAFER which was seeded with SRB. It was found that an optimum sulfide production occurred with an organic loading rate (OLR) of 6 kg d-1 m-3, while the theoretical oxygen demand to sulfate ratio (ThOD/SO4) ranged from 1.5 to 2.25. Also, the optimum total nitrogen and phosphorus demands were determined to be about 250 and 50 mg L-1 respectively. A total nitrogen concentration above 600 mg L-1 started showing toxicity and lowered the sulfide production. The optimum ThOD:N:P for sulfide production and growth of SRB in the UAFFR was 100:5:1 under optimum conditions.     

Influence of some technological parameters on the formation of dimethyl sulfide, 2-mercaptoethanol,methionol, and dimethyl sulfone in port wines

Volatile sulfur compounds of 15 young port wines and 12 old port wines were determined. As there is a great difference in the pool of sulfur compounds between the two groups of wines, an experimental protocol was performed to determine which technological parameter (dissolved O(2), free SO(2) levels, pH, and time/temperature) was related with the formation/consumption of these compounds. Four sulfur compounds were selected for this purpose: dimethyl sulfide, 2-mercaptoethanol, dimethyl sulfone, and methionol. The synergistic effects of increasing temperature and O(2) at lower pH had the largest impact. Dimethyl sulfide was formed during the experimental period in the presence of O(2). Dimethyl sulfone had the same behavior. Methionol decreased significantly in the presence of O(2), but no methional was formed. 2-Mercaptoethanol, considered to be an important "off-flavor" in dry wines, also decreased during the experimental period (54 days) in the presence of O(2), and the respective disulfide was formed. These results corroborate the fact that old port wine (barrel aged) never develops "off-flavors" associated with the presence of methionol (cauliflower), 2-mercaptoethanol (rubber/burnt), or methional (cooked potato). In fact, temperature and oxygen are the major factors in the consumption of these molecules. However, some notes of "quince" and "metallic" can appear during port wine aging, and these can be associated with the presence of dimethyl sulfide.     

Observations on the bismuth sulfide colorimetric procedure for sulfate analysis in soil

Abstract

The bismuth sulfide and methylene blue colorimetric finishes for soil sulfate determination by the Johnson‐Nishita distillation method were examined and compared. Both procedures gave comparable results when applied to soils and soil extracts, but the bismuth method was more rapid and more reliable. Nitrogen flow rate over the range 100–500 ml/min was not critical for the bismuth method, provided appropriate distillation times were employed. However, the release and transfer of hydrogen sulfide in the bismuth method was effected in one‐third of the time required for the méthylène blue finish, largely due to the elimination of a gas‐washing step. Predrying of soil extract samples increased recovery of hydrogen sulfide with the bismuth procedure arid could be used to increase sensitivity. Nitrate interference was observed with the bismuth procedure but attributed to interference during the reduction step. The bismuth procedure can readily be adapted for microdetermination in the 0–40 ppm sulfate‐S range.     

Evaluation of Arsenic Availability in Sulfidic Materials from Gold Mining Areas in Brazil

This study is aimed at evaluating the availability and mobility of arsenic in sulfidic materials from gold mining areas in Minas Gerais State, Brazil. Eight extraction media were employed in a sequential extraction scheme, as follows: exchangeable As; strongly adsorbed As; As coprecipitated with acid-volatile sulfide, carbonates, MnO₂, and Al₂O₃; As coprecipitated with amorphous iron; As linked to crystalline iron oxide; As coprecipitated with silicates; As coprecipitated with amorphous FeS₂ and As₂S₃, and residual As, which was determined by GFAAS. Results demonstrated that in spite of differences in arsenic concentrations, the availability of the metalloid was found to be low for all samples. In general, arsenic was found in less available forms. Nevertheless, most of the arsenic in the environment is retained in the fractions 3, 4, and 5 which are susceptible to dissolution in acid medium, which in turn might be due to oxidation of the sulfide present in the samples.     

Changes of Chemical Forms of Zinc and Zinc Sulfide During the Composting Process of Municipal Solid Waste

Changes of chemical forms of metallic zinc and zinc sulfide during the composting process of municipal solid waste in oxygen conditions have been determined. Speciation of zinc was carried out by means of sequential extraction. It has been found that contamination of the waste with Zn is dangerous to the environment because zinc accumulates in bioavailable forms - organically bound and carbonate. Zinc sulfide remains mainly in a less mobile sulfide form. The composting process increases the mobility of zinc insignificantly.     

Extractability and Bioavailability of Mercury from a Mercury Sulfide Contaminated Soil in Oak Ridge, Tennessee, USA

Historically as part of its national security mission, the U.S. Department of Energy’s Y-12 National Security Facility in Oak Ridge, TN acquired a significant fraction of the world’s supply of elemental mercury. During the 1950s and 1960s, a large amount of elemental mercury escaped confinement and is still present in the watershed surrounding the Y-12 facility. A series of remediation efforts have been deployed in the watersheds around the Oak Ridge site. However, most recently, concentration of total mercury in fish and water of the lower East Fork Poplar Creek (EFPC) of Oak Ridge has increased although majority of the mercury contamination in the local soils is present in the form of mercury sulfide. We have studied the extractability, solubility, and bioavailability of mercury sulfide in Oak Ridge soils. Dynamics of the dissolution of mercury sulfide by various extractants, including acids and a chelating agent, have been investigated. After three seasons of planting, soil mercury sulfide is more easily dissolved by both 4 M and 12 M nitric acid than is pure mercury sulfide reagent as indicated by their dissolution kinetics. Mercury release by EDTA from HgS-contaminated soil increased with time of reaction and soil mercury level. This chelating chemical increases the solubility of mercury in HgS-contaminated Oak Ridge soil. The results also show that mercury sulfide in contaminated Oak Ridge soils was still to some extent bioavailable to plants. The increase of bioavailability of soil mercury sulfide after three seasons of planting may contribute to the recent increase of mercury levels in water of the Lower East Fork Popular Creek (LEFPC) of Oak Ridge.     

Catalysis of Dissolved and Adsorbed Iron in Soil Suspension for Chromium（Ⅵ） Reduction by Sulfide

The kinetics of Cr（Ⅵ） reduction by sulfide in soil suspensions with various pHs, soil compositions, and Fe（Ⅱ） concentrations was examined using batch anaeroblc experimental systems at constant temperature. The results showed that the reaction rate of Cr（Ⅵ） reduction was in the order of red soil 〈 yellow-brown soil 〈 chernozem and was proportional to the concentration of HCl-extractable iron in the soils. Dissolved and adsorbed iron in soil suspensions played an important role in accelerating Cr（Ⅵ） reduction. The reaction involved in the Cr（Ⅵ） reduction by Fe（Ⅱ） to produce Fe（ⅡI）, which was reduced to Fe（Ⅱ） again by sulfide, could represent the catalytic pathway until about 70% of the initially present Cr（Ⅵ） was reduced. The catalysis occurred because the one-step reduction of Cr（Ⅵ） by sulfide was slower than the two-step process consisting of rapid Cr（Ⅵ） reduction by Fe（Ⅱ） followed by Fe（Ⅲ） reduction by sulfide. In essence, Fe（Ⅱ）/Fe（Ⅲ） species shuttle electrons from sulfide to Cr（Ⅵ）, facilitating the reaction. The effect of iron, however, could be completely blocked by adding a strong Fe（Ⅱ）-complexing ligand, 1,10-phenanthroline, to the soil suspensions. In all the experiments, initial sulfide concentration was much higher than initial Cr（Ⅵ） concentration. The plots of In e[Cr（Ⅵ）] versus reaction time were linear up to approximately 70% of Cr（Ⅵ） reduction, suggesting a first-order reaction kinetics with respect to Cr（Ⅵ）. Elemental sulfur, the product of sulfide oxidation, was found to accelerate Cr（Ⅵ） reduction at a later stage of the reaction, resulting in deviation from linearity for the In c[Cr（Ⅵ）] versus time plots.     

Re-evaluation of selectivity of malachite green test for presence of sulfite in mechanically deboned poultry

A study was undertaken to determine whether free chlorine or sulfide anions could yield positive results for the malachite green test in meat samples when sulfite was not present. Malachite green solution was added to a mechanically deboned poultry (MDP) sample spiked with either chlorine or sulfide ions. The presence of chlorine in MDP samples at any concentration tested did not yield a positive reaction for the malachite green test. When sulfide ions were introduced into MDP samples, positive results were observed at 40 micrograms sulfide ion/g MDP and above. Because aqueous solutions of sulfide at the levels mentioned have a relatively high pH, it was necessary to determine whether the pH or the presence of the sulfide ions had caused this positive reaction to the malachite green test. After a comparison of a solution of sulfide, and a solution of a matching pH, it was observed that the sulfide present caused the positive reaction to the malachite green test.     

ABSTRACTS of the Articles Printed in Journal of the Science of Soil and Manure,Japan

Sulfate-reducing bacteria, widely distributed in natural environments, have a specific ability to reduce sulfate and to form hydrogen sulfide, which reacts with iron or/and manganese present in the environments and forms a black precipitate of iron or/and manganese sulfide. This specific reaction is useful for the simple and selective detection of sulfate-reducing bacteria in mixed bacterial populations as in soil.     

Formation of 2-alkyl-(2H)-thiapyrans and 2-alkylthiophenes in cooked beef and lamb

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.     

Evolution of volatile sulfur compounds from soils treated with sulfur-containing organic materials

Release of volatile S compounds from soils treated with S-containing organic materials was studied by sensitive gas chromatographic techniques. Methyl mercaptan, dimethyl sulfide, dimethyl disulfide, carbonyl sulfide and carbon disulfide were identified as gaseous products of decomposition of animal manures, sewage sludges and plant materials in soils under aerobic or waterlogged conditions. No release of hydrogen sulfide was detected. Most of the S volatilized from soils treated with sludges was in the form of dimethyl sulfide and dimethyl disulfide. whereas most of the S volatilized from soils treated with manures and plant materials was in the form of methyl mercaptan and dimethyl sulfide. More S compounds were released, and more S was volatilized, by decomposition of manures, sludges or plant materials in soils under waterlogged conditions than by decomposition under aerobic conditions. When calculated as a percentage of the S added as organic material, the average amount of S volatilized under aerobic or waterlogged conditions was < 0.2% < 0.5% and < 3.4% for the sludges, manures and plant materials, respectively. The five volatile S compounds produced by decomposition of manures, sludges and plant materials in soils under aerobic and waterlogged conditions also were produced by decomposition of plant proteins (zein, gluten and gliadin). It is concluded that the volatile S compounds released by decomposition of the above organic materials in soils are largely, if not entirely, produced by microbial degradation of methionine and cystine in these materials.     

Cadmium sulfate application to sludge‐amended soils: II. Extraction of Cd,Zn and Mn from solid phases

Abstract

Cadmium, Zn and Mn in eleven paired soils (one which had a history of sludge application and a control from adjacent land where sludge had not been used) were partitioned into five fractions: exchangeable, adsorbed, organically bound, carbonate bound and sulfide, by the use of KNO₃, H₂0, NaOH, EDTA and HNO₃, respect‐ively. The data indicate that the major portion of the total metals was found in the carbonate, sulfide and organic fractions. Addition of CaCO₃caused an increase in the exchangeable + soluble fractions of added Cd in the soils, but had little effect on native or sludge derived Cd.