乙草胺和丁草胺在土壤中的移动性

利用土壤薄层层析法研究乙草胺和丁草胺在土壤中的移动性以灌溉河水为展开剂,得到乙草胺和丁草胺在北京海淀壤土中的相对移动值Rf的平均值分别为0.121和0.031,在河北白洋淀砂壤土中的相对移动值R_f的平均值分别为0.147和0.032.采用不同的土壤试验,乙草胺的移动性存在一定的差异.说明乙草胺在土壤中的移动性与土壤的性质有关,特别是土壤有机质含量,土壤吸附性能越强,越不易移动.乙草胺属于移动性弱的农药品种,移动等级为Ⅱ级,丁草胺属于移动性很弱的农药品种,移动等级为I级乙草胺和丁草胺虽然同属于酰胺类除草剂,但是,由于它们的水溶解度的差异,它们在土壤中的移动性有较大的差别.以30mg·L^-1的阴离子表面活性剂十二烷基苯磺酸钠水溶液(DDBS)和阳离子表面活性剂十六烷基三甲基溴化铵(HDTMA)为展开剂,乙草胺在北京海淀壤土中的R_f的平均值分别为0.159和0.098.阴离子表面活性剂能够促进农药在土壤中的迁移,阳离子表面活性剂能够促进农药在土壤中的吸附,从而阻止农药在土壤中的迁移.     

Change in the antimicrobial resistance profile of Pseudomonas aeruginosa from soil after exposure to herbicides

The extensive use of pesticides represents a risk to human health and to the environment. This study aimed to investigate if the exposure to atrazine and diuron, two herbicides widely used in Brazil, could induce changes in the susceptibility profile to aztreonam, colistin and polymyxin B antimicrobials in isolates of P. aeruginosa obtained from soil samples by using the determination of minimum inhibitory concentration (MIC) test. Three isolates had an increase of MIC to aztreonam after exposure to both herbicides and one isolate did not show any MIC change. The MexAB-OprM efflux pump has already been upregulated in these isolates and the herbicides atrazine and diuron did not increase MexAB-OprM overexpression. Therefore, the decrease in aztreonam susceptibility was not directly related to this pump, suggesting that probably other mechanisms should be involved.     

乙草胺和丁草胺的水解及其动力学

本文研究了乙草胺和丁草肢在恒温２５℃,ｐＨ值为４,７,１０蒸馏水和河水中的水解动力学．酰胺类除草剂的水解反应属于一级反应．结果显示乙草胺和丁草胺在蒸馏水和河水中的水解速度差不多,在ｐＨ ４水溶液中的水解速度较在ｐＨ７和１０的速度快,Ｈ＋有催化水解的作用．乙草胺在ｐＨ４,７,１０的速率常数分别为５×ｌ０－４ｄ－１,３×１０－４ｄ－１,３×１０－４ｄ－１．半衰期分别为１３８６ｄ,２３ｌ０ｄ,２３１０ｄ．丁草胺在ｐＨ４,７,１０的速率常数分别为 ｌ．１× １０－３ｄ－１,６ × １０－４ｄ－１,６ × １０－４ｄ－１．半衰期分别为 ６３０ｄ,１１５５ｄ,１１５５ｄ．     

Respiration induced by substrate and bacteria diversity after application of diuron,hexazinone, and sulfometuron-methyl alone and in mixture

Abstract

After application, herbicides often reach the soil and affect non-target soil microorganisms, decreasing their population, diversity or affecting metabolic activity. Therefore, laboratory studies were performed to evaluate the effects of diuron, hexazinone and sulfometuron-methyl alone and mixed upon carbon transformation by soil microorganisms in clayey and sandy soils and the effect on bacterial diversity and structure. Control treatment without herbicide application was also performed. Sub-samples from the control and herbicide treatments (10?g – in triplicate) were collected before herbicide application and 7, 14, 28 and 42?days after treatment (DAT), then 1?mL of ¹⁴C-glucose solution was applied. The released ¹⁴CO₂ was trapped in 2?M NaOH solution and the radioactivity was analyzed by liquid scintillation counting (LSC), 12?h after glucose application. The effect of herbicides on bacterial diversity was evaluated by T-RFLP. The experiment was conducted in a complete randomized design. Hexazinone did not affect ¹⁴CO₂ evolution. Diuron showed a greater ¹⁴CO₂ evolution in sandy and clayey soil, while sulfometuron-methyl led to an increase in sandy soil, at 42 DAT. A greater evolution of carbon was observed in the treatment with herbicide mixture in sandy soil, compared with the same treatment in clayey soil or control. However, the herbicide mixture application did not affect the soil biological activity measured by the respiration rate induced by substrate. On the other hand, the herbicide mixtures affected the bacterial diversity in both soils, being the strongest effect to diuron and sulfometuron-methyl in clayey soil and hexazinone in sandy soil.     

Effects of soil attributes and straw accumulation on the sorption of hexazinone and tebuthiuron in tropical soils cultivated with sugarcane

Brazil is the largest sugarcane producer in the world in which hexazinone (3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione) and tebuthiuron (1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea) are heavily used. Sugarcane harvesting is changing from the manual system with previous straw burning to the mechanized system without straw burning. The lack of burning results in soil organic carbon accumulation mainly in clayey soils, which should affect herbicides availability and fate. Therefore, we evaluated sorption of these herbicides in soil samples with and without straw burning. Both herbicides presented low apparent sorption coefficients (mean K_d,app= 0.6 and 2.4 L kg^?1 for hexazinone and tebuthiuron, respectively), suggesting that they may leach to groundwater. Moreover, their sorption correlated primarily with soil organic carbon (SOC), but iron oxide contents extracted with ammonium oxalate (Fe₂O₃^AOX) also affected it (K_d,app = ?0.228 + 0.0397 SOC + 0.117 Fe₂O₃^AOX for hexazinone and K_d,app = ?1.407 + 0.201 SOC + 0.348 Fe₂O₃^AOX for tebuthiuron). Soil organic carbon accumulation due to straw maintenance in the field positively affected sorption of both herbicides, but its effects were not enough to classify them as “non-leachers.”     

Host-guest complexes of phenoxy alkyl acid herbicides and cyclodextrins. MCPA and β-cyclodextrin

The chlorophenoxy herbicide MCPA (4-chloro-2-methylphenoxyacetic acid), widely used for the control of broad-leaf weeds primarily in cereal and grass seed crops, still remains one of the most often used herbicides in Portugal. As the formation of inclusion complexes with cyclodextrins can improve its solubility properties, the interaction between the herbicide MCPA and β-cyclodextrin was investigated. The stability constants describing the extent of formation of the complexes have been determined by phase-solubility studies. Different analytical techniques [ultraviolet-visible spectroscopy (UV-Vis), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (¹H NMR)] were employed for a thorough investigation of the structural characteristics of the obtained complexes, which exhibited distinct features and properties from both “guest” and “host” molecules. FTIR and ¹H NMR data obtained for the MCPA/β-CD complexes gave information about the interaction between MCPA and the nonpolar cyclodextrin cavity. The dramatic change observed in band frequency and proton displacements of OCH₂ group and H6 aromatic proton confirmed the inclusion of MCPA in β-CD.

The formation of an inclusion complex between MCPA and β-CD increased the aqueous solubility of this herbicide which could be a particularly advantageous property for some specific applications, namely to improve commercial formulation and for environmental protection.     

Trends in Pesticide Use and Efficacy During 26 Years of Changing Agriculture in Southern England

We report on trends in agricultural pesticide use from1970 to 1995 inclusive in arable crops on the SouthDowns, West Sussex, U.K. Information is given on theproportion of cropped area treated with pesticides,the percentage spray area, the number of pesticideapplications per field, and the number of compoundsapplied per field for herbicides, foliar fungicidesand insecticides. Compared to national publishedfigures, our data are broadly representative of thenational picture; they provide a complete and detailedtime series whereas national figures are available foronly 7 out of the 26 yr. In general, the areatreated (fungicides, insecticides) and the intensityof use (all three types of pesticide) increased overthe 26 yr. The spectrum of activity of theherbicides applied to arable crops increased from anaverage of 22 weed taxa susceptible in 1970 to 38 weedtaxa susceptible in 1995. The odds on herbicide andfungicide use in break crops were, respectively, 93%and 99% lower than average; odds on insecticide usein spring cereals were 98% lower than average. Comparing winter wheat on the most traditional farm(grass/cereal rotation) with the most modern one(monoculture winter wheat), the proportion of fieldstreated with herbicides was similar, but the odds onbeing treated with fungicides were 129% higher on themodern farm. Insecticides were used in only 2% ofthe fields on the traditional farm, while on themodern farm over the same time period, 79% of thefields were treated. This fits previously observeddifferences in wildlife abundance on the two farms.     

Fate of anilide and aniline herbicides in plant-materials-amended soils

The fate of herbicides trifluralin, pendimethalin, alachlor and metolachlor in paddy field soils amended with plant materials was investigated. The plant materials were purple sesbania, vegetable soybean and rice straw. The investigation was performed at two temperatures (25 and 40°C) and two soil water moistures (60 and 90% water-holding capacity). The results showed linear and Freudlich equations described the adsorption of amide compound to soil. Adsorption coefficient (K _d ) fit to linear equation were in general greater in plant material-amended soils than in non-amended soil, especially in soil amending with rice straw. Increasing temperature and soil water moisture content shortened the half-lives of compounds in various treated soils. The movement of compounds in the soil columns showed the maximum distribution of aniline type compound, trifluralin and pendimethalin, appeared at the upper top of 0 to 5 and 0 to 10 cm of soil column, respectively, and of anilide type, alachlor and metolachlor, were distributed at 0 to 25 cm of the soil column. The mobility of chemicals in the different treated soils was simulated by the behavior assessment model (BAM). There was no significant difference among different plant material incubated soils on dissipation and mobility of compounds in soils.     

QSPR for prediction of subcooled vapor pressures (log PL) of polychlorinated trans-azobenzenes

In this study the values of subcooled vapor pressures (log P_L) were estimated for 209 trans chloroazobenzenes (Ct-ABs) that fill some gaps in analytical and experimental data on these compounds. There are 209 chloro derivatives of trans azobenzenes that are relatively stable and more environmentally relevant than 209 chloro cis congeners. The calculations models were based on the Quantitative Structure-Property Relationship (QSPR) scheme using the semi-empirical method (PM6) in molecular package (MOPAC) software and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set) in Gaussian 03 software method and the artificial neural networks (ANNs) prediction. The values of log P_L predicted by models used varied between ?3.94 to ?2.66 for Mono-; ?4.85 to ?2.97 for Di-; ?5.18 to ?3.17 for Tri-; ?6.02 to ?3.77 for Tetra-; ?6.64 to ?4.64 for Penta-; ?7.36 to ?4.76 for Hexa-; ?7.54 to ?5.79 for Hepta-; ?7.75 to ?6.64 for Octa-; ?7.89 to ?7.44 for Nona-Ct-Abs; and ?8.09 and ?8.13 for Deca-Ct-AB. Based on these values Ct-ABs can be grouped localized among relatively low (log P_L ?4 to ?2) and low (log P_L < ?4) mobile Persistent Organic Pollutants (POPs). Both the calculation methods employed were characterized by similar prediction ability of subcooled vapor pressure values of Ct-ABs, while those of PM6 are much more efficient due to a cheaper hardware used and around 300-fold less time spent on calculations.     

Phytotoxicity and antioxidative enzymes of green microalga (Desmodesmus subspicatus) and duckweed (Lemna minor) exposed to herbicides MCPA,chloridazon and their mixtures

In this study, we evaluate the toxicity of MCPA (auxin-like growth inhibitor), chloridazon (CHD) (PSII-inhibitor) and their mixtures to floating plants and planktonic algae. Toxicity of MCPA (4-chloro-2-methylphenoxyacetic acid) and CHD (5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone) was first assessed in two growth inhibition tests with Lemna minor (ISO/DIS 20079) and Desmodesmus subspicatus (ISO 8692). Next, herbicide mixtures at concentrations corresponding to the EC values were used to assess their interactive effects, and the biomarkers were: for duckweed fresh weight, frond area, chlorophyll content and number of fronds, and for algae cell count and cell volume. The 3d EC₁₀ and EC₅₀ values using cell counts of D. subspicatus were 142.7 and 529.1 mg/L for MCPA and 1.7 and 5.1 mg/L for CHD. The 7d EC₁₀ and EC₅₀ values using frond number of L. minor amounted to 0.8 and 5.4 mg/L for MCPA and 0.7 and 10.4 mg/L for CHD. Higher sensitivity of reproductive (number of cells/fronds) than growth processes (cell volume/frond area) to herbicides applied individually and in mixtures was especially pronounced in the responses of Desmodesmus. Herbicide interactions were assessed by the two-way ANOVA and Abbott's formula. Generally, an antagonistic interaction with Lemna was revealed by MCPA and chloridazon, whereas additive effect of both herbicides was observed for Desmodesmus. A significant stimulation of SOD and APX activity by binary mixtures was noted in algal cells mainly after 24 and 48 hours of exposure. The extremely high stimulation of the activity of both enzymes was induced by the combination EC₁₀CHD + EC₅₀MCPA (48 h). Presumably due to oxidative stress, the treatment with CHD at concentration EC₅₀ after 72h was lethal for algae grown in aerated cultures, in contrast to standardized test conditions. Taking into account the consequences of risk assessment for herbicide mixtures we can state that a relatively low toxicity, as well as the lack of significant synergy between MCPA and CHD to non-target plants appears to be the most important result.