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.     

Safening activity of natural hydroxamic acids and analogous compounds against herbicide injury to maize

Abstract

Safening activities of natural compounds DIMBOA, DIBOA, and MBOA, as well as synthetic 1,4‐benzoxazin‐3‐ones were tested against acetochlor and EPTC injuries to maize. No safening activities of natural products and from low to moderate activity of synthetic benzoxazinones were observed. In order to explain inefficacy of natural compounds we studied the influence of these molecules on enzymes participating in metabolic detoxication of acetochlor and EPTC. Pretreatment with DIMBOA elevated maize cytochrome P450 levels. Pretreatments with chemicals containing 1,4‐benzoxazin‐3‐one backbone did not alter glutathione S‐transferase enzyme activities. However, all natural products inhibited glutathione S‐transferase activity of roots and shoots in vitro after addition to the enzyme. Safening ineffectiveness of natural hydroxamic acids may be explained by their inhibitory effects on GST enzymes due to their reaction with sulfhydryl groups on the enzyme.     

Field dissipation of 4-nonylphenol, 4-t-octylphenol, triclosan and bisphenol A following land application of biosolids

The persistence of contaminants entering the environment through land application of biosolids needs to be understood to assess the potential risks associated. This study used two biosolids treatments to examine the dissipation of four organic compounds: 4-nonylphenol, 4-t-octylphenol, bisphenol A and triclosan, under field conditions in South Australia. The pattern of dissipation was assessed to determine if a first-order or a biphasic model better described the data. The field dissipation data was compared to previously obtained laboratory degradation data. The concentrations of 4-nonylphenol, 4-t-octylphenol and bisphenol A decreased during the field study, whereas the concentration of triclosan showed no marked decrease. The time taken for 50% of the initial concentration of the compounds in the two biosolids to dissipate (DT50), based on a first-order model, was 257 and 248 d for 4-nonylphenol, 231 and 75 d for 4-t-octylphenol and 289 and 43 d for bisphenol A. These field DT50 values were 10- to 20-times longer for 4-nonylphenol and 4-t-octylphenol and 2.5-times longer for bisphenol A than DT50 values determined in the laboratory. A DT50 value could not be determined for triclosan as this compound showed no marked decrease in concentration. The biphasic model provided a significantly improved fit to the 4-t-octylphenol data in both biosolids treatments, however, for 4-nonylphenol and bisphenol A it only improved the fit for one treatment. This study shows that the use of laboratory experiments to predict field persistence of compounds in biosolids amended soils may greatly overestimate degradation rates and inaccurately predict patterns of dissipation.     

Anaerobic transformation of chlorophenols in methanogenic sludge unexposed to chlorophenols

Transformation of all 19 chlorophenol (CP) isomers was investigated in a laboratory anaerobic methanogenic sludge that had not been exposed to synthetic chemicals. Concentration of CP was analyzed over time to calculate disappearance rate constants using first-order reaction kinetics and all possible CP degradation pathways were estimated. The rate constants ranged between 0.46 x 10(-3) and 0.161 day(-1). CPs were transformed via dechlorination. The chlorine atom at the ortho-position was the most easily dechlorinated, whereas dechlorination rate at the para-position was lowest. The overall pathways of CP transformation were much less diverse than that we previously found for contaminated sediment. The Dolfing hypothesis of microbial selection of the most thermodynamically favorable pathways was not applicable for CP transformation in this study as well as previous study performed by our group.     

Study of the spatial variation of the biodegradation rate of the herbicide bentazone with soil depth using contrasting incubation methods

Vertical and horizontal spatial variability in the biodegradation of the herbicide bentazone was compared in sandy-loam soil from an agricultural field using sieved soil and intact soil cores. An initial experiment compared degradation at five depths between 0 and 80 cm using sieved soil. Degradation was shown to follow the first-order kinetics, and time to 50% degradation (DT(50)), declined progressively with soil depth from 56 d at 0-10 cm to 520 d at 70-80 cm. DT(50) was significantly correlated with organic matter, pH and dehydrogenase activity. In a subsequent experiment, degradation rate was compared after 127 d in sieved soil and intact cores from 0 to 10 and 50 to 60 cm depth from 10 locations across a 160x90 m portion of the field. Method of incubation significantly affected mean dissipation rate, although there were relatively small differences in the amount of pesticide remaining in intact cores and sieved soil, accounting for between 4.6% and 10.6% of that added. Spatial variability in degradation rate was higher in soil from 0 to 10 cm depth relative to that from 50 and 60 cm depth in both sieved soil and intact core assessments. Patterns of spatial variability measured using cores and sieved soil were similar at 50-60 cm, but not at 0-10 cm depth. This could reflect loss of environmental context following processing of sieved soil. In particular, moisture content, which was controlled in sieved soil, was found to be variable in cores, and was significantly correlated with degradation rate in intact topsoil cores from 0 to 10 cm depth.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 x 10(- 3) h(- 1) to 7.0 x 10(- 3) h(- 1). The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Dissipation pattern and residual levels of boscalid in cucumber and soil using liquid chromatography-tandem mass spectrometry

Abstract

To stipulate the rationale of spraying doses and to determine the safe interval period of boscalid suspension concentrate (SC), the degradation dynamics and residual levels were investigated in cucumber and soil using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Field trials were conducted according to Chinese Guideline on pesticide residue trials. Following application, the degradation kinetics was best ascribed to first-order kinetic models with half-life of 2.67–9.90 d in cucumber. Spraying boscalid SC at 1.5-fold the recommended dosage yield terminal residues, which are clearly lower than the maximum residue limit (MRL) established by China (MRL =5?mg.kg^?1) in cucumber. At variance, the dissipation dynamics in soil did not fit to first-order kinetics and the half-life was more than 17?days, the finding which denotes that the degradation behavior of boscalid in soil proceeds slowly. It has therefore been shown that boscalid is safe for use on cucumbers under the recommended dosage.     

Characterizing pesticide sorption and degradation in microscale biopurification systems using column displacement experiments

Biopurification systems treating pesticide contaminated water are very efficient, however they operate as a black box. Processes inside the system are not yet characterized. To optimize the performance, knowledge of degradation and retention processes needs to be generated. Therefore, displacement experiments were carried out for four pesticides (isoproturon, bentazone, metalaxyl, linuron) in columns containing different organic mixtures. Bromide, isoproturon and bentazone breakthrough curves (BTCs) were well described using the convection-dispersion equation (CDE) and a first-order degradation kinetic approach. Metalaxyl and linuron BTCs were well described using the CDE model expanded with Monod-type kinetics. Freundlich sorption, first-order degradation and Monod kinetics coefficients were fitted to the BTCs. Fitted values of the distribution coefficient K_f,column were much lower than those determined from batch experiments. Based on mobility, pesticides were ranked as: bentazone > metalaxyl - isoproturon > linuron. Based on degradability, pesticides were ranked as: linuron > metalaxyl - isoproturon > bentazone.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at lambda = 254 nm. The photolysis of (alpha + beta: 2 + 1) endosulfan, alpha-endosulfan and beta-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 x 10(-4) s(-1); 1 x 10(-4) s(-1); and 2 x 10(-5) s(-1), respectively, and the calculated quantum yields (phi) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.     

直接红染料的臭氧脱色与中间产物研究

以直接红B模拟染料废水为研究对象,考察了臭氧化过程中染料溶液的吸光度和TOC的变化,同时利用离子色谱仪和GC/MS对染料的降解过程进行了分析,最后用发光细菌法检测了染料溶液急性毒性的变化。结果表明,臭氧对染料的降解符合一级反应动力学,20 min时对染料的脱色率达到99.2%;反应40 min后TOC减少32.55%,染料分子有97.8%的S被氧化为SO^2-₄,偶氮键被臭氧化为N₂,分子中的仲胺基小部分转化成游离NH⁺₄和NO^-₃;在臭氧化过程前期新生成的醛类和酰胺类物质使溶液急性毒性迅速上升,25 min后溶液毒性开始逐渐下降。     

Study of atrazine degradation in subsurface flow constructed wetland under different salinity

To evaluate the treatment capability of subsurface flow constructed wetland (SFCW) and the effect of salinity on the degradation of atrazine, the degradation of atrazine in SFCW was studied. Under the static condition, the degradation of atrazine in SFCW followed first-order kinetics: c=0.09679 exp(-0.0396t) (c, residue concentration, mg l(-1); t, retention time, d), with a half-life of approximately 17.5 days. The atrazine degradation kinetic functions were established for salinities of 1.5, 3.0, 5.0, 10.0 and 15.0 g l(-1), respectively, which appeared to approach first-order kinetics. The effect of salinity on the atrazine treatment efficiency showed an exponential inhibition: lnk=3.204+0.04991 C (k, degradation constant; C, NaCl concentration, mg l(-1)). The attenuation of atrazine in SFCW cannot be a result of hydrolysis or sorption process. It was considered that some bacteria in the wetland system degraded atrazine into deethylatrazine (DEA) and deisopropylatrazine (DIA) and sequentially into CO(2) and H(2)O. Salinity impacted on the growth of bacteria resulting in a switch of the microbial community. With the increase of salinity, Shannon-Wiener Diversity Index in the SFCW system declined. The relationship between atrazine degradation constant (k) and Shannon Index was established as shown in linear phase, y=-0.07286+0.0363x. The positive correlation between them indicated that microbial community played an important role in the atrazine degradation process.     

Modelling the dissipation kinetics of six commonly used pesticides in two contrasting soils of New Zealand

We used three non-linear bi-phasic models, bi-exponential (BEXP), first-order double exponential decay (FODED), and first-order two-compartment (FOTC), to fit the measured degradation data for six commonly used pesticides (atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone) in two New Zealand soils. Corresponding DT₅₀ and DT₉₀ values for each compound were numerically obtained and compared against those estimated by simple first-order kinetic (SFOK) model. All 3 non-linear models gave good fit of the measured data under both soil depths and were well supported by the values obtained for the respective statistical indices (RMSE, CRM and r ²). The FOTC model gave by far the best fit for most compounds, followed by the FODED and BEXP models. Overall, DT₅₀ values derived by non-linear models for the six compounds in soils from both sites were lower than the values obtained by the SFOK model. Differences in the SFOK and the three non-linear models derived DT₉₀were, however, an order of magnitude higher for some compounds, while for others differences were very small. Although all three non-linear models described most data by giving excellent fits, in a few instances > 5–10% asymptotes hindered the estimation of DT₉₀ values. This work shows that when degradation deviates from first-order kinetic, application of non-linear decay models to describe the kinetics of degradation becomes important in order to derive the true end-points for pesticides in soil.     

Photochemical degradation of methylparathion in the presence of humic acid

Photochemical degradation of methylparathion (O,O,-dimethyl O-4 nitrophenylphosphorothioate) in the presence of humic acid between pH 2 and 7 was monitored by differential pulse polarography. Humic acid was not electro-active under the experimental conditions used in this study. Only the pesticide and its main degradation product at pH 2 exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by humic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation in the presence of humic acid was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 2 x 10(-3) to 6.3 x 10(-3) min(-1).     

Sorption behavior of dibutyl phthalate and dioctyl phthalate by aged refuse

Sorption is a fundamental process controlling the transformation, fate, degradation, and biological activity of hydrophobic organic contaminants in the environment. We investigated the kinetics, isotherms, and potential mechanisms for the sorption of two phthalic acid esters (PAEs), dibutyl phthalate (DBP) and dioctyl phthalate (DOP), on aged refuse. A two-compartment first-order model performed better than a one-compartment first-order model in describing the kinetic sorption of PAEs, with a fast sorption process dominating. Both the Freundlich and Dubinin–Astakhov (DA) models fit the sorption isotherms of DBP and DOP, with the DA model being of a better fit over the range of apparent equilibrium concentrations. The values of the fitting parameters (n, b, E) of the PAEs suggest nonlinear sorption characteristics. Higher predicted partition coefficient values and saturated sorption capacity existed in refuse containing larger quantities of organic matter. The sorption capacity of DOP was significantly higher than that of DBP. PAE sorption was dependent on liquid phase pH. Desorption hysteresis occurred in PAE desorption experiments, especially for the long-chain DOP. PAEs may therefore be a potential environmental risk in landfill.     

Degradation of zearalenone and ochratoxin A in three Danish agricultural soils

Degradation of two mycotoxins: zearalenone (ZON) produced by species of Fusarium and ochratoxin A (OTA) produced by species of Penicillium were followed in pot experiments using agricultural topsoils from Danish experimental farms: a sandy soil, a sandy clay soil and a gyttja soil with a high content of silt. Experiments with unplanted soil and pots planted with barley were included. Soil samples were withdrawn during a period of 225 days and analysed for the content of OTA and ZON. The degradation of both toxins consisted of an initial fast degradation followed by a slower transformation step and was described well by a sum of two first-order kinetic equations. The decay first-order rate constants for the first step (k1) were in the range 0.73-2.91 d(-1) for OTA and 0.0612-0.108 d(-1) for ZON, respectively. Half-lives (t0.5) for ZON using data from the first phase were between 6.4 and 11 days, whereas the half-lives for OTA were about 0.2-1 day. The slowest degradation was measured in soil rich in clay. After 225 days, neither OTA nor ZON was detected in any of the soil types. Generally, the degradation of ZON and OTA was faster in planted soil than in unplanted soil, probably due to higher microbial activity. Due to the fast degradation of ZON and OTA in surface soil leaching as soluble substances appears to be limited.     

Dissipation of some organochlorine insecticides in cropped and uncropped soil

Dissipation of four organochlorine insecticides, viz. aldrin, HCH, chlordane and heptachlor was studied in a sandy loam soil with and without crops during a period of 10 cropping seasons. Dissipation of all chemicals followed first-order kinetics (r(2)=0.537 - 0.976) with almost similar persistence in cropped and uncropped soils for all the insecticides. The average half-lives, (t(1/2) values) for total residues of aldrin, HCH, chlordane, and heptachlor in cropped treatments were 80.7, 58.8, 93.2, and 110 days. Their respective values in fallow plots were 78.4, 83.8, 154, and 116 days. None of the parent compounds or their isomers could be detected below the 20 cm depth at the termination of the experiment. Highest residue concentrations were observed in the surface 10 cm layer in fallow plots, but in the deeper (10-20 cm) layer in cropped plots. Analysis of plants and grains showed significant residues of all the chemicals. Degradation of these compounds in cropped and uncropped plots is discussed with regard to their volatilization, microbial degradation, leaching, and plant uptake.     

Plant uptake of aldicarb from contaminated soil and its enhanced degradation in the rhizosphere

Experiments were conducted to investigate the degradation of aldicarb, an oxime carbamate insecticide, in sterile, non-sterile and plant-grown soils, and the capability of different plant species to accumulate the pesticide. The degradation of aldicarb in soil followed first-order kinetics. Half lives (t1/2) of aldicarb in sterile and non-sterile soil were 12.0 and 2.7 days, respectively, which indicated that microorganisms played an important part in the degradation of aldicarb in soil. Aldicarb disappeared more quickly (p< or =0.05) in the soil with the presence of plants, and t1/2 of the pesticide were 1.6, 1.4 and 1.7 days in the soil grown with corn, mung bean and cowpea, respectively. Comparison of plant-promoted degradation and plant uptake showed that the enhanced removal of aldicarb in plant-grown soil was mainly due to plant-promoted degradation in the rhizosphere.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 × 10^{? 3} h^{? 1} to 7.0 × 10^{? 3} h^{? 1}. The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

TiO_2/NiPECO体系降解DMP的动力学和光电协同作用研究

以采用微波辅助法制备的TiO2/Ni光电极为阳极,纤维状石墨毡材料(graphite felt,GF)为阴极,饱和甘汞电极(saturated calomel electrode,SCE)为参比电极建立TiO2/Ni光电催化氧化(PECO)体系.以邻苯二甲酸二甲酯(dimethyphthalate,DMP)为目标物,研究其光电催化降解反应动力学和光电协同作用.结果显示:DMP的降解符合拟一级动力学规律;当DMP初始浓度一定时,影响DMP光电催化降解速率的因素由强到弱依次为:催化剂有效面积,紫外光强度,曝氧速率,外加偏转电压等.实验证明本体系中光电之间具有协同作用.     

Transformation products of 2-benzoxazolinone (BOA) in soil

Three degradation experiments were performed to examine the formation of transformation products from 2-benzoxazolinone (BOA) in different soil types and concentrations. In two experiments using BOA in low concentration (400 microgkg(-1)) only one unidentified transformation product was found, whereas in the degradation experiment in high concentration (400 mgkg(-1)) several metabolites occurred. Two of these metabolites, 2-amino-(3H)-phenoxazin-3-one (APO); and 2-acetylamino-(3H)-phenoxazin-3-one (AAPO) were synthesized to prove their identity. This is the first time that the successive formation of these types of compounds from BOA is shown in soil. A number of other APO related transformation products were detected and provisionally characterized. The formation of APO, which is a much more biologically active compound than BOA, and the concurrent formation of a number of other APO-related metabolites in soil underline the importance of performing transformation studies as part of the evaluation of the effect of allelochemicals on weeds and soil-borne diseases.