Microbial transformation products of benzoxazolinone and benzoxazinone allelochemicals--a review

Cyclic hydroxamic acids and lactams are allelochemicals present in the common agricultural crops wheat, rye, and maize. The hydroxamic acids are mainly present in the plants as glucosides. Upon injury or insect attack or when exuded to the soil environment, the hydroxamic acids occur in their unstable agluconic form. In the first step in the transformation of hydroxamic acids, benzoxazolinones are formed spontaneously. It is necessary to elucidate the further microbial transformation of these compounds in the soil environment for a purposeful exploitation of the allelopathic properties of wheat, rye, and maize. In the present paper, the existing knowledge on microbial transformation products of benzoxazolin-2-one (BOA), 6-methoxy-benzoxazolin-2-one (MBOA), and 2-hydroxy-1,4-benzoxazin-3-one (HBOA) was reviewed. Three main groups of transformation products were identified: aminophenoxazinones, malonamic acids, and acetamides. Future research needs concerning the transformation of these chemicals in soil are discussed, when their properties for suppressing weeds and soil-borne diseases are going to be exploited.     

Transformation kinetics of 6-methoxybenzoxazolin-2-one in soil

Wheat (Triticum aestivum L.) and other cereals produce allelochemicals as natural defense compounds against weeds, fungi, insects and soil-borne diseases. The main benzoxazinoid allelochemical of wheat is 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA), bound as beta-glucoside and released upon plant injury. When leached from wheat to soil, DIMBOA is microbially transformed to 6-methoxy-benzoxazolin-2-one (MBOA). Exploiting benzoxazinoids and their degradation products as substitutes for synthetic pesticides depends on knowledge of transformation pathways and kinetics. In an MBOA degradation experiment at a concentration of 2400 nmol g(-1) soil, the previously identified transformation products 2-amino-7-methoxy-phenoxazin-3-one (AMPO) and 2-acetylamino-7-methoxy-phenoxazin-3-one (AAMPO) were quantified. Three different kinetic models were applied to MBOA transformation kinetics; single first-order (SFO), first-order multi-compartment, and double first-order in parallel. SFO proved to be adequate and was subsequently applied to the transformations of MBOA, AMPO and AAMPO. Degradation endpoints, expressed as degradation time (DT), were calculated for MBOA, AMPO and AAMPO to test whether the maximum values for synthetic pesticides set by the European Commission and the Danish Environmental Protection Agency were exceeded. DT(50) values for MBOA and AMPO were 5.4 d and 321.5 d, respectively, and DT(90) values were 18.1 d and 1068 d, respectively. The DT(50) value for AMPO exceeded the maximum value. The persistence, concentrations and toxicity of metabolites such as AMPO should be considered when breeding cereal crops with increased levels of benzoxazinoids.     

Degradation of metribuzin in two soil types of Lebanon

The degradation of metribuzin [4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one] as influenced by soil type, temperature, humidity, organic fertilizers, soil sterilization, and ultra-violet radiation was studied in two soil types of Lebanon under laboratory conditions. The two soil types were sandy loam and clay. Deamination of metribuzin in the sandy loam soil to its deaminometribuzin (DA) derivative was basically a result of biological activity. In the clay soil the first metabolite diketometribuzin (DK) was a result of oxidative desulfuration, while diketo-deaminometribuzin (DADK) was the product of reductive deamination. The two soils represented major differences in the pesticide transformation processes. Photodecomposition on the soil surface and in aqueous media was also an important process in the degradation of metribuzin. Furthermore, the increase in soil organic matter enhanced degradation.     

Transport and transformation of sulfadiazine in soil columns packed with a silty loam and a loamy sand

Concerning the transport of the veterinary antibiotic sulfadiazine (SDZ) little is known about its possible degradation during transport. Also its sorption behaviour is not yet completely understood. We investigated the transport of SDZ in soil columns with a special emphasis on the detection of transformation products in the outflow of the soil columns and on modelling of the concentration distribution in the soil columns afterwards. We used disturbed soil columns near saturation, packed with a loamy sand and a silty loam. SDZ was applied as a 0.57 mg L(-1) solution at a constant flow rate of 0.25 cm h(-1) for 68 h. Breakthrough curves (BTC) of SDZ and its transformation products 4-(2-iminopyrimidin-1(2H)-yl)aniline and 4-hydroxy-SDZ were measured for both soils. For the silty loam we additionally measured a BTC for an unknown transformation product which we only detected in the outflow samples of this soil. After the leaching experiments the (14)C-concentration was quantified in different layers of the soil columns. The transformation rates were low with mean SDZ mass fractions in the outflow samples of 95% for the loamy sand compared to 97% for the silty loam. The formation of 4-(2-iminopyrimidin-1(2H)-yl)aniline appears to be light dependent and did probably not occur in the soils, but afterwards. In the soil columns most of the (14)C was found near the soil surface. The BTCs in both soils were described well by a model with one reversible (kinetic) and one irreversible sorption site. Sorption kinetics played a more prominent role than sorption capacity. The prediction of the (14)C -concentration profiles was improved by applying two empirical models other than first order to predict irreversible sorption, but also these models were not able to describe the (14)C concentration profiles correctly. Irreversible sorption of sulfadiazine still is not well understood.     

Biological assessment of bisphenol A degradation in water following direct photolysis and UV advanced oxidation

Endocrine disrupting compounds (EDCs) are exogenous environmental chemicals that can interfere with normal hormone function and present a potential threat to both environmental and human health. The fate, distribution and degradation of EDCs is a subject of considerable investigation. To date, several studies have demonstrated that conventional water treatment processes are ineffective for removal of most EDCs and in some instances produce multiple unknown transformation products. In this study we have investigated the use of direct photolysis with low-pressure (LP) Hg UV lamps and UV+hydrogen peroxide (H(2)O(2)) advanced oxidation process (AOP) for the degradation of a prototypic endocrine disrupter, bisphenol A (BPA), in laboratory water. Removal rates of BPA and formation of degradation products were determined by high performance liquid chromatography (HPLC) analysis. Changes in estrogenic activity were evaluated using both in vitro yeast estrogen screen (YES) and in vivo vitellogenin (VTG) assays with Japanese medaka fish (Oryzias latipes). Our results demonstrate that UV alone did not effectively degrade BPA. However, UV in combination with H(2)O(2) significantly removed BPA parent compound and aqueous estrogenic activity in vitro and in vivo. Removal rates of in vivo estrogenic activity were significantly lower than those observed in vitro, demonstrating differential sensitivities of these bioassays and that certain UV/AOP metabolites may retain estrogenic activity. Furthermore, the UV/H(2)O(2) AOP was effective for reducing larval lethality in treated BPA solutions, suggesting BPA degradation occurred and that the degradation process did not result in the production of acutely toxic intermediates.     

Unusual polar metabolites in the groundwater of a contaminated waste site indicate a new pathway of mononitrotoluene transformation

At a mononitrotoluene-contaminated waste disposal site, the groundwater was screened for polar transformation products of mononitrotoluenes, by means of HPLC-MS, HPLC-NMR and further off-line NMR and MS techniques. Besides expected metabolites such as aminotoluenes (ATs) and nitrobenzoic acids (NBAs), three unknowns (di- and tetrahydro-derivatives of (2-oxo-quinolin-3-yl) acetic acid) could be identified which, in the context of explosives and related compounds, are new metabolites. Evidence could be provided by microcosm experiments with 2-nitrotoluene (2-NT) that these metabolites are microbial transformation products of 2-NT under anaerobic conditions. The NMR and MS data are presented and the possible pathway for the formation of these metabolites after addition of 2-NT to fumarate is discussed.     

Heterogeneous photocatalysed reaction of three selected pesticide derivatives, propham, propachlor and tebuthiuron in aqueous suspensions of titanium dioxide

Heterogeneous photocatalysed reaction of three selected pesticide derivatives such as propham (1), propachlor (2) and tebuthiuron (3) has been investigated in aqueous suspensions of titanium dioxide by monitoring the change in substrate concentration employing UV Spectroscopic analysis and depletion in Total Organic Carbon (TOC) content as a function of irradiation time. The degradation kinetics was studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO(2) and in the presence of electron acceptors such as hydrogen peroxide (H(2)O(2)), potassium bromate (KBrO(3)) and ammonium persulphate (NH(4))(2)S(2)O(8) besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient as compared with other photocatalysts. The pesticide derivative propham (1) was found to degrade faster as compared to propachlor (2) and tebuthiuron (3). An attempt has also been made to identify the products formed during the photooxidation process through GC/MS analysis technique. All the model pollutants showed the formation of several intermediate products, which were identified on the basis of molecular ion and mass spectrometric fragmentation pattern. A probable mechanism for the formation of the products has been proposed.     

Degradation of Metribuzin in Two Soil Types of Lebanon

The degradation of metribuzin [4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one] as influenced by soil type, temperature, humidity, organic fertilizers, soil sterilization, and ultra-violet radiation was studied in two soil types of Lebanon under laboratory conditions. The two soil types were sandy loam and clay. Deamination of metribuzin in the sandy loam soil to its deaminometribuzin (DA) derivative was basically a result of biological activity. In the clay soil the first metabolite diketometribuzin (DK) was a result of oxidative desulfuration, while diketo-deaminometribuzin (DADK) was the product of reductive deamination. The two soils represented major differences in the pesticide transformation processes. Photodecomposition on the soil surface and in aqueous media was also an important process in the degradation of metribuzin. Furthermore, the increase in soil organic matter enhanced degradation.     

Studies of the behaviour and fate of the polymer-additives octadecyl-3-(3.5-di-t-butyl-4-hydroxyphenyl)propionate and tri-(2.4-di-t-butylphenyl)phosphite in the environment.

In order to evaluate the environmental risk potential of the polymer-additives octadecyl-3-(3.5-di-t-butyl-4-hydroxyphenyl)propionate (additive 1) and tri-(2.4-di-t-butylphenyl)phosphite (additive 2) we have studied the degradation of the 14C-labelled single components and their release from a polypropylene matrix in abiotic and biotic test systems as well as their transport behaviour in soil. The biotic degradation in waste compost, activated sludge and in soil was studied. In order to conduct release tests, waste disposal material were used as well. The abiotic degradation was effectuated by photooxidation at a catalytic surface. The highest mineralisation rates were obtained by photooxidative degradation of the two test substances. The maximum content of bounded residues was found for additive 1 in soil and for additive 2 in waste compost. In the extracts of soil and compost, the principal metabolites could be identified in the case of additive 1 as 7.9-di-t-butyl-1-oxaspiro[4.5]deca-6.9-dien-2.8-dion and in activated sludge as the methyl ester of 3-(3.5-di-t-butyl-4-hydroxyphenyl) propionic acid. Additive 2 metabolised in all degradation tests nearly completely under formation of two products. The main component was identified as tri-(2.4-di-t-butylphenyl)phosphate. Both polymer-additives were eluated from the chosen soil types. The transport behaviour of additive 1 was independent from the soil type. In all test matrices additive 1 as well as additive 2 were released from polypropylene. Because the amounts of additive 1 and 2 absorbed onto soil particles were taken into account, the highest liberation rates were found in the soil test.     

Degradation of fipronil under laboratory conditions in a tropical soil from sirinhaém pernambuco, Brazil

The objective of this research was to assess the degradation of fipronil [5-amino-1-(2,6-dichloro-alpha,alpha,alpha -trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile] in soils from sugar cane fields in Northeastern Brazil. Degradation experiments were carried out under laboratory conditions (controlled temperature and in the dark), where sterile and non-sterile soils (Ustoxs) were incubated [under moisture content of 55% of the water holding capacity (WHC)] and analyzed for fipronil disappearance and metabolite formation. Microbial communities present in the soil degrade fipronil. However, biodegradation seems to be dependent on the bioavailability of the fipronil and the half-life according to the zero-order model. Fipronil degradation rate appeared to be biphasic. Degradation fipronil ranged from 83 days (initial concentration = 978 ng g(-1); short-term experiment) to 200 days (initial concentration = 689 ng g(-1); long-term experiment). This an initial slower rate followed by a faster rate after 90 days of incubation may lead to shorter half-life than that calculated with the zero-order model. The sulfone derivative (an oxidation product) was the predominant metabolite, but the sulfide (a reduction product) and amide (a hydrolysis product) derivatives were also formed under non-sterile conditions after 120 days of incubation. The metabolites underwent further biodegradation, particularly the sulfone derivative. Bioavailability appears to affect fipronil degradation in soils with an effective capacity to adsorb fipronil (such as Ustoxs), while redox potential was important for the formation of metabolites. Despite the fine texture, more aerobic sites were present, thus favoring the formation of the sulfone metabolite over that of the sulfide metabolite. Therefore, microaggregation of Ustoxs, with high clay content, played a very important role in determining the types of metabolites formed.     

Degradation of fipronil under laboratory conditions in a tropical soil from sirinhaém pernambuco,Brazil

The objective of this research was to assess the degradation of fipronil [5-amino-1-(2,6-dichloro-α,α,α -trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile] in soils from sugar cane fields in Northeastern Brazil. Degradation experiments were carried out under laboratory conditions (controlled temperature and in the dark), where sterile and non-sterile soils (Ustoxs) were incubated [under moisture content of 55% of the water holding capacity (WHC)] and analyzed for fipronil disappearance and metabolite formation. Microbial communities present in the soil degrade fipronil. However, biodegradation seems to be dependent on the bioavailability of the fipronil and the half-life according to the zero-order model. Fipronil degradation rate appeared to be biphasic. Degradation fipronil ranged from 83 days (initial concentration = 978 ng g^{? 1}; short-term experiment) to 200 days (initial concentration = 689 ng g^{? 1}; long-term experiment). This an initial slower rate followed by a faster rate after 90 days of incubation may lead to shorter half-life than that calculated with the zero-order model. The sulfone derivative (an oxidation product) was the predominant metabolite, but the sulfide (a reduction product) and amide (a hydrolysis product) derivatives were also formed under non-sterile conditions after 120 days of incubation. The metabolites underwent further biodegradation, particularly the sulfone derivative. Bioavailability appears to affect fipronil degradation in soils with an effective capacity to adsorb fipronil (such as Ustoxs), while redox potential was important for the formation of metabolites. Despite the fine texture, more aerobic sites were present, thus favoring the formation of the sulfone metabolite over that of the sulfide metabolite. Therefore, microaggregation of Ustoxs, with high clay content, played a very important role in determining the types of metabolites formed.     

Investigations of the determination and transformations of diazinon and malathion under environmental conditions using gas chromatography coupled with a flame ionisation detector

Degradation of two model insecticides, diazinon and malathion, and their degradation products 2-isopropyl-6-methyl-4-pyrimidinol--IMP (diazinon hydrolysis product) and malaoxon (malathion oxidation product) was compared and studied in the environment. The pesticides and their metabolites were extracted from samples (water, soil, chicory) with ethyl acetate and subsequently the extracts were analyzed by GC/FID. It was shown that hydrolysis is the major process in the degradation of these pesticides in water. In fact, 95% of diazinon was degraded, and only 10% of malathion was oxidised. In soil 30% of diazinon exposed to the sunlight was decomposed by photolysis, whereas in soil left in the darkness no degradation products were observed. In soil left under environmental conditions, 90% of diazinon was degraded and 40% from its initial concentration was transformed into IMP. The concentrations of the pesticides after 21 days on chicory were under maximal allowable concentration, which is 0.5 ppm for malathion and for diazinon. The concentration of malaoxon was more than twice as high as the allowable value, which is for the sum of malathion and malaoxon 3 ppm.     

Tracing the transformation of labelled [1-13C]phenanthrene in a soil bioreactor

[1-(13)C]-labelled phenanthrene was incubated in a closed bioreactor to study the flux and biotransformation of polycyclic aromatic hydrocarbon (PAH) in contaminated soils on a bulk and molecular level. The degradation of extractable phenanthrene was observed by GC-MS measurements and the mineralisation was monitored by (13)CO(2) production. The transformation of the (13)C-label into non-extractable soil-bound residues was determined by carbon isotopic measurements. With these data we were able to calculate a carbon budget of the (13)C-label. Moreover, the chemical structure of non-extractable bound residues was characterised by applying selective chemical degradation reactions to cleave xenobiotic subunits from the macromolecular organic soil matrix. The obtained low molecular weight products yielded (13)C-labelled compounds which were identified using IRM (isotope ratio monitoring)-GC-MS and structurally characterised with GC-MS. Most of the (13)C-labelled products obtained by chemical degradation of non-extractable bound residues are well-known metabolites of phenanthrene. Thus, metabolites of [1-(13)C]phenanthrene formed during biodegradation appear to be reactive components which are subsequently involved in the bound residue formation. Hydrolysable amino acids of the soil residues were significantly labelled with (13)C as confirmed by IRM-GC-MS measurements. Therefore, phenanthrene-derived carbon was transformed by anabolic microbial processes into typical biologically derived compounds. These substances are likely to be incorporated into humic-like material after cell death.     

Degradation of short-chain alkyl- and alkanolamines by TiO2- and Pt/TiO2-assisted photocatalysis

The photooxidation of C2H5NH2, (C2H5)2NH, HOC2H4NH2, (HOC2H4)2NH and (HOC2H4)3N using TiO2 and Pt/TiO2 as photocatalysts has been investigated. A laboratory set up was designed and a study on the influence of the concentration of the photocatalyst, the pH-value and the structure of the amine performed. The photocatalytic process was optimized with respect to the concentrations of the model substances during degradation. The decrease of the amine concentrations was found to be maximum at a pH of 10. The time-dependence of the formation of cationic breakdown products, such as NH3/NH4 and short-chain alkyl- and alkanolamines was studied by analyses with single column ion chromatography. The experimental data show that the photodegradation follows a Langmuir-Hinshelwood kinetic. The mineralization of the model substances also was monitored by measurements of the decrease of the TOC and of the formation of NO2 and NO3. The different mineralization efficiencies for the model substances studied are discussed with regard to their structure and adsorption behaviour on the photocatalyst. A possible breakdown mechanism involving the electrophilic attack of the hydroxyl radical is given. The applicability of the TiO2-assisted photocatalytic degradation of C2H5NH2 and (C2H5)2NH was tested at the pilot plant-scale with real solar radiation. The degradation rates and products obtained were similar to those found in the laboratory experiments.     

Degradation in soil and water and ecotoxicity of rimsulfuron and its metabolites.

The degradation and ecotoxicity of sulfonylurea herbicide rimsulfuron and its major metabolites were examined in batch samples of an alluvial sandy loam and in freshwater. An HPLC-DAD method was adapted to simultaneously identify and quantify rimsulfuron and its metabolites, which was successfully validated by GC-MS analysis. In aqueous solutions, pure rimsulfuron was rapidly hydrolyzed into metabolite 1 (N-(4,6-dimethoxypyrimidin-2-yl)-N-(3-(ethylsulfonyl)-2-pyridinylurea)), which itself was transformed into the more stable metabolite 2 (N-((3-(ethylsulfonyl)-2-pyridinyl)-4,6-dimethoxy-2-pyrimidineamine)), with half-life (t(1/2)) values of 2 and 2.5 days, respectively. Hydrolysis was instantaneous under alkaline conditions (pH = 10). In aqueous suspensions of the alluvial soil (pH = 8), formulated rimsulfuron had a half-life of 7 days, whereas that of metabolite 1 was similar to that in water (about 3.5 days). The degradation of the two major metabolites was also studied in soil suspensions with the pure compounds at concentrations ranging from 1 to 10 mg l(-1). The half-life of metabolite 1 ranged from 3.9 to 5 days, close to the previous values. Metabolite 2 was more persistent and its degradation is strongly dependent on the initial concentration (C0): half-life values ranged from 8.1 to 55 days at 2-10 mg l(-1), respectively. These values are higher than those determined from the kinetics of metabolite 1 transformation into metabolite 2 (t(1/2) = 8-19 days). The ecotoxicity of the three chemicals was evaluated through their effect on Daphnia magna and Vibrio fischeri (Microtox bioassay). No effect was observed on D. magna with 24 and 48 h acute toxicity tests. Similarly, no toxic effect was observed with the Microtox test for the three chemicals in the range of concentrations tested that included the field application dose. Thus, being of low persistence and lacking acute toxicity, these chemicals present a low environmental risk. However, chronic effects should be studied in order to confirm the safety of rimsulfuron and its major metabolites.     

Metabolites from fungal laccase-catalysed transformation of sulfonamides

Soil metabolism of sulfonamides is largely unknown. Hence the sulfonamides sulfanilamide (SAA), sulfadimethoxine (SDT) and sulfapyridine (SPY) were reacted in model experiments with a fungal laccase from Trametes versicolor. Enzymatic transformation after a reaction time of 15 d ranged from 10.0% for SAA up to 95.6% for SPY and the difference was attributed to the different molecular substituents. Metabolites were first tentatively assigned after LC–ESI⁺–MS full-scan analysis. Secondly, the proposed metabolites were further confirmed employing either multiple reaction monitoring in comparison with standard substances or precursor ion scan LC–ESI⁺–MS/MS experiments striving for the precursor and two to three product ions. Aniline was confirmed as a breakdown product of SPY and further metabolites of SPY and of SDT were identified as rearranged SO₂ extrusion products. Thirdly, some of the metabolites matched those that were previously reported for sulfonamide photodegradation and degradation in soil. It was concluded that enzymatic metabolism as investigated here also occurs in soil.     

Biodegradation of juvenoid diastereoisomers: radio-HPLC and MS analysis

Microbial degradation of two diastereoisomeric forms 2 and 3 of a selected juvenoid (insect juvenile hormone bioanalog), ethyl N-{2-{4-[(2-hydroxycyclohexyl)methyl]phenoxy}ethyl}carbamate was studied and the degradation products analyzed. Degradation experiments were performed using simple modeling under laboratory conditions. A Candida sp. strain T1, isolated from soil, was chosen as a biodegradation species. Radiolabeling of the studied compounds 2 and 3 was used in combination with radio-HPLC and MS analysis to increase the limits of detection, monitoring and isolation of trace quantities of the products of degradation and/or transformation. Resulting from the microbial processes using 2 or 3 as source compounds, three identical products (4-6) of their biodegradation were produced. Compound 2 also afforded two additional products (7, 8). Radio-HPLC analysis and separation, and subsequent MS analysis of the degradation mixtures resulted in identification of the degradation products. The degree and the rate of biodegradation of 2 and 3 were analyzed after 1, 3 and 7 days from the beginning of the experiment.     

Aerobic biodegradability of the calcium channel antagonist verapamil and identification of a microbial dead-end transformation product studied by LC-MS/MS

In recent years pharmaceuticals and personal care products have been detected in increasing concentrations in hospital effluents, sewage treatment plants (STP) as well as in different environmental compartments such as surface water, groundwater and soil. Little is known about the elimination of these substances during sewage treatment or about the formation of potential metabolites in the environment caused by bacterial biotransformation. To assess the biodegradability of the popular cardiovascular drug verapamil and the possible formation of potential microbial degradation products, two tests from the OECD series were used in the present study: the widely used Closed Bottle test (OECD 301 D) and the modified Zahn-Wellens test (OECD 302 B). In the Closed Bottle test, a screening test that simulates the conditions of an environmental surface water compartment, no biological degradation was observed for verapamil at concentrations of 2.33mgl(-1). In the Zahn-Wellens test, a test for inherent biodegradability which allows evaluation of aerobic degradation at high bacterial density, only a partial biological degradation was found. Analysis of test samples by high performance liquid chromatography coupled to multiple stage mass spectrometry (HPLC-MSn) revealed 2-(3,4-dimethoxyphenyl)-2-isopropyl-5-(methylamino)pentane nitrile, already known as D617 (Knoll nomenclature), a metabolite of mammalian metabolism, which is the major degradation product and dead-end transformation product of aerobic degradation of verapamil.     

Heterogeneous photocatalytic degradation of picloram, dicamba, and floumeturon in aqueous suspensions of titanium dioxide

Heterogeneous photocatalytic degradation of three-selected herbicide derivatives: (1) picloram (4-Amino-3,5,6-trichloropyridine-2-carboxylic acid, (2) dicamba (2-Methoxy-3,6-dichlorobenzoic acid, and (3) floumeturon (N,N-Dimethyl-N-[3-(trifluoromethyl)phenyl]-urea) has been investigated in aqueous suspensions of titanium dioxide under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic technique and decrease in total organic carbon (TOC) content as a function of irradiation time under a variety of conditions. The degradation of the herbicide was studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO2, and in the presence of electron acceptors such as hydrogen peroxide (H2O2), potassium bromate (KBrO3), and ammonium persulphate (NH4)2S2O8 besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient as compared with other photocatalysts in the case of dicamba (2) and floumeturon (3), whereas Hombikat UV100 was found to be better for the degradation of picloram (1). The herbicide picloram (1) was found to degrade faster as compared to dicamba (2) and floumeturon (3). The degradation products were analyzed by gas chromatography-mass spectrometry (GC/MS) technique, and plausible mechanisms for the formation of products have been proposed.     

Experimental in situ chemical peroxidation of atrazine in contaminated soil

Lab-scale experiments of in situ chemical oxidation (ISCO), were performed on soil contaminated with 100 mg kg(-1) of atrazine (CIET). The oxidant used was hydrogen peroxide catalysed by naturally occurring minerals or by soluble Fe(II) sulphate, added in aqueous solution. The oxidation conditions were: CIET:H2O2=1:1100, 2 PV or 3 PV reaction volume, Fe(II):H2O2=0, 1:22, 1:11. Stabilized (with KH2PO4 at a concentration of 16 g l(-1)) or non-stabilized hydrogen peroxide was used. The pH of the reagents was adjusted to pH=1 with sulphuric acid, or was not altered. Results showed that the addition of soluble Fe(II) increased the temperature of the soil slurry and the use of stabilized hydrogen peroxide resulted in a lower heat generation. The treatment reduced the COD of the soil of about 40%, pH was lowered and natural organic matter became less hydrophobic. The highest atrazine conversion (89%) was obtained in the conditions: 3 PV, Fe(II):H2O2=1:11 with stabilized hydrogen peroxide added in two steps. The stabilizer only increased H2O2 life-time significantly when soluble Fe(II) was added. Results indicate as preferential degradation pathway of atrazine in soil dechlorination instead of dealkylation.