Nucleophilic reactions of phorate and terbufos with reduced sulfur species under anoxic conditions

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.     

Hydrolysis of terbufos using simulated environmental conditions: rates, mechanisms, and product analysis.

This study focuses on the hydrolysis of terbufos, an organophosphorus pesticide. Combining GC-MS and wet chemistry methods, di-tert-butyl disulfide and formaldehyde were identified and quantified as major degradation products. Diethyl dithiophosphate was also indirectly identified as a degradation product under alkaline conditions. Hydrolysis rate constants of terbufos under homogeneous conditions were comparable to those of phorate and show relative insensitivity to pH under slightly acidic to neutral pH conditions, as the observed rate constants varied only in the range of (4.5-5.0) x 10(-6) s(-1) between pH 5.7 and 9.4; neutral hydrolysis is thus the most dominant hydrolysis pathway of terbufos in ambient waters. The mechanisms for terbufos hydrolysis and the formation of the major products and their temporal profiles are discussed. To assess the environmental impact of degradation products of this widely used pesticide, Microtox was used to analyze the toxicity of terbufos and two of its degradation products: diethyl dithiophosphate and di-tert-butyl disulfide; the EC(50) of terbufos was found to be >17 microM, whereas the EC(50) of di-tert-butyl disulfide was 1.3 microM.     

Aging effects and grape variety dependence on the content of sulfur volatiles in wine

Thirteen sulfur compounds (boiling points from 35 to 231 degrees C), usually considered as possible off-flavoring volatiles, were quantified by a concurrent headspace-solid phase microextraction method coupled with gas chromatography-mass spectrometry (HS-SPME/GC-MS) on 80 not off-flavoring wines of four varieties (Merlot, Marzemino, and Teroldego as red wines and Chardonnay as a white one) and of five vintages produced in the North Italian Trentino region. The results of the research, the first Italian data-bank per variety on such volatiles, allow us to make a comparison with the data of other winegrowing areas, to investigate the aging effect on the considered volatiles, and, finally, to try a variety discrimination using statistical procedures. Dimethyl sulfide, 3-(methylthio)-1-propanol, diethyl sulfide, and diethyl disulfide were found to increase with time whereas 2-mercaptoethanol and ethylmercaptan showed a decreasing trend. Furthermore, the concentration of several compounds was found to be dependent on the variety. For instance, sulfide, disulfides, benzothiazole, and thioalcohols are at higher levels in Merlot wines, whereas thiols and thioacetates are more abundant in Marzemino and Teroldego wines. Chardonnay products, well apart from the other wines, are the poorest in 3-(methylthio)-1-propanol and rather rich in dimethyl disulfide and in diethyl disulfide, mostly in the aged wines. Applying the principal component analysis to the data, it was possible to demonstrate that Chardonnay and Merlot wines are well-discriminated from the Italian native varietal wines, which on their turn are only partially distinguishable among them. A contribution of these compounds to the variety characteristics of wine is reasonable.     

Identification of characteristic aroma components of Thai fried chili paste

Three forms of Thai fried chili pastes (CP) were prepared, consisting of an unheated CP (UH-CP), a CP heated at 100 degrees C for 25 min (H25-CP, typical product), and a CP excessively heated for 50 min (H50-CP). The potent odorants in the CPs were investigated by two gas chromatography-olfactometry methods: dynamic headspace dilution analysis (DHDA) and aroma extract dilution analysis (AEDA). DHDA revealed that the predominant odorants in heated CPs were mainly sulfur-containing compounds, followed by lipid-derived compounds, Strecker aldehydes, and Maillard reaction products. Dimethyl sulfide, allyl mercaptan, 2- (or 3-) methylbutanal, ally methyl sulfide, 2,3-butanedione, 3,3'-thiobis(1-propene), and methyl propyl disulfide were among the most potent headspace odorants detected by DHDA. By AEDA, 2-vinyl-4 H-1,3-dithiin and diallyl trisulfide had the highest FD factors in H25-CP. On the basis of their high FD factors by both GCO methods, the predominant odorants in H25-CP were 3-vinyl-4 H-1,2-dithiin, allyl methyl disulfide, and allyl methyl trisulfide. Furthermore, dimethyl trisulfide and diallyl disulfide had the highest odor activity values in H25-CP, suggesting that these were also potent odorants in CP. In addition, methional, 3-methylbutanoic acid, 4-hydroxy-2,5-dimethyl-3-(2 H)-furanone, and 3-hydroxy-4,5-dimethyl-2( 5H)-furanone (sotolon) were indicated as potent thermally derived odorants of H25-CP.     

Pathways for the hydrolysis of phorate: product studies by (31)P NMR and GC-MS

A new intramolecular mechanism is proposed for the hydrolysis of phorate. (31)P NMR was used to study the formation of P-containing products of phorate hydrolysis in situ. When hydrolysis was followed by (31)P NMR, a dominant P-containing product was found and was identified to be diethyl dithiophosphate using methylation and GC-MS. Combining the data from phorate hydrolysis at three different temperatures, thermodynamic parameters were calculated. The contributions of various possible pathways to phorate hydrolysis are discussed.     

Volatile compounds thermally generated from S-propylcysteine and S-propylcysteine sulfoxide-aroma precursors of Allium vegetables.

Two nonvolatile flavor precursors occurring in Allium vegetables, S-propyl-L-cysteine and its sulfoxide, were heated in closed model systems at different temperatures (from 80 to 200 degrees C) in the presence of variable amounts of water (0-98%) for 1-60 min. It seems to be indisputable that thermally generated breakdown products of both S-propyl-L-cysteine and particularly S-propyl-L-cysteine sulfoxide can significantly participate in the aroma formation of culinary processed Alliumvegetables. Dipropyl disulfide, dipropyl trisulfide, propylthiol, and dipropyl thiosulfonate were identified as the predominant volatile compounds generated by thermal degradation of S-propylcysteine sulfoxide. Dipropyl disulfide and 2-(propylthio)ethylamine were the major breakdown products formed from S-propylcysteine. Substantial amounts of various alkyl- and alkylthio-substituted pyridines were also generated from both S-propylcysteine and its sulfoxide.     

Influence of insecticides on microbial transformation of nitrogen and phosphorus in Typic Orchragualf soil

Four insecticides, viz., BHC, phorate, carbofuran, and fenvalerate, were applied at the rate of 7.5, 1.5, 1.0, and 0.35 kg a.i. ha(-)(1), respectively, to investigate their effects on the growth and activities of N(2)-fixing and phosphate-solubilizing microorganisms in relation to the availability of N and P in laterite (Typic Orchragualf) soil. Insecticides in general, and BHC and phorate in particular, stimulated the proliferation of aerobic nonsymbiotic N(2)-fixing bacteria and phosphate-solubilizing microorganisms and also their biochemical activities, such as nonsymbiotic N(2)-fixing and phosphate-solubilizing capacities, which resulted in greater release of available N (NH(4)(+) and NO(3)(-)) and P in soil. All the insecticides were persistent in soil for a short period of time, and the rate of dissipation was highest for fenvalerate followed by phorate, carbofuran, and BHC, depicting the half-lives (T(1/2)) 8.8, 9.7, 16.9, and 20.6 days, respectively. The insecticides followed first-order reaction kinetics during their dissipation in soil.     

Nonvolatile oxidation products of glucose in Maillard model systems: formation of saccharinic and aldonic acids and their corresponding lactones

By using pyrolysis-gas chromatography-mass spectrometry-based methodologies, nonvolatile oxidation products of isotopically labeled glucose/glycine model systems were studied through a postpyrolytic in situ derivatization technique by using trimethylsilyldiethylamine. Analysis of the data indicated that the known reactive sugar intermediates such as glucosone and its deoxy derivatives can undergo in Maillard model systems three types of transformations: oxidation of the aldehydic groups into carboxylic acids, oxidative cleavage of alpha-dicarbonyl moieties into aldonic acids, and benzylic acid rearrangement of 1-deoxy-glucosone into saccharinic acids. The aldonic and saccharinic acids were identified through silylation of their lactone derivatives, and their origin was verified through (13)C-labeling studies. The following lactones were identified in glucose and glucose/glycine model systems: trans-dihydro-3,4-bis[(trimethylsilyl)oxy]-2(3 H)-furanone, cis-dihydro-3,4-bis[(trimethylsilyl)oxy]-2(3H)-furanone, 2-C-methyl-2,3,5-tris-O-(trimethylsilyl)-D-ribonic acid gamma-lactone, 3-deoxy-2,5,6-tris-O-(trimethylsilyl)-D-ribo-hexonic acid gamma-lactone, 2-deoxy-3,5-bis-O-(trimethylsilyl)-pentonic acid gamma-lactone, and 2,3,5-tris-O-(trimethylsilyl)-D-arabinonic acid gamma-lactone. The observed reduction in color and aroma in Maillard reactions performed under oxidative conditions may be attributed to the oxidation of reactive dicarbonyls into the corresponding carboxylic acids or their corresponding lactones.     

Formation of volatile sulfur compounds by microbial decomposition of sulfur-containing amino acids in soils

Evolution of volatile sulfur compounds from soils treated with S-containing amino acids was studied by sensitive gas chromatographic techniques involving use of a flame photometric detector fitted with a sulfur filter. The following volatile sulfur compounds were identified as products of microbial decomposition of S-containing amino acids in soils under aerobic or waterlogged conditions: methyl mercaptan, dimethyl sulfide and dimethyl disulfide (evolved from soils treated with methionine, methionine sulfoxide, methionine sulfone or S-methyl cysteine); ethyl mercaptan, ethyl methyl sulfide and diethyl disulfide (evolved from soils treated with ethionine or S-ethyl cysteine); and carbon disulfide (evolved from soils treated with cystine, cysteine, lanthionine or djenkolic acid). Small amounts of dimethyl sulfide and carbon disulfide were evolved from soils treated with homocystine, and trace amounts of carbonyl sulfide were evolved from soils treated with lanthionine or djenkolic acid. No volatile sulfur compounds were evolved from soils treated with cysteic acid, taurine, or S-methyl methionine. The amounts of sulfur volatilized from soils treated with the 14 S-containing amino acids studied represented from less than 0·1 per cent to more than 50 per cent of the sulfur added as amino acid. Hydrogen sulfide could not be detected as a gaseous product of microbial decomposition of S-containing amino acids in soils under aerobic or waterlogged conditions.     

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

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

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.     

Cholesterol oxidation in meat products and its regulation by supplementation of sodium nitrite and apple polyphenol before processing

The levels of cholesterol oxidation derivatives (OxChol) in eight commercial species of meat products were examined. These products contained more than 1 mg/100 g of OxChol, and 7beta-hydroxycholesterol + 5beta-epoxycholesterol (111-1092 microg/100 g), 5alpha-epoxycholesterol (80-712 microg/100 g), cholestanetriol (0-368 microg/100 g), and 7-ketocholesterol (708-1204 microg/100 g) were detected. To know the interaction of sodium nitrite supplementation against cholesterol oxidation in meat products, sausage was produced with or without varying levels of sodium nitrite and stored in the refrigerator for 15 days. As a result, cholesterol oxidation in sausage was inhibited by addition of sodium nitrite in a dose-dependent manner. This observation may be associated with inactivation of O(2)(-) radical and stabilization of polyunsaturated fatty acids (PUFAs). In fact, the levels of OxChol in sausage increased, accompanying the decrease of coexisting linoleic acid when sodium nitrite was not added to sausage meat. Thus, cholesterol oxidation in meat products seems to be considarably promoted by the oxidation of coexisting PUFAs. On the other hand, additive apple polyphenol also inhibited linoleic acid oxidation in sausage and then suppressed cholesterol oxidation through its radical scavenging effects. Therefore, apple polyphenol, having a large amount of an oligomer of catechin, may interfere with cholesterol oxidation in meat processing or storage of meat products through its antioxidative action and be useful as a new antioxitant for meat products when it is added to the original meat before processing.     

Assessment of the Effect of Organic Matter on the Retention of Pb+2 in Artificial Soils

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...     

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.     

Major degradation pathway of thiuram in tap water processed by oxidation with sodium hypochlorite.

Thiuram (3 microM), a fungicide, was incubated in deionized water by adding 0-100 mg/L free chlorine at 30 degrees C for 30 min, and the solution was analyzed by HPLC and IC. The byproducts were identified by LC/MS, EI-MS, infrared, and (13)C NMR spectra and a reduction technique using 2-mercaptoethanol. On the basis of these results, it was found that the oxidation of thiuram with sodium hypochlorite initially produced an intermediate dimethylthiocarbamoyl dimethylcarbamoyl disulfide, which was finally degraded to bis(dimethylcarbamoyl) disulfide, its trisulfide, and dimethylamine. Subsequently, it was suggested that monitoring of bis(dimethylcarbamoyl) disulfide, its trisulfide, and dimethylamine should be included for the management and control of thiuram in tap water processed by oxidation with sodium hypochlorite.     

Effects of food materials on removal of Allium-specific volatile sulfur compounds

Effects of food materials were investigated on removal of several kinds of thiols, sulfides, and disulfides, which arise from vegetables of Allium species during food preparation and eating. Methanethiol, propanethiol, and 2-propenethiol were captured by raw foods such as fruits, vegetables, and mushrooms or a mixture of their acetone powders and phenolic compounds. The odor of diallyl disulfide was remarkably reduced by kiwi fruit, spinach, cutting lettuce, parsley, basil, mushrooms, and, particularly, cow's milk, raw egg, boiled rice, and bovine serum albumin (BSA). This suggests that the removal of diallyl disulfide could be caused by a physical and chemical interaction between the disulfide and foods. Furthermore, milk and BSA captured propanethiol, 2-propenethiol, dipropyl sulfide, diallyl sulfide, dimethyl disulfide, and dipropyl disulfide very well. An enzymatic degradation of diallyl disulfide by spinach and asparagus was also observed. These results demonstrate that the deodorization with foods is achieved by multiple actions including physical and chemical interaction between volatile sulfur compounds and foods, enzymatic degradation of disulfides, and addition of thiols to polyphenolic compounds, catalyzed by polyphenol oxidases or peroxidases.     

Simultaneous Determination of Phorate and Oxyfluorfen in Well Water Samples with High Accuracy by GC-MS After Binary Dispersive Liquid-Liquid Microextraction

The potential risk of pesticides to cause harm to humans and other organisms even at trace levels calls for sensitive and accurate analytical techniques for their simultaneous qualitative and quantitative determinations. In this study, a sensitive binary dispersive liquid-liquid microextraction (B-DLLME) strategy was developed for the simultaneous determination of phorate and oxyfluorfen by gas chromatography mass spectrometry after extraction/preconcentration from aqueous solution. An experimental design was used to optimize parameters of the B-DLLME method to obtain maximum outcome. Under the optimum conditions of B-DLLME, the limit of detection (LOD) for phorate and oxyfluorfen were found to be 0.41 μg L^?1 and 0.54 μg L^?1, respectively. The detection limits correlate to about 37 and 73 folds enhancement in detection powers when compared to direct GC-MS determination of phorate and oxyfluorfen, respectively. In order to find out the applicability of developed method to real samples, recovery tests were performed for 20 μg L^?1 of phorate and oxyfluorfen spiked in well water samples. Percent recovery values were found to be 94.5% for phorate and 101.9% for oxyfluorfen.     

Volatile sulfur compounds in irradiated precooked turkey breast analyzed with pulsed flame photometric detection

Ionizing radiation is an effective processing technology for pathogen inactivation on various foods. However, the generation of off-odor is a concern for some irradiated meats. This study was conducted to investigate volatile sulfur compounds of precooked ready-to-eat turkey breast as functions of radiation dose and subsequent storage. Precooked turkey breast was exposed to 0, 1, 2, 3, 4, and 5 kGy of gamma radiation and stored for 14 days at 5 degrees C. Volatile sulfur compounds were extracted using solid phase microextraction (SPME), followed by gas chromatographic separation and pulsed flame photometric detection. Irradiation dramatically increased concentrations of hydrogen sulfide, sulfur dioxide, methanethiol, and dimethyl disulfide. The rate of increase was higher at low doses (0-2 kGy) than at higher doses of 3-5 kGy. Carbon disulfide was the only volatile sulfur compound that was reduced by irradiation. Concentrations of all volatile sulfur compounds decreased in both irradiated and nonirradiated samples stored at 5 degrees C.     

Heterocyclic volatiles formed by heating cysteine or hydrogen sulfide with 4-hydroxy-5-methyl-3(2H)-furanone at pH 6.5

The reaction of 4-hydroxy-5-methyl-3(2H)-furanone (HMF) with cysteine or hydrogen sulfide at pH 6.5 for 60 min at 140 degrees C produced complex mixtures of volatile compounds, the majority of these containing either sulfur or nitrogen. Of the 68 compounds detected, 63 were identified, some tentatively, by GC-MS. Among the identified compounds were thiophenes (10), thiophenones (6), thienothiophenes (5), thiazoles (5), trithiolanes (4), pyrazines (6), and oxazoles (4). More compounds were produced in the reaction of HMF with cysteine (63) than were formed in the reaction with hydrogen sulfide (33). In both systems, thiophenones were major reaction products, accounting for 25-36% of the total volatiles formed. Possible reasons for the differences in the composition of the two systems are discussed. The contributions of these reactions, and their products, to the flavor of heated foods are considered.     

Inhibition of nitrification in soils by volatile sulfur compounds

Carbon disulfide, dimethyl disulfide, methyl mercaptan, dimethyl sulfide, and hydrogen sulfide retard nitrification of ammonium in soils incubated in closed systems. The inhibitory effects of these volatile sulfur compounds on nitrification decrease in the order listed. Hydrogen sulfide is a relatively weak inhibitor of nitrification, but carbon disulfide is considerably more effective than patented nitrification inhibitors (N-Serve. AM, and ST) for inhibition of nitrification in closed systems.It is concluded from the work reported that the inhibitory effects of methionine, cystine, cysteine, and other nonvolatile organic sulfur compounds on nitrification in soils may be at least partly due to decomposition of these compounds by soil microorganisms with formation of volatile sulfur compounds that retard nitrification.