Capacity of model biobeds to retain and degrade mecoprop and isoproturon

Biobeds are used to increase the adsorption and degradation of pesticide spillage on sites used for mixing and loading and for cleaning of sprayers. The adsorption and the rate of degradation of 14C-labelled isoproturon and mecoprop (MCPP) at concentrations from 0.0005 to 25 000 mgkg(-1) were determined in biobed soil. Further leaching of the two herbicides was determined in a model biobed with a surface area of 2 m2. The biobed material showed enhanced ability to adsorb the two herbicides. Kd was 5.2 litre kg(-1) for isoproturon and 1.6 litre kg(-1) for MCPP in biobed material, which is higher than in natural soil. In different experiments with natural soil, Kd ranges from 0.07 to 0.6 litrekg(-1) for MCPP and from 1.5 to 4.6 litre kg(-1) for isoproturon in soils with varying organic carbon content. Degradation of MCPP was rapid at concentrations from 0.0005 to 500 mg kg(-1), delayed at 5000 mg kg(-1), and very slow at 25 000 mg kg(-1). For isoproturon, the relative degradation was most rapid at the lowest concentration and decreasing with increasing concentrations. After 120 days, between 55% and 8% 14C was evolved as 14CO2 at concentrations between 0.0005 and 25 000 mg kg(-1). The rate of evolution of 14CO2 indicated that degradation rates at low concentrations were of first-order and at higher concentrations of zero-order. Leaching of MCPP and isoproturon was determined in a newly established model biobed during a 2-year period. About 13% of applied MCPP and 1.4% of applied isoproturon leached out during the winter following the first autumn application (worst-case scenario). Leaching was completely prevented when the biobed had a well-developed grass cover and was covered during the winter.     

Degradation of atrazine and isoproturon in the unsaturated zone: a study from Southern England

The potential for degradation of atrazine or isoproturon in the unsaturated zone of two boreholes was studied under laboratory conditions. Intact and uncontaminated samples were obtained from regular depths of 0–16.45 m and 0–9 m using a percussion coring technique. The results showed that the deep unsaturated zone contained micro-organisms capable of degrading atrazine or isoproturon. The rate of degradation was much faster in surface soil than in most unsaturated materials of both boreholes. The amount of atrazine remaining six months after incubation also varied between the two boreholes. A relatively small amount of atrazine was lost from sterilised samples, suggesting a significant role for microbial degradation. The addition of nutrient and energy sources into materials of low degradation capacity did not enhance the degradation of atrazine. Degradation rate was more related to the presence of a competent microbial population rather than to the presence of indigenous organic matter. However, the competent micro-organisms are more likely to be present when the organic matter content is high. The type and activity of these micro-organisms and their physical environment may have considerable influence on atrazine degradation and are likely to be responsible for much of the variation in the rate of degradation observed at different depths. © 1999 Society of Chemical Industry     

Degradation of atrazine and isoproturon in surface and sub-surface soil materials undergoing different moisture and aeration conditions

The influence of different moisture and aeration conditions on the degradation of atrazine and isoproturon was investigated in environmental samples aseptically collected from surface and sub-surface zones of agricultural land. The materials were maintained at two moisture contents corresponding to just above field capacity or 90% of field capacity. Another two groups of samples were adjusted with water to above field capacity, and, at zero time, exposed to drying-rewetting cycles. Atrazine was more persistent (t(1/2) = 22-35 days) than isoproturon (t(1/2) = 5-17 days) in samples maintained at constant moisture conditions. The rate of degradation for both herbicides was higher in samples maintained at a moisture content of 90% of field capacity than in samples with higher moisture contents. The reduction in moisture content in samples undergoing desiccation from above field capacity to much lower than field capacity enhanced the degradation of isoproturon (t(1/2) = 9-12 days) but reduced the rate of atrazine degradation (t(1/2) = 23-35 days). This demonstrates the variability between different micro-organisms in their susceptibility to desiccation. Under anaerobic conditions generated in anaerobic jars, atrazine degraded much more rapidly than isoproturon in materials taken from three soil profiles (0-250 cm depth). It is suggested that some specific micro-organisms are able to survive and degrade herbicide under severe conditions of desiccation.     

Degradation of isoproturon and bentazone in peat- and compost-based biomixtures

BACKGROUND: The composition and properties of a biomixture used in a biobed are decisive for pesticide sorption and degradation. This study was performed to investigate the capability of compost‐based substrates in mixtures with citrus peel and vine branch straw and peat‐based substrates in mixtures with soil and vine branch straw at different levels in order to degrade isoproturon and bentazone. RESULTS: Dissipation and mineralisation rates of both pesticides were determined, and metabolic activity was followed as respiration. Compost‐based substrates showed faster pesticide dissipation in the presence of lignocellulosic materials, as in garden compost and vine branch straw. The increasing content of vine branch straw in peat‐based substrates does not seem to affect dissipation of the parent compounds. Low mineralisation rate was observed in all treatments. CONCLUSION: Higher pesticide degradation was observed in the lignocellulosic substrates, probably because of the development of lignin‐degrading microorganisms which have shown to be robust and are able to degrade recalcitrant pesticides. Copyright © 2010 Society of Chemical Industry     

Mineralization of 2,4‐D,mecoprop, isoproturon and terbuthylazine in a chalk aquifer

The potential to mineralize 2,4‐dichlorophenoxyacetic acid (2,4‐D), mecoprop, isoproturon and terbuthylazine was studied in soil and aquifer chalk sampled at an agricultural field near Aalborg, Denmark. Laboratory microcosms were incubated for 258 days under aerobic conditions at 10 °C with soil and chalk from 0.15–4.45 m below the surface. The [ring‐U‐¹⁴C]‐labeled herbicides were added to obtain a concentration of 6 µg kg^?1 and mineralization was measured as evolved [¹⁴C]carbon dioxide. The herbicides were readily mineralized in soil from the plough layer, except for terbuthylazine, which was mineralized only to a limited extent. In the chalk, lag periods of at least 40 days were observed, and a maximum of 51%, 33% and 6% of the added 2,4‐D, mecoprop and isoproturon, respectively, were recovered as [¹⁴C]carbon dioxide. Large variations in both rate and extent of mineralization were observed within replicates in chalk. No mineralization of terbuthylazine in chalk was observed. As a measure of the general metabolic activity towards aromatic compounds, [ring‐U‐¹⁴C]‐benzoic acid was included. It was readily mineralized at all depths. © 2000 Society of Chemical Industry     

Lysimeter study to investigate the effect of rainfall patterns on leaching of isoproturon

The influence of five rainfall treatments on water and solute leaching through two contrasting soil types was investigated. Undisturbed lysimeters (diameter 0.25 m, length 0.5 m) from a sandy loam (Wick series) and a moderately structured clay loam (Hodnet series) received autumn applications of the radio-labelled pesticide isoproturon and bromide tracer. Target rainfall plus irrigation from the end of November 1997 to May 1998 ranged from drier to wetter than average (235 to 414 mm); monthly rainfall was varied according to a pre-selected pattern or kept constant (triplicate lysimeters per regime). Leachate was collected at intervals and concentrations of the solutes were determined. Total flow (0.27-0.94 pore volumes) and losses of bromide (3-80% of applied) increased with increasing inputs of water and were larger from the Wick sandy loam than from the Hodnet clay loam soil. Matrix flow appeared to be the main mechanism for transport of isoproturon through the Wick soil whereas there was a greater influence of preferential flow for the Hodnet lysimeters. The total leached load of isoproturon from the Wick lysimeters was 0.02-0.26% of that applied. There was no clear variation in transport processes between the rainfall treatments investigated for this soil and there was an approximately linear relationship (r2 = 0.81) between leached load and total flow. Losses of isoproturon from the Hodnet soil were 0.03-0.39% of applied and there was evidence of enhanced preferential flow in the driest and wettest treatments. Leaching of isoproturon was best described by an exponential relationship between load and total flow (r2 = 0.62). A 45% increase in flow between the two wettest treatments gave a 100% increase in leaching of isoproturon from the Wick soil. For the Hodnet lysimeters, a 35% increase in flow between the same treatments increased herbicide loss by 325%.     

A field tracer study of attenuation of atrazine,hexazinone and procymidone in a pumice sand aquifer

A field tracer experiment, simulating point source contamination, was conducted to investigate attenuation and transport of atrazine, hexazinone and procymidone in a volcanic pumice sand aquifer. Preliminary laboratory incubation tests were also carried out to determine degradation rates. Field transport of the pesticides was observed to be significant under non‐equilibrium conditions. Therefore, a two‐region/two‐site non‐equilibrium transport model, N3DADE, was used for analysis of the field data. A lump reduction rate constant was used in this paper to encompass all the irreversible reduction processes (eg degradation, irreversible adsorption, complexation and filtration for the pesticides adsorbed into particles and colloids) which are assumed to follow a first‐order rate law. Results from the field experiment suggest that (a) hexazinone was the most mobile (retardation factor R = 1.4) and underwent least mass reduction; (b) procymidone was the least mobile (R = 9.26) and underwent the greatest mass reduction; (c) the mobility of atrazine (R = 4.45) was similar to that of rhodamine WT (R = 4.10). Hence, rhodamine WT can be used to delimit the appearance of atrazine in pumice sand groundwater. Results from the incubation tests suggest that (a) hexazinone was degraded only in the mixture of groundwater and aquifer material (degradation rate constant = 4.36 × 10^?3 day^?1); (b) procymidone was degraded not only in the mixture of groundwater and aquifer material (rate constant = 1.12 × 10^?2 day^?1) but also in the groundwater alone (rate constant = 2.79 × 10^?2 day^?1); (c) atrazine was not degraded over 57 days incubation in either the mixture of aquifer material and groundwater or the groundwater alone. Degradation rates measured in the batch tests were much lower than the total reduction rates. This suggests that not only degradation but also other irreversible processes are important in attenuating pesticides under field conditions. Hence, the use of laboratory‐determined degradation rates could underestimate reduction of pesticides in field conditions. © 2001 Society of Chemical Industry     

QuEChERS-超高效液相色谱-串联质谱法同时测定大米、小麦和动物源食品中异丙隆及其代谢物脱甲基异丙隆残留

本研究建立了超高效液相色谱-串联质谱法(UHPLC-MS/MS)同时测定异丙隆及其代谢物脱甲基异丙隆在大米、小麦、牛肉、牛奶、鸡肉和鸡蛋的残留检测方法。样品经2%甲酸乙腈提取,以N-丙基乙二胺(PSA)净化,利用乙腈和0.2%甲酸水作为流动相梯度洗脱,T3色谱柱分离,在多反应监测模式下定量分析,基质外标法定量。结果表明:异丙隆及其代谢物脱甲基异丙隆溶剂标准曲线和基质标准曲线在1~1 000μg/L范围内线性关系良好,相关系数均大于0.99。在4个加标水平下,异丙隆日内平均回收率为74.0%~107.0%,相对标准偏差0.7%~12.9%;日间平均回收率为76.2%~108.7%,相对标准偏差1.1%~19.8%。脱甲基异丙隆日内平均回收率为76.9%~113.5%,相对标准偏差0.6%~13.9%;日间平均回收率为77.7%~107.4%,相对标准偏差2.2%~17.4%。异丙隆和脱甲基异丙隆的定量限均为1.0μg/kg。该方法简便、快捷、准确、灵敏度高,适用于异丙隆和脱甲基异丙隆在大米、小麦、牛肉、牛奶、鸡肉和鸡蛋6种基质中残留的检测,为解决异丙隆和脱甲基异丙隆在食品中残留的安全问题提供技术方法。     

Resistance of barnyardgrass (Echinochloa crus-galli) to atrazine and quinclorac

Two populations of Echinochloa crus-galli (R and I) exhibited resistance to quinclorac. Another population (X) exhibited resistance to quinclorac and atrazine. The R and I populations were collected from monocultures of rice in southern Spain. The X population was collected from maize fields subjected to the application of atrazine over several years. The susceptible (S) population of the same genus was collected from locations which had never been treated with herbicides. The quinclorac ED₅₀ value (dose causing 50% reduction in shoot fresh weight) for the R and I biotypes were 26- and 6-fold greater than for the S biotype. The X biotype was 10 times more tolerant to quinclorac than the S biotype and also showed cross-resistance to atrazine, being 82-fold more resistant to atrazine than the R, I and S biotypes. Chlorophyll fluorescence and Hill reaction analysis supported the view that the mechanism of resistance to atrazine in the X biotype was modification of the target site, the DI protein. Quinclorac at 20 mg litre^-1 did not inhibit photosynthetic electron transport in any of the test biotypes. The quinclorac I₅₀ values (herbicide dose needed for 50% Hill reaction reduction) of the S population was over 50000-fold higher than the atrazine I₅₀ value for the same S population, indicating that quinclorac is not a PS II inhibiting herbicide. Propanil at doses greater than 0·5 kg ha^-1 controlled all the biotypes. © 1997 SCI     

Degradation and sorption of atrazine, hexazinone and procymidone in coastal sand aquifer media

The degradation, sorption and transport of atrazine, hexazinone and procymidone in saturated coastal sand aquifer media were investigated in batch and column experiments. The pesticides were incubated with sterilised and non-sterilised groundwater or a mixture of groundwater and the aquifer material in the dark at 15 degrees C for 120 days. The estimated half-lives of the pesticides (and their ranges) in the mixture of groundwater and aquifer sand were 36 (31-40), 54 (40-77) and 84 (46-260) days for atrazine, procymidone and hexazinone, respectively. Compared with the relevant results for the groundwater-sand mixture phase, the estimated half-life of pesticides in the groundwater phase alone was shorter for procymidone (21 days) but longer for hexazinone (134 days); atrazine was not degraded in the groundwater phase. Chemical degradation appeared to have played the predominant role in the degradation of hexazinone and procymidone in the aquifer system, while both chemical and biological processes seemed to be important for the degradation of atrazine. Batch isothermal experiments were carried out at pH 4.6-4.7 to obtain sorption coefficients under equilibrium conditions. The isothermal data of the pesticides fitted well with the non-linear Freundlich function with an exponent of sorption coefficient that was greater than one. Contrary to reports in the literature, sorption of atrazine was the greatest, and procymidone was slightly more sorbed than hexazinone. A column experiment was conducted at a typical field-flow velocity of 0.5 m day(-1) over 60 days to study pesticide attenuation and transport in flow dynamic conditions. Retardation factors, R, derived from a two-site sorption/desorption model were 8.22, 1.76 and 1.63 for atrazine, procymidone and hexazinone, respectively. Atrazine displayed the lowest mobility and the mobility of procymidone was only slightly less than that of hexazinone, which is consistent with observations in the batch experiment. A possible explanation for these observations is that ionic atrazine is bound to oppositely charged ionic oxides, and ionic oxides have less effect on the sorption of the non-ionic procymidone. The significant tailing in the pesticide breakthrough curves (BTCs) in comparison with the bromide BTC, together with model-simulated results, suggests that the transport of the pesticides was under chemical non-equilibrium conditions with R values that were less than their equivalent values predicted using the batch equilibrium isothermal data. As a result of non-linear kinetic sorption, retardation factors of the pesticides in groundwater systems would not be constant and will decrease with decreasing pesticide concentrations and increasing flow velocities. Hence, the use of equilibrium isotherm data will probably over-predict the sorption of pesticides in groundwater systems. Rhodamine WT, a commonly used groundwater tracer, was significantly retarded (R = 5.48) and its BTC was much more spread out than the bromide BTC. Therefore, it would not be a good tracer for the indication of groundwater flow velocity and dispersion for the coastal sand aquifer system. In contrast to some aquifer media, the dye tracer was unsuitable as a marker of the appearance of atrazine in a coastal sand aquifer system.     

莠去津土壤残留生物修复菌肥作用原理与田间应用

莠去津是玉米田应用的优秀除草剂品种,然而由于其在土壤中残留时间长,常对轮作后茬敏感作物造成严重毒害。采用生物修复菌肥做种肥、结合菌肥拌种和叶面喷施方法,研究对玉米后茬旱直播水稻生长发育及药害修复机理,对土壤中莠去津残留量、水稻生长和生理指标、土壤酶活性进行测定。结果表明:颗粒菌肥做种肥+粉剂菌肥拌种+水剂菌肥叶面喷施是莠去津土壤残留毒害修复的最佳方法,土壤中莠去津含量在喷施菌肥后7 d从施用菌肥前的0.9 mg/kg下降到0.1 mg/kg,水稻叶片叶绿素含量显著增加33.74%,超氧化物歧化酶和过氧化物酶酶活性分别显著提高23.39%和92.57%,丙二醛含量则显著降低48.01%;水稻株高、地上部鲜重、干重分别比对照显著增加22.33%、67.51%和74.80%,根系鲜重和干重分别比对照显著增加33.98%和55.43%;土壤磷酸酶、脲酶及纤维素酶含量分别显著增加49.17%、528.65%和35.21%。     

Monitoring of atrazine treatment on soil bacterial,fungal and atrazine-degrading communities by quantitative competitive PCR

We report the development of quantitative competitive (QC) PCR assays for quantifying the 16S, 18S ribosomal and atzC genes in nucleic acids directly extracted from soil. QC-PCR assays were standardised, calibrated and evaluated with an experimental study aiming to evaluate the impact of atrazine application on soil microflora. Comparison of QC-PCR 16S and 18S results with those of soil microbial biomass showed that, following atrazine application, the microbial biomass was not affected and that the amount of 16S rDNA gene representing 'bacteria' increased transitorily, while the amount of 18S rDNA gene representing fungi decreased in soil. In addition, comparison of atzC QC-PCR results with those of atrazine mineralisation revealed that, in response to atrazine treatment, the amount of atzC gene increased transitorily in soil pre-treated with atrazine, suggesting that accelerated atrazine biodegradation in soil could be due to a transient increase in the size of the atrazine mineralising community.     

分散固相萃取-超高效液相色谱-串联质谱法同时检测大豆植株及土壤中烟嘧磺隆、莠去津及其代谢物残留

土壤中烟嘧磺隆和莠去津的高残留往往会导致后茬大豆药害问题。本研究建立了一种分散固相萃取-超高效液相色谱-串联质谱法同时检测大豆植株及土壤中烟嘧磺隆、莠去津及其代谢物残留方法。样品经含2%甲酸的乙腈提取, 经分散固相萃取净化, 以乙腈和0.2%甲酸水为流动相, 采用Poroshell 120 EC-C18色谱柱梯度洗脱, 基质匹配标准曲线外标法定量分析。结果表明:在0.01、0.10 mg/kg和1.00 mg/kg添加水平下, 烟嘧磺隆、莠去津及其代谢物的平均回收率为70%~113%, 相对标准偏差为0.3%~11.8%, 目标化合物质量浓度与对应的峰面积之间在0.001~1 mg/kg范围内线性关系良好, 决定系数R2≥0.984 1, 方法的定量限为0.01 mg/kg。该方法简便、快捷、准确, 适用于土壤和幼苗期至鼓粒期大豆植株中烟嘧磺隆、莠去津及其代谢物的检测。本研究为烟嘧磺隆和莠去津的科学使用及后茬作物的安全种植提供有效监测方法。     

Resistance to ACCase-inhibiting herbicides and isoproturon in UK populations of Lolium multiflorum: mechanisms of resistance and implications for control

Herbicide-resistant Lolium multiflorum (Italian rye-grass) was first reported in the UK in 1993 and had been confirmed on 25 farms by 1999. In this study, resistance to five herbicides belonging to the aryloxyphenoxypropionate, cyclohexanedione and phenyl-urea classes was determined in six populations of L multiflorum from the UK under glasshouse and simulated field conditions. Glasshouse conditions tended to exaggerate the degree of resistance, but experiments performed in both environments detected resistance in four populations of L multiflorum. Four populations (Essex A1, Lincs A1, Wilts B1, Yorks A2) were resistant to diclofop-methyl, fluazifop-P-butyl, tralkoxydim and partially resistant to isoproturon, but only the population from Yorkshire (Yorks A2) showed resistance to cycloxydim. Biochemical analyses of acetyl coenzyme A carboxylase (ACCase) activity, oxygen consumption by thylakoids, diclofop metabolism and glutathione S-transferase activity showed that, in three of the resistant populations, an enhanced rate of herbicide metabolism conferred resistance. This is the first report world-wide of an enhanced metabolism mechanism of diclofop resistance in L multiflorum. In the Yorks A2 population, an insensitive ACCase was detected (target-site resistance) which also conferred cross-resistance to all of the other ACCase inhibitors investigated.     

Test of the Root Zone Water Quality Model (RZWQM) for predicting runoff of atrazine, alachlor and fenamiphos species from conventional-tillage corn mesoplots

The Root Zone Water Quality Model (RZWQM) is a comprehensive, integrated physical, biological and chemical process model that simulates plant growth and movement of water, nutrients and pesticides in a representative area of an agricultural system. We tested the ability of RZWQM to predict surface runoff losses of atrazine, alachlor, fenamiphos and two fenamiphos oxidative degradates against results from a 2-year mesoplot rainfall simulation experiment. Model inputs included site-specific soil properties and weather, but default values were used for most other parameters, including pesticide properties. No attempts were made to calibrate the model except for soil crust/seal hydraulic conductivity and an adjustment of pesticide persistence in near-surface soil. Approximately 2.5 (+/- 0.9), 3.0 (+/- 0.8) and 0.3 (+/- 0.2)% of the applied alachlor, atrazine and fenamiphos were lost in surface water runoff, respectively. Runoff losses in the 'critical' events--those occurring 24 h after pesticide application--were respectively 91 (+/- 5), 86 (+/- 6) and 96 (+/- 3)% of total runoff losses for these pesticides. RZWQM adequately predicted runoff water volumes, giving a predicted/observed ratio of 1.2 (+/- 0.5) for all events. Predicted pesticide concentrations and loads from the 'critical' events were generally within a factor of 2, but atrazine losses from these events were underestimated, which was probably a formulation effect, and fenamiphos losses were overestimated due to rapid oxidation. The ratios of predicted to measured pesticide concentrations in all runoff events varied between 0.2 and 147, with an average of 7. Large over-predictions of pesticide runoff occurred in runoff events later in the season when both loads and concentrations were small. The normalized root mean square error for pesticide runoff concentration predictions varied between 42 and 122%, with an average of 84%. Pesticide runoff loads were predicted with a similar accuracy. These results indicate that the soil-water mixing model used in RZWQM is a robust predictor of pesticide entrainment and runoff.     

Communication to the Editor Degradation of Bromoxynil,Ioxynil, Dichlobenil and their Mixtures by Agrobacterium radiobacter 8/4

Degradation of three benzonitrile herbicides, bromoxynil (3,5-dibromo-4-hydroxybenzonitrile), ioxynil (3,5-diiodo-4-hydroxybenzonitrile), dichlobenil (2,6-dichlorobenzonitrile), and their mixtures by the soil micro-organism Agrobacterium radiobacter 8/4 was studied in batch cultures. Bromoxynil was found to be most rapidly degraded, while dichlobenil had the lowest toxicity to our strain. All transformations of studied benzonitriles were performed by the nitrile hydratase which has been shown to act on a broad range of substituted aromatic nitriles. © 1997 SCI.     

北京南部地区地下水氟化物分布特征及成因分析

以大兴区为研究对象,基于全区99眼机井的地下水水质调查结果,应用数学统计分析方法和水文化学分析软件,研究了北京南部地区地下水中氟化物的分布特征及成因。结果表明:该区域地下水化学类型相对比较简单,以HCO3-Ca.Mg型为主。氟化物在研究区地下水中广泛分布,影响着地下水水质状况。浅层地下水中氟化物浓度变化范围在0.13～1.76mg/L之间,浓度高值区主要分布在研究区南部和东南部。与浅层地下水相比,深层地下水中氟化物浓度较低,未出现超标现象。地下水中氟化物浓度与pH值及Ca2+浓度分别呈正、负相关关系,与取水深度也存在一定相关关系。地下水中氟化物主要由自然因素造成,但近年来人类频繁活动也影响着水体中氟化物浓度变化。     

新疆奎屯河流域地下水资源开发引起的生态环境问题及对策

简要介绍了奎屯河流域水文地质条件及"三水"转化特征,分析了地下水资源开发利用现状,进而对不合理开发利用地下水,引发的一系列生态环境负效应,如:区域地下水位下降,植被退化,土地沙化,土地盐渍化等进行了剖析。针对存在的问题,提出了奎屯河流域地下水资源合理开发利用对策及维持地下水位的生态意义。