敌草胺在土壤中的吸附及其与持久性和生物有效性之间的关系（英文）

土壤吸附是农药在环境中归趋的关键支配因素,也是支配农药在环境中的持久性和生物有效性的重要因素之一。该文采用高效液相色谱法研究了除草剂敌草胺在不同性质土壤中的吸附、持久性和生物有效性以及吸附与土壤持久性、蚯蚓生物有效性之间的关系。结果表明,在供试浓度范围内,采用批量平衡技术测定的敌草胺土壤吸附等温线可用Freundlich模型表征(r0.99),土壤有机质含量(P0.01)是影响敌草胺在土壤中吸附的主要因素,其次为黏粒含量(P0.1)。敌草胺在土壤中的持久性较长,其降解过程符合一级动力学特征,降解速率随土壤有机质含量的升高而加快,半衰期(t50)在61.3-97.6 d之间;微生物对敌草胺在土壤中的持久性影响显著,微生物降解是敌草胺在土壤环境中降解的主要途径,灭菌处理后其在土壤中的半衰期延长了2.09~3.65倍。蚯蚓Eisenia foetida对敌草胺的吸收和生物积累也主要取决于土壤性质,特别是土壤的有机质含量水平(P0.05);敌草胺在土壤中的吸附系数与其半衰期(r=–0.885,P0.05)、生物积累因子(BAF)(r=–0.796,P0.05)之间均存在负相关关系,相应回归方程分别为t50=94.210–3.535 K_f和BAF=0.264–0.014 K_f,表明吸附系数可用作模型参数来评价敌草胺在土壤中的持久性和生物有效性。     

烟嘧磺隆在土壤中的吸附及与土壤性质的相关性研究

采用平衡振荡法研究了烟嘧磺隆在8种不同类型土壤中的吸附,结果表明,其吸附过程均符合经典的Freundlich模型,最大吸附常数为6.891,最小吸附常数为0.798。根据土壤有机吸附常数和吸附自由能的大小对该除草剂的移动性能进行了评价,认为其在8种土壤中均以物理吸附为主,且具有中等或较高的移动性能。通过对吸附常数Kf与土壤有机质含量、粘土含量和pH值的关系进行分析,发现土壤有机质含量、粘土含量和pH值在吸附过程中均属支配因素,Kf与土壤有机质含量、粘土含量呈正相关,而与土壤pH值呈负相关。     

七种农药在3种不同类型土壤中的吸附及淋溶特性

采用振荡平衡法和土柱淋溶法研究了2,4-滴酸、丁噻隆、毒草胺、炔草酸、氟环唑、甲基磺草酮和烯啶虫胺7种农药在江西红壤、太湖水稻土及东北黑土3种不同理化性质土壤中的吸附及淋溶特性,探讨了农药性质及土壤理化性质对供试农药在土壤中吸附、淋溶行为的影响。结果表明:农药的水溶性越大,其在土壤中的吸附性越弱,淋溶性越强;农药在土壤中的吸附性与土壤pH值、有机质含量以及阳离子交换量之间有较好的相关性。土壤pH值、有机质含量以及农药性质是影响农药在土壤中淋溶及迁移的主要因素。     

氯胺嘧草醚在土壤中的吸附行为研究

为评价氯胺嘧草醚的环境安全性,采用批量平衡法测定了氯胺嘧草醚在5种土壤中的吸附-解吸行为,并运用数学模型对其吸附-解吸特性及移动性能进行了分析。结果表明:氯胺嘧草醚在5种土壤中的等温吸附-解吸曲线符合Freundlich模型,吸附常数（Kf值）范围在6.991~18.49之间;不同土壤对其的吸附作用强弱依次为:黑土 > 水稻土 > 褐土 > 潮土 > 红土。氯胺嘧草醚在5种土壤中的有机碳吸附常数（KOC）范围在704.4~1 579之间,推测其在土壤中具有低移动性;薄层层析试验也表明,氯胺嘧草醚在土壤中的移动性较弱。氯胺嘧草醚在5种土壤中的吸附自由能绝对值均小于40 kJ/mol,表明其吸附机理主要是物理吸附。其Kf值与土壤有机质含量、黏粒含量呈正相关,而与土壤pH值呈负相关。解吸试验表明,氯胺醚在其中3种土壤中的解吸过程存在滞后现象。研究表明,在正常使用情况下,氯胺嘧草醚不易对地表水或地下水造成污染风险。     

咪鲜胺及其制剂在六种水稻土中的吸附

研究了咪鲜胺(prochloraz)及其制剂施保克(Sportak,25%咪鲜胺乳油)在6种水稻土中的吸附行为和吸附机理。结果表明:咪鲜胺和施保克在水稻土中的吸附平衡时间为5~10 h,其吸附过程符合Freundlich吸附等温式;咪鲜胺和施保克在6种水稻土中有机质吸附常数(KOM)的平均值分别为 2 439和2 111,表明它们易被水稻土吸附,属难移动的物质,且吸附反应自由能的变化量均小于40 kJ/mol, 表现为物理吸附过程;吸附常数(Kf值)与土壤理化性质的相关性分析结果表明,咪鲜胺和施保克在土壤中的吸附主要受土壤有机质含量、阳离子交换量和粘粒含量的影响,并呈正相关;咪鲜胺在加工成制剂后,不但在土壤中的吸附量减少了,而且Kf值也下降了近1/3。     

稻丰散在土壤和水中的降解及其在土壤中的吸附

在室内模拟条件下,研究了稻丰散在土壤和水中的降解及其在土壤中的吸附行为。结果表明:稻丰散的降解速率随土壤温度的升高和土壤含水量的增加而加快;微生物的存在有利于其在土壤中的降解;在20 ℃时,稻丰散在pH为5、7、9的水溶液中的降解半衰期分别为10.66、11.65和6.53 d。3种供试土壤对稻丰散的吸附均符合Freundich方程,且有机质含量越高,土壤对稻丰散的吸附越强。     

精异丙甲草胺在土壤中的吸附行为及环境影响因素研究

采用平衡振荡法研究了精异丙甲草胺在粘壤土、粘土及砂壤土中的吸附和解吸附行为。结果表明,3种土壤的吸附等温线均属L型并符合Freundlich模型,吸附常数(Kf)分别为4.01、6.15及8.62,且Kf 和1/n(n为经验常数)的乘积与土壤有机质含量呈正相关性。解吸附实验结果表明,精异丙甲草胺在土壤中的解吸附与吸附并不一致,显示出明显的滞后性。温度及pH值等环境因素对吸附影响的结果显示,随温度升高精异丙甲草胺在土壤中的吸附量有所减少,中性环境下土壤吸附量较低。     

农药对蚯蚓的毒理学效应研究进展

农药在使用过程中会通过液滴飞溅漂移、包装残留、加工泄露以及生物体排泄等多种方式不可避免地进入土壤环境，给土壤生物带来潜在的环境风险。蚯蚓是土壤中主要的生物类群，也是评估农药毒性风险最合适的土壤模式生物。本文基于当前国内外关于农药对蚯蚓毒理学效应影响的研究，概括了农药进入土壤中的途径及其在土壤中的残留现状、农药在蚯蚓体内的富集与消除行为；归纳了农药暴露对蚯蚓产生的生长及生殖毒性、细胞毒性、神经毒性、遗传毒性和氧化应激等毒性影响，着重综述了转录组学、代谢组学及微生物组学等组学方法在揭示农药对蚯蚓毒性作用机制方面的最新研究应用进展。本文可为农药的土壤生态风险评估提供必要的数据支撑，并为农药土壤污染风险管控和修复提供科学依据。     

双氟磺草胺在不同类型土壤中的吸附与淋溶特性研究

农药在土壤中的吸附和淋溶特性是评价其环境行为的重要指标。采用批量平衡法和土柱淋溶法,研究了双氟磺草胺在小麦种植区3种代表性土壤中的吸附和淋溶特性。结果表明:双氟磺草胺在安徽黏土、山东砂质壤土和河南砂质黏壤土中的吸附规律均可以较好地用Freundlich方程描述,其吸附系数(Kf)在0.39~0.62之间;土壤有机碳归一化吸附系数(Koc)在66.91~81.35之间,表明双氟磺草胺在3种土壤中均属于难吸附型;吸附自由能(ΔG)在-10.90~-10.42kJ/mol之间,均属于物理吸附。双氟磺草胺在3种土壤中的淋出率在71.7%~74.1%之间,说明其在3种土壤中的淋溶性均较强。双氟磺草胺初始添加量和腐殖酸对淋出率具有一定影响。综合试验结果,认为双氟磺草胺在3种土壤中的吸附和淋溶可能受土壤有机质含量、黏粒含量、阳离子交换量和土壤pH值等多个因素的综合影响,其对地下水的污染风险较大,因此应引起高度重视。     

三种新烟碱类杀虫剂在土壤中的残留降解及影响因子

建立了吡虫啉、啶虫脒和噻虫嗪在土壤中的高效液相色谱-串联质谱（HPLC-MS/MS）检测方法。样品经乙腈提取和QuEChERS法净化后,采用HPLC-MS/MS检测,外标法定量,在0.01~1.0 mg/kg添加水平下,3种新烟碱类杀虫剂在土壤中的回收率在89%~103%之间,相对标准偏差（RSD）在1.3%~10.3%之间,定量限均为0.01 mg/kg。采用建立的方法,在室内模拟条件下,研究了土壤微生物、温度、土壤含水量及农药初始浓度对土壤中吡虫啉、啶虫脒和噻虫嗪降解的影响。结果表明:土壤微生物是影响农药残留降解的首要因素,灭菌处理土壤中农药残留降解速率明显低于非灭菌土壤。此外,环境温度、土壤含水量、初始浓度等因素也会对农药残留降解产生不同影响,土壤含水量为最大持水量的60%左右时降解最快,半衰期分别为15.6、7.2和25.8 d;农药初始浓度越高,降解速度越慢;在5~35℃范围内,随着温度的升高,降解速度加快。     

Adsorption of acetanilide herbicides on soils and its correlation with soil properties

The adsorption of metolachlor, acetochlor, pretilachlor and butachlor, as a group of acetanilide herbicides, on eight soils with various physical and chemical properties was studied. The adsorption isotherms fit the Freundlich equation well. The extent of adsorption increased in the order: metolachlor < acetochlor < pretilachlor < butachlor. The product of the Freundlich adsorption constants, K_f(1/n), showed good correlation with organic matter content (OM) of soils for each of these herbicides, suggesting that the latter is the main factor controlling the adsorption process of these acetanilide herbicides. Multivariant correlation regression between K_f(1/n) and two factors, water solubility (S_w) of herbicides and OM, was also performed. K_f(1/n) correlated well with 1/S_w and OM/S_w, showing that high S_w corresponds to a weak tendency to adsorb on soils. IR spectra and ESR parameters confirmed that multifunctional H bonds and charge-transfer bonds between humic acids (HA) and the herbicides were the main adsorption mechanisms of the latter. The ability of herbicides to form these adsorption bonds with HA increased in the same order as the extent of adsorption. © 1999 Society of Chemical Industry     

Co‐solvent effects on the adsorption of carbofuran by two Indian soils

The adsorption of carbofuran on soils from water‐methanol mixtures has been evaluated by batch shake testing. Two uncontaminated soils having different physicochemical properties were used in these experiments. The volume fraction of methanol in the liquid phase (f_s) was varied from 0.25 to 1.0. Higher adsorption of carbofuran was observed in medium black (silt loam) soil than in alluvial (sandy loam) soil; calculated values of the Freundlich constant (K^m) and distribution coefficient (K_d) showed that adsorption of carbofuran in both soils decreased with increase in f_S values. The decreased carbofuran adsorption in methanol–water mixtures meant a greater potential of ground‐water contamination through leaching from potential sites. The data have been used to evaluate the co‐solvent theory for describing adsorption of carbofuran in methanol–water mixtures. The aqueous phase partition coefficient K_dw (mol g⁻¹) normalized with respect to f_oc and the aqueous phase adsorption constant K_w for carbofuran were evaluated by extrapolating to f_S = 0. © 2000 Society of Chemical Industry     

Fate of chlorsulfuron in the environment. 1. Laboratory evaluations

The behaviour and fate of chlorsulfuron in aqueous and soil systems were examined in laboratory studies. Aqueous hydrolysis was pH-dependent and followed pseudo-first-order degradation kinetics at 25°C, with faster hydrolysis occurring at pH 5 (half-life 24 days) than at either pH 7 or 9 (half-lives >365 days). Degradation occurred primarily by cleavage of the sulfonylurea bridge to form the major metabolites chlorobenzenesulfonamide (2-chlorobenzenesulfonamide) and triazine amine (4-methoxy-6-methyl-1,3,5-triazin-2-amine). This route is a major degradation pathway in water and soil systems. Aqueous photolysis (corrected for hydrolysis) proceeded much more slowly (half-life 198 days) than aqueous hydrolysis and is not expected to contribute significantly to overall degradation. Hydrolysis in soil thin-layer plates exposed to light (half-life 80 days), however, progressed at a much faster rate than in dark controls (half life 130 days), which suggests that a mechanism other than direct photolysis may have been operative. An aerobic soil metabolism study (25°C) in a Keyport silt loam soil (pH 6·4, 2·8% OM) showed that degradation was rapid (half-life 20 days). Dissipation in an anaerobic sediment/water system (initial pH of water phase 6·7, final pH 7·4) progressed much more slowly (half-life >365 days) than in aerobic soil systems. Major degradation products in aerobic soil included the chlorobenzenesulfonamide and triazine amine as in the aqueous hydrolysis study. Neither of these degradation products exhibited phytotoxicity to a variety of crop and weed species in a glasshouse experiment, and both exhibited an acute toxicological profile similar to that of chlorsulfuron in a battery of standard tests. Demethylation of the 4-methoxy group on the triazine moiety and subsequent cleavage of the triazine ring is another pathway found in both aqueous solution and soils, though different bonds on the triazine amine appear to be cleaved in the two systems. Hydroxylation of the benzenesulfonamide moiety is a minor degradation pathway found in soils. Two soils amended with 0·1 and 1·0 mg kg^-1 chlorsulfuron showed slight stimulation of nitrification. The 1·0 mg kg^-1 concentration of chlorsulfuron resulted in minor stimulation and inhibition of ¹⁴C-cellulose and ¹⁴C-protein degradation, respectively, in the same soils. Batch equilibrium adsorption studies conducted on four soils showed that adsorption was low in this system (K_oc 13–54). Soil thin-layer chromatography of chlorsulfuron (R_f=0·55–0·86) and its major degradation products demonstrated that the chlorobenzenesulfonamide (R_f=0·34–0·68) had slightly less mobility and that the triazine amine (R_f=0·035–0·40) was much less mobile than chlorsulfuron. In an aged column leaching study, subsamples of a Fallsington sandy loam (pH_water 5·6, OM 1·4%) or a Flanagan silt loam (pH_water 6·4, OM 4·0%) were treated with chlorsulfuron, aged moist for 30 days in a glasshouse and then placed upon a prewet column of the same soil type prior to initiation of leaching. This treatment resulted in the retention of much more total radioactivity (including degradation products) than by a prewet column, where initiation of leaching began immediately after chlorsulfuron application, without aging (primarily chlorsulfuron parent). © 1998 SCI     

Bentazone Leaching in Spanish Soils

Adsorption, incubation and soil-column experiments with bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide] were carried out in ten different soils from the marches surrounding the Doñana National Park (Huelva, SW Spain). Adsorption isotherms for the different soils showed a good fit with the Freundlich equation. Bentazone was poorly adsorbed in all the soils studied, with no significant relationship between theK_f values and soil characteristics. A significant correlation was obtained between the soil organic matter content and the distribution constant values (K_d) calculated at an equilibrium concentration of 200 μg cm⁻³. The low adsorption and non-degradation of bentazone on these soils suggest that the herbicide readily percolates through soils to reach the surface and ground waters. The mobility of bentazone through three soil columns was also studied. The mass balances carried out showed that bentazone was totally eluted from the soil columns. The theoretical model applied to explain bentazone leaching under our experimental conditions seems to be suitable for soil columns with a uniform water-flow rate.     

Degradation and adsorption of terbuthylazine and chlorpyrifos in biobed biomixtures from composted cotton crop residues

BACKGROUND: Biobeds have been well studied in northern Europe, whereas little is known regarding their use in southern Europe. The degradation and adsorption of terbuthylazine (TA) and chlorpyrifos (CP) were studied in three different biomixtures composed of composted cotton crop residues, soil and straw in various proportions, and also in sterilised and non‐sterilised soil. RESULTS: Compost biomixtures degraded the less hydrophobic TA at a faster rate than soil, while the opposite was evident for the more hydrophobic CP. These results were attributed to the rapid abiotic hydrolysis of CP in the alkaline soil (pH 8.5) compared with the lower pH of the compost (6.6), but also to the increasing adsorption (K_d = 746 mL g^?1) and reduced bioavailability of CP in the biomixtures compared with soil (K_d = 17 mL g^?1), as verified by the adsorption studies. CONCLUSIONS: Compost had a dual but contrasting effect on degradation that depended on the chemical nature of the pesticide studied: a positive effect towards TA owing to increasing biodegradation and a negative effect towards CP owing to increasing adsorption. Overall, composted cotton crop residues could be potentially used in local biobed systems in Greece, as they promoted the degradation of hydrophilic pesticides and the adsorption of hydrophobic pesticides. Copyright © 2010 Society of Chemical Industry     

新饲玉11号氮磷钾最佳施肥量及肥效模型拟合研究

为了解决新疆地区青贮玉米高产施肥配比问题,本试验以青贮玉米品种“新饲玉11号”为材料,采用3414试验方法,设计了不同的氮磷钾配比,在新疆农垦科学院试验地田间试验研究玉米的氮、磷、钾肥料效应并配置相应的肥效函数,以筛选出适合当地青贮玉米高产的最佳氮磷钾配比.结果表明:供试土壤中有效养分含量丰缺程度为N含量为低水平,K20、P205含量为中水平.14个处理中以N2P2K2处理的产量最高,产量为8066.79 kg·667m-2；用二次回归分析,得出氮磷钾的肥料效应函数方程为:Y=4659.93+ 79.56N-5.06N2+ 101.7P-33.81P2+286.4K-10.28K2+ 24.87NP+ 2.66NK-12.97PK;通过模型寻优得出“新饲玉11号”的最佳施肥量为667m2施N 21kg,P2O5 5 kg,K2O 22 kg,在此配方组合下能够获得最佳产量7692.96 kg·667m-2.     

应用粒子滤波同化条件植被温度指数的土壤水分估测

为了准确地获取2013—2015年关中平原冬小麦主要生育期土壤含水量(0~20 cm)的时空信息,基于Landsat-8遥感数据反演条件植被温度指数(CVTI),并结合CVTI和实测土壤水分间的线性相关性构建土壤水分反演模型。应用粒子滤波(PF)算法同化基于CVTI反演的和CERES-Wheat模型模拟的土壤水分,得到以天为步长的土壤水分同化值,利用土壤水分实测值分别检验土壤水分模拟值、反演值和同化值的精度。结果表明,CVTI和实测土壤水分间的线性相关性显著,尤其在小麦拔节期和抽穗~灌浆期,其相关性达到极显著水平(P0.01);土壤水分同化值和实测值间的线性相关性(r=0.96,P0.001)大于土壤水分模拟值和实测值间的相关性(r=0.71,P0.01)以及土壤水分反演值和实测值间的相关性(r=0.89,P0.001);土壤水分同化值的均方根误差(RMSE)和平均相对误差(MRE)比土壤水分模拟值的RMSE和MRE分别降低了0.025 cm~3·cm~(-3)和2.70%,比土壤水分反演值的RMSE和MRE分别降低了0.016 cm~3·cm~(-3)和4.15%,同化过程提高了时间序列土壤含水量的估测精度。因此,基于CVTI和PF算法能够较为准确估测关中平原小麦主要生育期的土壤含水量。     

生物菌肥和钾肥配施对苹果钾素吸收及果实品质的影响

为了研究生物菌肥和钾肥对苹果果实品质及生长发育的协同作用,以7 a生'瓦里短枝'(Vallee spur Del)为研究对象,设置T1(K2O 420 kg·hm-2)、T2(生物菌肥2520 kg·hm-2)、T3(生物菌肥2520 kg·hm-2+K2O 294 kg·hm-2)、T4(生物菌肥2520 kg·hm...