Degradation of chloroacetanilide herbicides by anodic fenton treatment

Anodic Fenton treatment (AFT) is an electrochemical treatment employing the Fenton reaction for the generation of hydroxyl radicals, strong oxidants that can degrade organic compounds via hydrogen abstraction. AFT has potential use for the remediation of aqueous pesticide waste. The degradation rates of chloroacetanilides by AFT were investigated in this work, which demonstrates that AFT can be used to rapidly and completely remove chloroacetanilide herbicides from aqueous solutions. Acetochlor, alachlor, butachlor, metolachlor, and propachlor were treated by AFT, and parent compound concentrations were analyzed over the course of the treatment time. Degradation curves were plotted and fitted by the AFT kinetic model for each herbicide, and AFT model kinetic parameters were used to calculate degradation rate constants. The reactivity order of these five active ingredients toward hydroxyl radical was acetochlor approximately metolachlor > butachlor approximately alachlor > propachlor. Treatment of the chloroacetanilides by AFT removed the parent compounds but did not completely mineralize them. However, AFT did result in an increase in the biodegradability of chloroacetanilide aqueous solutions, as evidenced by an increase in the 5-day biochemical oxygen demand to chemical oxygen demand ratio (BOD5/COD) to >0.3, indicating completely biodegradable solutions. Several degradation products were formed and subsequently degraded, although not always completely. Some of these were identified by mass spectral analyses. Among the products, isomers of phenolic and carbonyl derivatives of parent compounds were common to each of the herbicides analyzed. More extensively oxidized products were not detected. Degradation pathways are proposed for each of the parent compounds and identified products.     

Discriminating multiple impacts of biogas residues amendment in selectively decontaminating chloroacetanilide herbicides

There is increasing concern about modifications to pesticide persistence in soil from the application of organic wastes as fertilizers. This study was conducted to discriminate the multiple effects of biogas residues (BR) amendment, including soil nutrients, soil microbial activity and biodiversity, and adsorption and degradation of chloroacetanilide herbicides (acetochlor, metolachlor, and butachlor). Addition of BR to soil increased the release of organic materials (i.e., dissolved organic carbon, dissolved organic nitrogen, and active phosphorus). It not only stimulated soil microorganisms and caused changes to microorganism diversity but also increased herbicide adsorption. Such multiple effects led to selective decontamination of chloroacetanilide herbicides, depending on herbicide structures and BR amendment levels. Stereoselectivity in degradation of acetochlor and metolachlor with biphasic character was magnified by BR amendment, which was well explained by integrating the impacts of BR amendment. Interestingly, BR amendment induced significant accumulation of herbicidally active aS,CS-metolachlor, facilitating the utilization of herbicidal activity.     

Pressurized fluid extraction for quantitative recovery of chloroacetanilide and nitrogen heterocyclic herbicides in soil

Pressurized fluid extraction (PFE) is a new sample extraction method operated at elevated temperatures and pressures with liquid solvents. The use of PFE was investigated for the extraction of four Hawaiian clayey soils fortified with the selected chloroacetanilide and nitrogen heterocyclic herbicides Alachlor, Bromacil, Hexazinone, Metribuzin, and Tebuthiuron. The effects of operation temperature, pressure, flush volume, and static cycles on PFE performance were studied. Water was the most effective modifier of PFE for quantitative recoveries of the five herbicides in soils. The simple extraction method required pretreatment of the soil with 37.6% water and subsequent two-static-cycle extraction with a total of 32 mL of acetone at 1500 psi and 100 degrees C. Average recoveries of Alachlor, Bromacil, Hexazinone, Metribuzin, and Tebuthiuron ranged from 93 to 103% by the water-assisted PFE, compared with only 68-83% recoveries of the corresponding chemicals when no water was used. The extraction time and total organic solvent consumption were reduced from 18 h and 300 mL by Soxhlet to 22 min or less and 80 mL or less of organic solvent by PFE.     

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.     

Kinetics and mechanism of imazosulfuron hydrolysis

Knowledge of the kinetics and pathways of hydrolytic degradation is crucial to the prediction of the fate and transport mechanism of chemicals. This work first describes the kinetics of the chemical hydrolysis of imazosulfuron, a new sulfonylurea herbicide, and evaluates the results to propose a degradation pathway. The hydrolysis of imazosulfuron has been studied in aqueous buffers both within the pH range 1.9-12.3 at ambient temperature (thermostated at 25 +/- 2 degrees C) and at pH 3.6 within the temperature range of 15-55 degrees C. The hydrolysis rate of imazosulfuron was characterized by a first-order kinetics, pH- and temperature-dependent, and accelerated by acidic conditions and higher temperatures. The calculated half-lives at pH 4.5 and 5.9 were 36.5 and 578 days, respectively. At pH 6.6, 7.4, 9.2, and 12.3 no significant change in imazosulfuron concentration was observed after 150 days. Half-lives were much lower at pH <4 (= imazosulfuron pK(a)), at which they ranged from 3.3 to 6.3 days. Moreover, a change in temperature from 15 to 25 degrees C in acidic conditions (pH 3.6) decreased the half-life of imazosulfuron by a factor of approximately 4.0; in any case, a 3-5-fold increase in the rate of hydrolysis was found for each 10 degrees C increase in temperature. In acidic conditions the only hydrolysis products were the two molecules resulting from the cleavage of the sulfonylurea bridge.     

Determination of triazine and chloroacetanilide herbicides in soils by microwave-assisted extraction (MAE) coupled to gas chromatographic analysis with either GC-NPD or GC-MS

A simple and rapid method based on microwave-assisted extraction (MAE) coupled to gas chromatographic analysis was developed for the analysis of triazine (atrazine, cyanazine, metribuzine, simazine and deethylatrazine, and deisopropylatrazine) and chloroacetanilide (acetochlor, alachlor, and metolachlor) herbicide residues in soils. Soil samples are processed by MAE for 5 min at 80 degrees C in the presence of acetonitrile (20 mL/sample). Mean recovery values of most solutes are >80% in the 10 to 500 microg/kg fortification range with respective RSDs (relative standard deviations) < 20%. The limits of quantification (LOQ) and limits of detection (LOD) are 10 and 1 to 5 microg/kg, respectively. The method was validated with two types of soils containing 1.5 and 3.0% organic matter content, respectively; no statistically significant differences were found between solute recovery values from the two types of soils. The solute mean recovery values from freshly spiked (24 h aging) and spiked samples stored refrigerated for one week before processed were also not statistically different. Residue levels determined in field weathered soils were higher when soils were processed by MAE than with a comparison method based on flask-shaking of soil suspensions overnight. Extracts were analyzed by a gas chromatographic system equipped either with a thermionic (GC-NPD) or a mass spectrometric detector (GC-MS).     

Kinetics and mechanism of lactosylation of alpha-lactalbumin

The lactosylation of alpha-lactalbumin in aqueous solution was followed at pH(c) = 6.0, 6.3, 7.0, 7.3, and 7.9 and constant ionic strength (I = 0.080) at 50-60 degrees C by reversed-phase high-performance liquid chromatography (RP-HPLC) and electrospray mass spectrometry (MS). The rate of the lactosylation reaction increased with increasing pH and with temperature most significantly at lower pH. The rate of lactosylation could be described by an acid dissociation curve corresponding to pK(a) of the epsilon-amino group of lysine in alpha-lactalbumin. From initial rates for conditions of excess of lactose, pseudo-first-order rate constants were calculated and further transferred into second-order rate constants by dividing with the lactose concentration. Second-order rate constants for protonated and unprotonated lysine in alpha-lactalbumin both showed Arrhenius behavior, and using transition-state theory, DeltaH# = 31 +/- 2 kJ/mol and DeltaS# = -266 +/- 48 J/(mol . K) were determined for the unprotonated form and DeltaH# = 158 +/- 49 kJ/mol and DeltaS# = 80 +/- 150 J/(mol . K) for the protonated form, respectively. On the basis of the marked differences in activation parameters, initial formation of a lactosylamine is suggested as rate-determining for reaction between lactose and a protonated lysine in alpha-lactalbumin, while subsequent water elimination to form a Schiff base becomes rate-determining for the unprotonated form.     

土壤中磺酰脲除草剂降解机制研究进展

磺酰脲除草剂是一种高效、低毒、低用量(10～40g/hm~2)的新型除草剂,广泛应用于水稻、小麦和玉米等田间杂草的控制,在土壤中降解途径主要为水溶性光分解、醇解、化学水解和微生物分解,且4种降解途径下各自产生不同的降解产物。对土壤中磺酰脲除草剂降解产物的测定多采用气相色谱、液相色谱、酶连免疫吸附和生物检测,各测定方法均有利弊,色谱法需繁琐的纯化程序提纯样品以达到检测极限0.1μg/kg,生物检测和免疫吸附法测定快速、灵敏度高但缺乏专一性。结合生物降解模型研究,阐述了磺酰脲除草剂的降解机制。     

Transformation kinetics and mechanism of the sulfonylurea herbicides pyrazosulfuron ethyl and halosulfuron methyl in aqueous solutions

Pyrazosulfuron ethyl (PE) and halosulfuron methyl (HM) are two new highly active sulfonylurea herbicides that have been widely used for weed control in a variety of vegetables and other crops. These two herbicides have similar molecular structures, differing only in the substitutions on the pyrazole ring. Chemical hydrolysis is a primary process affecting the environmental fate of sulfonylurea pesticides. The hydrolytic transformation kinetics of PE and HM were investigated as a function of pH and temperature. For both herbicides, the hydrolysis rate was pH-dependent and increased with increasing temperature. The hydrolysis of both sulfonylureas was much faster in acidic or basic media than under neutral conditions. Identification of hydrolytic products by liquid chromatography-mass spectrometry (LC-MS) suggested that both PE and HM were subject to cleavage and contraction of the sulfonylurea bridge. The hydrolysis rate of HM was significantly higher than that of PE in alkaline solutions, despite their structural similarity. A chlorine substitution on HM's pyrazole ring makes HM more susceptible to bridge contraction than PE under basic conditions. The hydrolysis of HM and PE was relatively unaffected by the presence of cyclic oligosaccharides (cyclodextrins), indicating that natural OH-containing organic compounds occurring in aquatic environments may have little impact on the transformation of these sulfonylurea herbicides.     

Kinetics and mechanism of cymoxanil degradation in buffer solutions

The kinetics and mechanism(s) of the hydrolytic degradation of a compound are needed to evaluate a compound's abiotic degradation in the environment. In this paper, the hydrolysis of cymoxanil [2-cyano-N-[(ethylamino)carbonyl]-2-(methoxyimino) acetamide] was investigated in dark sterile aqueous solutions under a variety of pH conditions (pH 2.8-9.2) and temperatures (15-50 degrees C). Hydrolysis of cymoxanil was described by first-order kinetics, which was dependent on pH and temperature. Cymoxanil degraded rapidly at pH 9 (half-life = 31 min) and relatively slowly at pH 2.8 (half-life = 722 days). The effect of temperature on the rate of cymoxanil degradation was characterized using the Arrhenius equation with an estimated energy of activation of 117.1 kJ mol(-)(1). An increase in temperature of 10 degrees C resulted in a decrease in half-life by a factor of approximately 5. Three competing degradation pathways are proposed for the hydrolysis of cymoxanil, with two of the pathways accounting for approximately 90% of cymoxanil degradation. These two pathways involved either initial cyclization to 1-ethyldihydro-6-imino-2,3,5(3H)-pyrimidinetrione-5-(O-methyloxime) (1, Figure 1) or direct cleavage of the C-1 amide bond to form cyano(methoxyimino) acetic acid (7). The third pathway of degradation involved initial cyclization to 3-ethyl-4-(methoxyimino)-2,5-dioxo-4-imidazolidinecarbonitrile (8), which rapidly degrades into 1-ethyl-5-(methoxyimino)-2,4-imidazoline-2,4-dione (9). All three pathways eventually lead to the formation of the polar metabolite oxalic acid.     

Effects of soil-cation composition on reactions of four herbicides in a candler fine sand

Sorption, persistence and transport of herbicides in soils depend on the relative saturation of soils with cations from various soil amendments. Current research was conducted to study the effect of preequilibration of a Candler fine sand (Hyperthermic uncoated typic Quartzipsamments; 0–30 cm depth) with AlCl₃, CaCl₂, CuCl₂, FeCl₃, or KCl salt solutions on sorption in bromacil, simazine, norflurazon, and diuron herbicides commonly used in Florida citrus groves. Preequilibration of the soil with either FeCl₃, or AlCl₃ significantly decreased the sorption and therefore increased internal leaching potential, of all four herbicides as compared to their sorption in untreated soil. This decrease in sorption was much greater for bromacil and simazine (24 to 35%) than for norflurazon and diuron (7 to 8%). The desorption of bromacil and diuron in 1M NH₄OAc was also significantly lower in soils preequilibrated with FeCl₃ or AlCl₃ than the untreated soil. However, the reverse was true in the case of simazine and norflurazon. Preequilibration of the soil with CuCl₂, KCl, and CaCl₂ resulted in a significant decrease in sorption of norflurazon, diuron, and simazine but did not affect bromacil sorption. Accordingly, the species of adsorbed cation had varying effects on the sorption/desorption of each of the herbicides and varied their leaching potential.     

Free radicals in electron donor-acceptor reactions between a soil humic acid and photosynthesis inhibitor herbicides

Products obtained by interaction of a soil humic acid with a number of s-triazines and substituted ureas, well known to act as photosynthesis inhibitor herbicides, were studied by infrared (IR) and electron spin resonance (ESR) spectrometries. Analysis of spectroscopic results showed that single-electron transfer processes take place reasonably between ring or chain donor groups of the herbicide molecule and acceptor quinone units of the humic acid, thus producing additional unpairing of electrons in the resulting charge-transfer complexes. Experimental and theoretical considerations suggested the hypothesis that the investigated herbicides may react chemically with humic compounds by simulating analogous processes that take place on biological scale in chloroplasts, on the basis of similar electron donor-acceptor reactions involving free radicals.     

Glyphosate and glufosinate-based herbicides: fate in soil,transfer to,and effects on land snails

Purpose  

The aim of this work was to assess the transfer and effects of two widely used herbicides on the land snail Helix aspersa during long-term exposure under laboratory conditions.     

Kinetics and mechanism of free fatty acid formation on the surface of milled rice

The presence of free fatty acid (FFA) is an important factor in determining rice quality for brewing. FFA formation in milled rice during storage was monitored, and a two-parameter semiempirical kinetic model giving product concentration as a function of time is proposed to describe FFA formation on milled rice during storage. The model was tested using sets of data obtained from partially milled rice samples stored at 24, 37, and 50 degrees C and fully milled rice stored at 37 degrees C and 70% relative humidity. The predicted values provide very good fits (R(2) >or= 97%) of the experimental data at all storage temperatures. A two-substrate reaction mechanism representing a two-phase process is also presented. Milled rice FFA at a given storage time varied with storage temperatures. The kinetic model and mechanisms proposed could be useful in describing and predicting FFA contents of milled rice during storage and transportation.     

Denitrification in soil: Effects of herbicides

The effects of 20 herbicides on denitrification of nitrate in three soils were studied by determining the effects of 10 and 50μgg^?1 soil of each herbicide on the amounts of nitrate lost and the amounts of nitrite, N₂O and N₂ produced when soil samples were incubated anaerobically after treatment with nitrate. The herbicides used were butylate, EPTC, chlorpropham, propham, diuron, linuron, monuron, siduron, alachlor, trifluralin, 2,4-D amine, 2,4-D ester, atrazine, cyanazine, metribuzin, simazine, dalapon, chloramben, dicamba and dinoseb.None of the herbicides studied significantly affected denitrification of nitrate when applied at the rate of 10 μg g^?1 soil, but dinoseb increased the ratio of N₂ to N₂O in the gaseous products of denitrification when applied at this rate. Butylate, EPTC, diuron, simazine and dalapon had no significant effect on denitrification when applied at the rate of 50μgg^?1 soil, whereas metribuzin and dinoseb enhanced denitrification when applied at this rate. The influence of the other herbicides on denitrification when applied at the rate of 50μgg^?1soil depended on the soil, but all enhanced or inhibited denitrification in at least one soil.     

Kinetics of reactions of chelates FeEDDHA and FeEDDHMA as affected by pH and competing ions

Abstract

Iron chelates are widely used in fertigation because of their high stability and solubility. However, sudden changes of pH or concentrations of accompanying ions affect chelate stability and make kinetics as relevant as equilibrium data. The kinetics of FeEDDHA and FeEDDHMA reactions at acidic pH values in the presence and absence of calcium (Ca), magnesium (Mg), phosphorus (P), copper (Cu), nickel (Ni), and zinc (Zn) were studied. The FeEDDHA and FeEDDHMA decompound in few seconds at low pH values. The extension of the decomposition reaction is affected by the kind of chelate and concentration. Calcium, Mg, P, Cu, and Zn slightly slow down the reaction. The recovery of both chelates is observed when pH increases. The reaction is quick and practically complete in absence of competing ions, although the percentage of recompound chelate is affected by the chelating agent and pH. FeEDDHMA recompounds in a larger extension than FeEDDHA. The percentage of recompound chelate increases from pH 4 to 7. The rate of reaction and the quantity of recompound chelate are not modified by the presence of Ca or Mg ions. However, phosphate diminishes the percentages of recovery, and its effect is larger as higher is the relationship [P]/[chelate]. The occurrence of Cu, Ni, manganese (Mn), and Zn slows down the reaction at low chelate concentrations. They also decrease the percentage of recompound chelate. The negative effect of the microelements is higher on the recovery of FeEDDHMA than on FeEDDHA, but for both chelates, the influence of the competing ions diminishes as the chelate concentration increases. Copper has the greatest impact on the recomposition of the chelates FeEDDHA and FeEDDHMA, although Ni, a high concentrations, can end up impeding the recovery of FeEDDHMA.     

Influence of pyrolytic and aqueous-phase reactions on the mechanism of formation of Maillard products

The influence of the reaction phase on the mechanism of formation of Maillard products was studied by comparison of (13)C-label incorporation patterns of the common products formed in model systems consisting of labeled glycine and D-glucoses subjected to both pyrolysis and heating in aqueous solutions. Pyrolysis experiments were performed at 250 degrees C for 20 s, and aqueous model systems were heated in sealed vials for 3 h at 120 degrees C followed by GC/MS analysis. Label incorporation patterns of the following compounds were analyzed: cyclotene, furanmethanol, acetylpyrrole, 5-methyl-pyrrole, trimethylpyrazine, acetic acid, 3-hydroxy-2-butanone, 2,3-butanedione, and 2-methyl-4, 5-dihydro-3(2H)-furanone. Although pyrolysis reaction produced higher number of products, however, the major pathways of formation of variety of important Maillard products followed the same mechanism under both pyrolytic and aqueous systems. Furthermore, contrary to literature speculations, 2-methyl-4, 5-dihydro-3(2H)-furanone was shown to be formed by ring contraction of 2,3-dihydro-3,5-dihydroxy-6-methyl-4(H)-pyran-4-one, through benzilic acid rearrangement, followed by decarboxylation.     

Kinetics of moisture-induced hydrolysis in powder blends stored at and below the deliquescence relative humidity: investigation of sucrose-citric acid mixtures

Previous studies have shown that deliquescent organic compounds frequently exhibit chemical instability when stored in environmental conditions above their deliquescence relative humidity (RH). The goal of the current study was to investigate the effect of atmospheric moisture on the long-term chemical stability of crystalline sucrose-citric acid mixtures following storage at RHs at and below the mutual deliquescence relative humidity (MDRH). Interestingly, it was found that sucrose hydrolysis can occur below the MDRH of 64% and was observed for samples stored at 54% RH. However, hydrolysis was not seen for samples stored at 33 or 43% RH. The rate of sucrose hydrolysis could be modeled by taking into account the rate and extent of moisture uptake, which in turn was dependent on the composition of the powder and the storage RH. A reaction mechanism initiated by capillary condensation and involving additional deliquescence lowering by the degradation products formed as a result of sucrose hydrolysis (glucose and fructose) was proposed.     

Synthesis of dimethyl derivatives of imidazolinone herbicides: their use in efficient gas chromatographic methods for the determination of these herbicides

The dimethyl derivatives of imazaquin, imazapyr, imazmethapyr, imazethapyr, 2-[4,5 dihydro-1, 4-dimethyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-methoxymethyl- 3-pyridine carboxylic acid, 2-[4,5-dihydro-1,4 -dimethyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4-methyl benzoic acid, and 2-[4,5-dihydro-1,4-dimethyl-4-(1-methyl ethyl)-5-oxo-1H-imidazol-2-yl]-5-methyl benzoic acid were prepared and fully characterized. The availability of these derivatives has led to the development of efficient and multiresidue gas chromatographic methods for trace level analysis of imidazolinone herbicides in matrixes such as water, soybean, and soil.