Rapid reductive dechlorination of atrazine by zero-valent iron under acidic conditions

The dechlorination of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) via reaction with metallic iron under low-oxygen conditions was studied using reaction mixture pH values of 2.0, 3.0, and 3.8. The pH control was achieved through addition of sulfuric acid throughout the duration of the reaction. The lower the pH of the reaction mixture, the faster the degradation of atrazine. The surface area of the sulfuric acid-treated iron particles was 0.31 (+/- 0.01) m2 g-1 and the surface area normalized initial pseudo-first order rate constants (kSA, where rate = kSA x (surface area/l) x [Atrazine]) at pH values of 2.0, 3.0, and 3.8 were equal to, respectively, 3.0 (+/- 0.4) x 10(-3) min-1 m-2 l, 5 (+/- 3) x 10(-4) min-1 m-2 l, and 1 (+/- 1) x 10(-4) min-1 m-2 l. The observed products of the degradation reaction were dechlorinated atrazine (2-ethylamino-4-isopropylamino-1,3,5-triazine) and possibly hydroxyatrazine (2-ethylamino-4-isopropylamino-6-hydroxy-s-triazine). Triazine ring protonation may account, at least in part, for the observed effect of pH on atrazine dechlorination via metallic iron.     

Photolysis of atrazine and ametryne herbicides in Barbados sugar cane plantation soils and water

The photodegradation kinetics of atrazine (2-chloro-6-(ethylamino)-4-isopropylamino-1,3,5-triazine) and ametryne (2-methylthio-4-ethylamino-6-isopropylamino-s-triazine), in fresh and coastal salt water from Barbados, were measured under irradiation with artificial solar and UV254-radiation. The first-order rate constants were greater for ametryne than for atrazine, and the rates were reduced in seawater relative to fresh water, and in soil slurries relative to fresh water. However, rates were accelerated in the presence of iron(III) at pH 3 due to photo-Fenton type processes. This rate enhancement was reduced at ambient pH values (pH 7-7.5) representative of surface water in Barbados. These results have important implications for the relative persistence of these contaminants in aquatic environments in tropical areas.     

Age dependent acute oral toxicity of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and two anaerobic N-nitroso metabolites in deer mice (Peromyscus maniculatus)

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) transforms anaerobically into N-nitroso compounds: hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX), hexahydro-1,3-dinitroso-5-nitro-1,3,5-triazine (DNX), and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX). Exposure to these N-nitroso metabolites may occur in areas contaminated with explosives, as anaerobic degradation occurs via some bacteria and is one remediation strategy used for RDX. Few papers report acute oral toxicity and none have evaluated age dependent toxicity of RDX or its N-nitroso metabolites. Median lethal dose (LD₅₀) was determined in deer mice (Peromyscus maniculatus) of three age classifications 21 d, 50 d, and 200 d for RDX, MNX, and TNX using the US EPA up-and-down procedure (UDP). Hexahydro-1,3,5-trinitro-1,3,5-triazine and N-nitroso metabolites caused similar overt signs of toxicity. Median lethal dose for 21 d deer mice were 136, 181, and 338 mg/kg for RDX, MNX, and TNX, respectively. Median lethal dose for 50 d deer mice were 319, 575, and 338 mg/kg for RDX, MNX, and TNX, respectively. Median lethal dose for 200 d deer mice were 158, 542, and 999 mg/kg for RDX, MNX, and TNX, respectively. These data suggest that RDX is the most potent compound tested, and age dependent toxicity may exist for all compounds and could play a role in RDX and RDX N-nitroso metabolite ecological risk evaluation of terrestrial wildlife at RDX contaminated sites.     

Toxicity of the explosive metabolites hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX) and hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) to the earthworm Eisenia fetida

Toxicity of hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX) to earthworm was evaluated. Both MNX and TNX had lethal and sublethal effects on earthworms. Exposure to MNX- or TNX-contaminated soil caused a significant concentration-dependent decrease in earthworm survival and growth. The lowest observed lethal concentration (LOLC) for both MNX and TNX was 100 and 200 mgkg(-1) soil dry weight in the sandy loam soil and in the silt loam soil, respectively. No earthworms survived for 14 days in MNX- or TNX-spiked soil at 500 mgkg(-1) soil dry weight. After 7 days exposure, the lowest observed effect concentration (LOEC) for earthworm growth was 50 mgkg(-1) soil dry weight for TNX and 100 mgkg(-1) soil dry weight for MNX in both soil types. The LC20 and LC50 for MNX in sandy loam soil were 114 and 262 mgkg(-1) and for TNX, they were 114 and 254 mgkg(-1) soil dry weight, respectively. The corresponding values for MNX and TNX in silt loam soil were 234 and 390 mgkg(-1) soil dry weight, respectively, and 200 and 362 mgkg(-1) soil dry weight, respectively. After 35 days exposure, earthworm growth was reduced 8-39% by TNX in sandy loam soil, whereas TNX only inhibited earthworm growth 5-18% at the same concentration range in silt loam soil. LC20 and LC50 for TNX were slightly lower than for MNX; this indicates that TNX was more toxic than MNX. No significant morphological or developmental abnormalities were observed in earthworms surviving exposure.     

Metabolism of the explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in a contaminated vadose zone

The aim of this study was to explore biodegradation potential of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in a deep contaminated unsaturated zone over Israel's coastal aquifer. While anaerobic biodegradation potential was observed throughout the profile down to the water table at a depth of 45 m, aerobic biodegradation was limited to the surface of the unsaturated zone. Traces of nitroso-RDX intermediates were detected in the soil samples, indicating possible in situ activity. Polymerase chain reaction and denaturing gradient gel electrophoresis analysis revealed that the microbial population in the soil consisted of protobacteria, but no known RDX degraders were detected. However, a 16S rRNA gene sequence most similar to Sphingomonas sp. was detected at all depths. Biodegradation rates were faster in the surface (0 and 1m) versus deeper soil samples (22 and 45 m) and were not affected under anaerobic conditions by the presence of nitrate, indicating a concurrent reduction of both compounds. RDX half-life in the surface soil was mostly dependent on carbon content and to lesser extent on soil moisture. Biomineralization of RDX to CO(2) was confirmed by incubating surface soil with (14)C-labeled RDX. An aerobic RDX-degrading bacterium, identified as Gordonia sp., was isolated from the soil: it degraded RDX aerobically and produced 4-nitro-2,4-diazabutanal. This study, the first to explore RDX biodegradation in the deep vadoze zone, indicates biodegradation potential throughout the profile, which is likely to support natural attenuation.     

Toxicity of hexahydro-1,3,5-trinitro-1,3,5-triazine to larval zebrafish (Danio rerio)

Hexahydro-1,3,5-trinitro-1,3,5-triazine, a cyclonitramine commonly known as RDX, is used in the production of military munitions. Contamination of soil, sediment, and ground and surface waters with RDX has been reported in different places around the world. Acute and subacute toxicities of RDX have been relatively well documented in terrestrial vertebrates, but among aquatic vertebrates the information available is limited. The objective of this study was to characterize the acute toxicity of RDX to larval zebrafish. Mortality (LC50) and incidence of vertebral column deformities (EC50) were two of the end points measured in this study. The 96-h LC50 was estimated at 22.98 and 25.64 mgl(-1) in two different tests. The estimated no-observed-effective-concentration (NOEC) values of RDX on lethality were 13.27+/-0.05 and 15.32+/-0.30 mgl(-1); and the lowest-observed-effective-concentration (LOEC) values were 16.52+/-0.05 and 19.09+/-0.23 mgl(-1) in these two tests, respectively. The 96-h EC50 for vertebral deformities on survivors from one of the acute lethality tests was estimated at 20.84 mgl(-1), with NOEC and LOEC of 9.75+/-0.34 and 12.84+/-0.34 mgl(-1), respectively. Behavioral aberrations were also noted in this acute toxicity study, including the occurrence of whirling movement and lethargic behavior. The acute effects of RDX on survival, incidence of deformities, and behavior of larval zebrafish occurred at the high end of the most frequently reported concentrations of RDX in aquatic environments. The chronic effects of RDX in aquatic vertebrates need to be determined for an adequate assessment of the ecological risk of environmental RDX.     

Sorption of Pesticides on Kaolinite and Montmorillonite as a Function of Hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.     

Sorption of pesticides on kaolinite and montmorillonite as a function of hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.     

Dissolution and sorption of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues from detonated mineral surfaces

Composition B (Comp B) is a commonly used military formulation composed of the toxic explosive compounds 2,4,6-trinitrotoluene (TNT), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Numerous studies of the temporal fate of explosive compounds in soils, surface water and laboratory batch reactors have been conducted. However, most of these investigations relied on the application of explosive compounds to the media via aqueous addition and thus these studies do not provide information on the real world loading of explosive residues during detonation events. To address this we investigated the dissolution and sorption of TNT and RDX from Comp B residues loaded to pure mineral phases through controlled detonation. Mineral phases included nontronite, vermiculite, biotite and Ottawa sand (quartz with minor calcite). High Performance Liquid Chromatography and Attenuated Total Reflectance Fourier Transform Infrared spectroscopy were used to investigate the dissolution and sorption of TNT and RDX residues loaded onto the mineral surfaces. Detonation resulted in heterogeneous loading of TNT and RDX onto the mineral surfaces. Explosive compound residues dissolved rapidly (within 9 h) in all samples but maximum concentrations for TNT and RDX were not consistent over time due to precipitation from solution, sorption onto mineral surfaces, and/or chemical reactions between explosive compounds and mineral surfaces. We provide a conceptual model of the physical and chemical processes governing the fate of explosive compound residues in soil minerals controlled by sorption-desorption processes.     

Biodegradation pathways of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by Clostridium acetobutylicum cell-free extract

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), a military high explosive, is becoming an increasingly important pollutant in the US. The cleanup of RDX-contaminated soil and groundwater has been a serious challenge due to its recalcitrance in the environment. This study was conducted to determine the biodegradation kinetics of RDX by crude cell extract of Clostridium acetobutylicum (ATCC 824), and to examine whether this bacterium will carry out reductive transformation pathways similar to the transformation of 2,4,6-trinitrotoluene (TNT), 2,4- and 2,6-dinitrotoluenes (DNTs) we have reported previously. Batch studies on the anaerobic transformation of RDX were conducted in serum bottles with U-ring-14C-RDX. RDX and its transformation products were quantified by HPLC and qualified by LC/ MS interfaced to two soft ionization techniques--an atmospheric pressure ionization and an electron spray ionization (API-ES). Results demonstrated that C. acetobutylicum is capable of transforming RDX with H2 as the electron donor. The transformation followed a zero-order kinetics and the rates increased with increasing H2. RDX was transformed into several polar intermediates that could not be separated by reverse-phase HPLC and its molecular ions were unstable under the condition of commonly used electron impact detector. Using a polar and water immiscible solvent (ethyl acetate) and the softer MS ionization techniques, mass spectroscopy detected the presence of several RDX derivatives including mononitroso-, monohydroxylamino-, mononitrosomonohydroxylamino-, monoamino-, diamino-, and triamino-compounds. The presence of hydroxylamino compounds is analogous to the transformation of TNT and DNTs we elucidated previously.     

Destruction of halogen-containing pesticides by means of detonation combustion

Pesticides that contain a halogen functional group have been destructed by means of detonative combustion. The following compounds were examined: (1) atrazine—2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine—herbicide; (2) bromophos—O,4-bromo-2,5-dichlorophenyl O,O-dimethyl phosphorothioate—insecticide; (3) chloridazon—5-amino-4-chloro-2-phenylopyridazin-3(2H)-one—herbicide; (4) linuron—3-(3,4-dichlorophenyl)-1-metoxy-1-methylurea—herbicide; (5) metoxychlor—1,1,1-trichloro-2,2-bis(4-metoxyphenyl)ethane—insecticide and acaricide; and (6) trichlorfon—dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate—insecticide. Explosive material has been produced on the basis of ammonium nitrate, which served as an oxidizer while the pesticides were used as fuels. Composition of the explosive was adjusted in such a way as to respect thermodynamic parameters. Detonative decomposition of the mixtures has been carried out in shot-holes pre-drilled in soil. Efficiency of the pesticide decomposition has been examined with gas chromatography in order to determine pesticides residues in the environment. It was found that for some, the amount of pesticides in some compounds in the analyzed samples after decomposition was below the determination threshold of the applied method.     

Influence of chlorination pH and chlorine dose on the formation of mutagenic activity and the strong bacterial mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-5(2H)-furanone (MX) in water

Samples from two Dutch raw water sources were chlorinated in the laboratory at different pH:s and chlorine doses, and were analysed for mutagenic activity and the mutagenic compound 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX). Chlorination produced mutagenic activity as well as MX in both waters. The formation of MX was favoured by acidic reaction conditions and high chlorine doses, but in waters treated with excess chlorine at pH 9, no MX was detected. The mutagenicity was approximately on the same level after chlorination of both water types but the MX concentration was significantly higher in the water containing mainly humic material.

MX was found to be quantitatively extracted from acidified waters by the XAD resin adsorption technique.     

Light-induced transformation of tribenuron-methyl on glass, soil, and plant surface

Photolysis of tribenuron-methyl (methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5triazin-2-yl)methylamino]carbonyl]amino]sulfonyl]benzoate), a sulfonylurea herbicide, was studied as thin film on glass surface, soil surface, and plant surface. A number of photoproducts such as 4-methoxy-6-methyl-2-aminomethyl-1,3,5-triazine; methyl-2-(aminosulfonyl) benzoate; N-(2-carbomethoxyphenyl)-N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-methylurea; N-(2-carbomethoxyphenyl sulfonyl)-N-methyl urea; o-benzoic sulfimide and 4-methoxy-6-methyl-2-amino-1,3,5-triazine were identified by comparison of their GC-MS with the authentic standards. The rate of degradation in all the cases followed first-order kinetics with a statistically significant correlation coefficient. Rate of photodegradation was greater on glass surface than on soil surface.     

Geochemical and microbiological processes contributing to the transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in contaminated aquifer material

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a potential human carcinogen, and its contamination of subsurface environments is a significant threat to public health. This study investigated abiotic and biological degradation of RDX in contaminated aquifer material. Anoxic batch systems were started with and without pre-aeration of aquifer material to distinguish initial biological RDX reduction from abiotic RDX reduction. Aerating the sediment eliminated chemical reductants in the native aquifer sediment, primarily Fe(II) sorbed to mineral surfaces. RDX (50 μM) was completely reduced and transformed to ring cleavage products when excess concentrations (2 mM) of acetate or lactate were provided as the electron donor for aerated sediment. RDX was reduced concurrently with Fe(III) when acetate was provided, while RDX, Fe(III), and sulfate were reduced simultaneously with lactate amendment. Betaproteobacteria were the dominant microorganisms associated with RDX and Fe(III)/sulfate reduction. In particular, Rhodoferax spp. increased from 21% to 35% and from 28% to 60% after biostimulation by acetate and lactate, respectively. Rarefaction analyses demonstrated that microbial diversity decreased in electron-donor-amended systems with active RDX degradation. Although significant amounts of Fe(III) and/or sulfate were reduced after biostimulation, solid-phase reactive minerals such as magnetite or ferrous sulfides were not observed, suggesting that RDX reduction in the aquifer sediment is due to Fe(II) adsorbed to solid surfaces as a result of Fe(III)-reducing microbial activity. These results suggest that both biotic and abiotic processes play an important role in RDX reduction under in situ conditions.     

Temperature activated degradation (mineralization) of 4-chloro-3-methyl phenol by Fenton's reagent

With the aim to evaluate the effect of temperature, 4-chloro-3-methyl phenol (CMP) degradation by Fenton's reagent was investigated at 25 and 70 degrees C under the following initial conditions: [CMP]0 = 10 mM, [Fe2+]0 = 0.5 mM; ([H2O2]0/[CMP]0) = 80, pH0 = 3. The results indicated that CMP degradation was strongly influenced by temperature. In fact, the maximum TOC removal, achieved after ca. 24h, was by far greater at 70 degrees C (85%) than at 25 degrees C (36%). The same happened for organic chlorine (TOX) conversion into inorganic chloride, i.e. 100%, after 3 h at 70 degrees C, and 87%, after 27 h at 25 degrees C. As the recorded trends of CMP removal and chloride formation were basically the same, hydroxy substitution (ipso-substitution) was hypothesised as one likely mechanism of CMP degradation. The higher level of mineralization recorded at 70 degrees C was ascribed to: (i) a greater *OH concentration; (ii) a consequently greater extent of CMP oxidation to organic acids; (iii) a higher decarboxylation rate of such acids. An interesting consequence of such extended organic acids decarboxylation was a pH increase up to 8 that, in turn, caused, in the treated mixture, the decomposition of excess H2O2 as well as the precipitation of iron ions. These two latter outcomes are technologically important considering that usually, before discharging Fenton treated wastewater, specific polishing steps are required just to remove iron ions, decompose excess hydrogen peroxide and neutralise the pH.     

Chlorination of bisphenol A: kinetics and by-products formation

The kinetics of initial chlorination of bisphenol A (BPA) was studied between pH 2 and 11 at room temperature (20 +/- 2 degrees C). pH Profile of the apparent second-order rate constant of the reaction of BPA with chlorine were modeled considering the elementary reactions of HOCl with BPA species and an acid-catalyzed reaction. The predominant reactions at near neutral pH were the reactions of HOCl with the two phenolate species of BPA (k = 3.10 x 10(4) M(-1)s(-1) for BPA- and 6.62 x 10(4) M(-1) s(-1) for BPA(2-)). At near neutral pH, half-life times of BPA were calculated to be less than 1.5 h for chlorine residual higher than 0.2 mg l(-1). Chlorination of synthetic treated waters spiked with BPA showed that BPA disappeared within 4 h and that chlorinated bisphenol A congeners were rapidly formed and remained in solution for up to 10-20 h when low chlorine dosages are applied (0.5-1 mg l(-1)). To limit their presence in drinking water networks, it is then necessary to maintain high chlorine residuals that rapidly produce and decompose chlorinated bisphenol A congeners.     

Herbicide movement and dissipation at four Midwestern sites

This study was conducted to evaluate atrazine (2-chloro-4-ethylamino-6-isopropyl-1,3,5-triazine) and alachlor (2-chloro-N-(methoxymethyl)acetamide) dissipation and movement to shallow aquifers across the Northern Sand Plains region of the United States. Sites were located at Minnesota on a Zimmerman fine sand, North Dakota on Hecla sandy loam, South Dakota on a Brandt silty clay loam, and Wisconsin on a Sparta sand. Herbicide concentrations were determined in soil samples taken to 90 cm four times during the growing season and water samples taken from the top one m of aquifer at least once every three months. Herbicides were detected to a depth of 30 cm in Sparta sand and 90 cm in all other soils. Some aquifer samples from each site contained atrazine with the highest concentration in the aquifer beneath the Sparta sand (1.28 microg L(-1)). Alachlor was detected only once in the aquifer at the SD site. The time to 50% atrazine dissipation (DT50) in the top 15 cm of soil averaged about 21 d in Sparta and Zimmerman sands and more than 45 d for Brandt and Hecla soils. Atrazine DT50 was correlated positively with % clay and organic carbon (OC), and negatively with % fine sand. Alachlor DT50 ranged from 12 to 32 d for Zimmerman and Brandt soils, respectively, and was correlated negatively with % clay and OC and positively with % sand.     

Chlorinated herbicide (triallate) dehalogenation by iron powder

The reductive degradation of a chlorinated herbicide by iron powder was investigated at lab scale. The studied substrate was triallate (S-2,3,3-trichloroallyl di-isopropyl thiocarbamate) which contains a trichloroethylene moiety potentially reducible by zero-valent iron. Degradation reactions were carried out in batch, at 25 degrees C, in the absence of oxygen, by contacting electrolytic iron powder (size range: 20-50 microm) with a triallate aqueous solution (2.5 mgl(-1)). Herbicide decay, corresponding evolutions of TOC, TOX and chloride ion release were regularly monitored throughout the reactions. Furthermore, the main degradation by-products were identified by HPLC/MS. The results showed that, after 5 days, herbicide degradation extent was about 97% and that the reaction proceeded through the formation of a dechlorinated alkyne by-product (S-2-propinyl di-isopropyl thiocarbamate) resulting from the complete dechlorination of triallate. The subsequent reduction of such an alkyne intermediate gave S-allyl di-isopropyl thiocarbamate as main end by-product. The identified by-products suggested that dechlorination took place mainly via reductive beta-elimination. However, as traces of dichloroallyl di-isopropyl thiocarbamate were also detected, a role, although minor, was assigned even to hydrogenolysis in the overall dechlorination process.     

Detoxification of hexachlorobenzene by dechlorination with potassium-sodium alloy

Dechlorination of hexachlorobenzene (HCB) was achieved by a liquid potassium–sodium (K–Na)-alloy. HCB in a cyclohexane/benzene solution (22 mmol/l, 4.67 g/l as chlorine) was dechlorinated by almost 100% after a 30-min reaction, indicating high reactivity of K–Na alloy and high proton donating power of cyclohexane. Decreasing orders of chlorobenzenes identified after a 15-min reaction, by amount were 1,2,3,4- > 1,2,3,5- > 1,2,4,5- for tetrachlorobenzenes, 1,2,4- > 1,2,3- > 1,3,5- for trichlorobenzenes, and 1,4- > 1,3- > 1,2- for dichlorobenzenes. It was hypothesized that once one chlorine atom in HCB was replaced with a proton, the adjacent chlorine atom to the proton tended to be replaced with another hydrogen atom. A total of 63 PCBs formed via the Wurtz–Fittig reaction were identified as by-products in the sample after a 15-min reaction. Among PCBs found, 2,3^′,4^′,5-tetrachlorobiphenyl, which was a product from 1,2,4-trichlorobenzene formed via the Wurtz–Fittig reaction, was detected in relatively high concentration (48.9 nmol/ml). The sample obtained from a reaction mixture after 30 min contained only 14 PCBs in trace amounts, indicating that the PCBs formed were also further dechlorinated by K–Na alloy. Non-chlorinated compounds––such as methylbenzene, dimethylbenzene, dimer of tetrahydrofuran, and dicyclohexyl (dimer of cyclohexane)––were also identified in the samples. A method using K–Na alloy developed in the present study dechlorinated satisfactorily HCB at room temperature.     

Fate of atrazine and chlorpyrifos during solid state fermentation--examination of processes

Solid state fermentation (SSF) was investigated as a means to dispose of two commonly used pesticides, chlorpyrifos (O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate) and atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine). SSF experiments were carried out in bench-scale bioreactors (equipped with CO2 and volatile organic traps) containing a mixture of lignocellulosic materials and a radiolabeled pesticide. Ethyl acetate-extractable, alkali soluble, and alkali insoluble fractions were evaluated for radioactivity following a 60-d incubation period at 40 degrees C. The majority of the [2,6-pyridyl-14C]chlorpyrifos was associated with the ethyl acetate extract (about 74%), 17% was trapped as organic volatiles by polyurethane foam traps and < 0.5% of the chlorpyrifos was mineralized to CO2. Only small amounts of the radioactivity were associated with alkali soluble (0.0003%) and alkali insoluble (0.3%) fractions. In the [14C-U-ring]atrazine bioreactors, very little of the radioactivity volatilized (<0.5%) and less than 0.5% was mineralized to CO2. Approximately 57% of the applied radioactivity was associated with the ethyl acetate extract while 9% and 24% of the radioactivity was associated with the alkali soluble (humic and fulvic acids) and alkali insoluble fractions, respectively. Possible reaction mechanisms by which covalent bonds could be formed between atrazine (or metabolites) and humic substances were investigated. The issue of bound atrazine residue (alkali soluble fraction) was at least partially resolved. Oxidative coupling experiments revealed that formation of covalent bond linkages between amino substituent groups of atrazine residue and humic substances is highly unlikely.