Ethylcellulose formulations for controlled release of the herbicide alachlor in a sandy soil

The development of controlled-release formulations of alachlor to diminish its leaching in sandy soils, avoiding groundwater contamination and maintaining its efficacy, was studied. For this purpose, ethylcellulose (EC) microencapsulated formulations (MEFs) of alachlor were prepared under different conditions and applied to soil columns to study their mobility. The results show that in all cases the release into water of alachlor from MEFs was retarded when compared with commercial formulation. Total leaching losses in soil columns were reduced to 59% from 98%. The mobility of alachlor from EC microspheres into soil columns has been greatly diminished in comparison with its current commercial formulation (CF), above all with increasing EC/herbicide ratios. Distribution of alachlor applied as MEFs at different depths in the soil was higher in the soil surface (66.3-81.3% of herbicide applied at the first 12 cm). In contrast, the residues from CF along the complete soil column were only 20.4%. From the results of bioassays, MEFs showed a higher efficacy than CF at 30 days after the treatment. The use of ME formulations could provide an advantage in minimizing the risk of groundwater contamination by alachlor and reducing the application rates, as a result of maintaining the desired concentration of the herbicide in the top soil layer, obtaining longer periods of weed control.     

Development of controlled release formulations of carbofuran and evaluation of their efficacy against Meloidogyne incognita

Controlled release (CR) formulations of the insecti-nematicide carbofuran have been prepared using commercially available rosin, sodium carboxymethylcellulose and sodium carboxymethylcellulose with clay (bentonite, kaolinite, and Fuller's earth). The kinetics of carbofuran release in soil from the different formulations were studied in comparison with that of the commercially available granules (3G). Release from the commercial formulation was faster than with the new CR formulations. Addition of clay in the biodegradable polymer matrix reduced the rate of release. The diffusion exponent (n value) of carbofuran in soil ranged from 0.462 to 0.740 in the tested formulations. The half-release (t1/2) values ranged between 4.79 and 25.11 days, and the period of optimum availability (POA) of carbofuran ranged from 15.10 to 43.97 days. The mean EC50 of the commercial formulation against Meloidogyne incognita was quite high as compared to those of CR formulations. The effective duration (te) of carbofuran from the CR and commercial formulations was predicted by fitting the mean EC50 values of test formulations in the model (M(infinity) - Me)/M(infinity) = Kdte. It was 0.7 day in commercial 3G in comparison with 17.8 days for CMC-bentonite. The bioassay studies revealed that with the rosin-yellow polymer, the dose of carbofuran could be reduced to half of its recommended dose for nematode control. Overall, a comparison of CR formulations with the commercial one showed an earlier degradation of carbofuran in the latter and relatively prolonged activity in the former.     

两种不同剂型毒死蜱对四种环境生物的毒性评价

按照化学农药环境安全评价试验准则方法,测定了40%毒死蜱乳油和30%毒死蜱微囊悬浮剂对鱼类、鸟类、家蚕和蜜蜂4种环境生物的毒性。结果表明,毒死蜱乳油对斑马鱼LC50值（96 h）为0.68 mg.L^-1,毒死蜱微囊悬浮剂的LC50为47.30 mg.L^-1;毒死蜱乳油对鹌鹑的毒性LD50为7.45 mg.kg^-1,毒死蜱微囊悬浮剂的LD50为56.97 mg.kg^-1。食下毒叶法结果表明,毒死蜱乳油对2-4龄家蚕幼虫LC50值（48 h,25℃）分别为0.82、1.87 mg.L^-1与4.35 mg.L^-1,毒死蜱微囊悬浮剂为2.48、4.22 mg.L-1与8.35 mg.L^-1;家蚕幼虫在药膜上爬行1、10、30 min与60 min后,毒死蜱乳油对3龄家蚕幼虫的LD50值（48 h,25℃）分别为3.18、0.68、0.41μg.cm^-2与0.38μg.cm^-2,其微囊悬浮剂LD50值分别为6.92、1.58、1.18μg.cm^-2与0.48μg.cm^-2;毒死蜱乳油和微囊悬浮剂对蜜蜂48 h的LC50分别为0.53 mg.L^-1和2.32 mg.L^-1。上述结果表明,毒死蜱微囊悬浮剂对4种环境生物的安全性明显高于乳油。     

不同啶虫脒剂型对烟粉虱的毒力差异及原因分析

为探讨农药剂型对烟粉虱的毒力差异,分别以甘蓝和黄瓜叶片作为生物测定载体,比较了啶虫脒乳油(EC)、微乳剂(ME)、可溶性液剂(SL)、可溶性粉剂(SP)及可湿性粉剂(WP)等5种剂型对烟粉虱成虫的毒力,并通过对植物叶片临界表面张力、啶虫脒药液表面张力、动态接触角及叶片持液量的测定,分析了不同啶虫脒剂型间毒力差异形成的原因。结果表明:以甘蓝叶片为生物测定载体,不同啶虫脒剂型间对烟粉虱的毒力差异明显;以黄瓜叶片为生物测定载体,不同剂型间毒力差异不明显。啶虫脒SL、SP、WP在两种生物测定载体间的毒力差异大于EC和ME。甘蓝和黄瓜叶片的临界表面张力值分别为30.73 mN.m 1和57.91~63.30 mN.m 1。啶虫脒有效成分浓度大于7.81 mg.L 1时,啶虫脒EC和ME溶液表面张力即小于甘蓝和黄瓜叶片的临界表面张力;啶虫脒有效成分浓度大于500 mg.L 1时,啶虫脒SL、SP、WP溶液的表面张力才小于甘蓝叶片的临界表面张力。啶虫脒ME溶液液滴接触两种植物叶片的瞬间(0 s),液滴与叶片间的接触角就明显小于90°。甘蓝叶片对低浓度的啶虫脒ME和EC溶液的持液量高于其他3种剂型,黄瓜叶片对啶虫脒各剂型溶液的持液量无明显差异。植物叶片表面性质和不同剂型溶液表面张力的差异是导致剂型间产生毒力变化的重要原因。     

Determining kinetic and nonequilibrium sorption behavior for chlopyrifos using a hybrid batch/column experiment

Pesticide mobility in soil is strongly coupled to the chemical's sorption characteristics. A modified soil column batch experiment was conducted to measure the transient nature of chlorpyrifos sorption and desorption from Cecil soil. This experimental system minimizes many shortcomings associated with obtaining sorption parameters by fitting soil column data to an advective-dispersive transport equation. Several chlorpyrifos formulations were investigated to determine how formulations affect soil sorption, and if this effect is adequately described using transient sorption/desorption algorithms. Both a second-order sorption with first-order desorption kinetic model and the two-site kinetic/equilibrium model were found to yield reasonable comparisons to experimental observations. In general, the formulation temporarily decreases the sorptivity of chlorpyrifos and alters the time for equilibrium to be achieved. Care must be exercised when extrapolating sorption data for a pure molecule in a laboratory setting to formulated materials used in field applications when environmental fate predictions are sought.     

百菌清和毒死蜱在大棚番茄中的分布与降解特征

大棚和露地环境下,分别对番茄植株一次性喷洒推荐剂量的百菌清（CHT）和毒死蜱（CHP）,研究喷药后两周内农药在番茄根、茎、叶和果实中分布的持久性及其动态降解规律。实验结果表明,百菌清在大棚番茄中的残留浓度分布呈现为叶片垌果实〉茎〉根;毒死蜱呈现为叶片〉果实垌茎〉根。大棚番茄各部位的最高残留浓度出现时间滞后于喷药时间8~60h;空间浓度分布上表现为大棚中间区域浓度高于两侧,这与棚内的空气对流有关。大棚番茄果实中百菌清和毒死蜱的残留半衰期分别为5.8d和7.2d,明显高于文献报道。     

转Bt基因棉粉碎叶、蕾样Bt蛋白降解

以转Bt基因棉Bt冀668为材料,室内采用ELISA法,测定粉碎叶、蕾样Bt蛋白在土壤、水中不同时间的残留量以及不同环境处理下的残留量,以研究转Bt基因棉粉碎叶、蕾样Bt蛋白在不同基质中的降解动态以及与环境影响因子的关系.结果显示,粉碎叶、蕾样Bt蛋白分别在熟土、生土和水中前40d、48d取样天数间的残留量差异显著,中...     

阿维菌素3种剂型的光解研究

以太阳光为光源,利用玻片药膜法和高效液相色谱法研究浓度、水质硬度、pH和共存离子等因子对阿维菌素乳油、水乳剂和微乳剂3种液体剂型光解的影响。结果表明：3种阿维菌素液体剂型光解率随光照时间延长而逐渐增大。在试验初始浓度范围内,3种阿维菌素制剂光解均符合一级动力学方程,且与药液浓度呈负相关。在不同浓度、pH、共存离子条件下,阿维菌素的光解速率均表现为乳油〉水乳剂〉微乳剂,pH对单一剂型光解有较大影响,而共存离子对其影响作用较小。在不同浓度硬水条件下则表现为随水质硬度增加,微乳剂半衰期减少,水乳剂和乳油略微增大,在蒸馏水下的半衰期为微乳剂〉水乳剂〉乳油,而在684mg·L-1硬水时半衰期为水乳剂〉微乳剂≈乳油。相比于乳油,微乳剂和水乳剂光解速率较慢,可以有效延长阿维菌素持效期,进一步提高阿维菌素在田间的应用效果。     

Cross-enhancement of accelerated biodegradation of organophosphorus compounds in soils: Dependence on structural similarity of compounds

Rates of degradation of seven organophosphate nematicides and insecticides were examined in two soils known to show accelerated biodegradation of fenamiphos and one soil known to show accelerated biodegradation of chlorpyrifos. The results indicated that several organophosphate insecticides and one nematicide were susceptible to cross-enhanced degradation in the soil showing accelerated biodegradation of chlorpyrifos. No cross-enhancement was observed in the two soils showing accelerated degradation of fenamiphos. Fumigation resulted in the complete inhibition of pesticide degradation in all soils. The data suggested that the cross-enhancement of selected pesticides in chlorpyrifos-degrading soil was dependent on the structural similarity of the compounds. Mechanisms of degradation of pesticide in soil support this hypothesis, where structurally similar compounds (diazinon, parathion, coumaphos and isazofos) were hydrolysed by microbial activity in chlorpyrifos-degrading soil but the degradation products were accumulated. Enhanced degradation of chlorpyrifos and fenamiphos was found to be stable in the laboratory condition for a period of one year.     

Volatilization of alachlor from polymeric formulations

Pesticides may be dispersed throughout the environment by several means, including groundwater contamination, surface water contamination, and volatilization with subsequent atmospheric transport and deposition. In earlier research primarily directed at reducing the potential for groundwater contamination, a number of herbicides were microencapsulated within several different polymers. These polymeric formulations were evaluated for efficacy in the greenhouse. In the studies described in this paper, three polymeric alachlor formulations that were the most effective in the greenhouse were evaluated in laboratory volatility studies using pure alachlor and a commercial formulation (Lasso 4EC) for comparison purposes. In a given experiment, technical alachlor, Lasso 4EC, and two polymeric formulations were applied to soil and evaluated in a contained system under 53% humidity with a fixed flow rate. Evolved alachlor was collected in ethylene glycol, recovered with C18 solid phase extraction cartridges, and analyzed by reverse-phase high-performance thin-layer chromatography with densitometry. Duration of the studies ranged from 32 to 39 days. In studies in which all formulations were uniformly incorporated in the soil, total alachlor volatilization from the polymeric microcapsules was consistently lower than that from the alachlor and Lasso 4EC formulations. In studies in which the polymeric formulations were sprinkled on the surface of the soil, microcapsules prepared with the polymer cellulose acetate butyrate released the smallest quantity of volatilized alachlor.     

设施油桃果实发育过程中有机酸代谢的研究

以设施栽培"超红珠"油桃为试材,测定了果实发育过程有机酸含量及相关代谢酶——柠檬酸合酶(CS)、苹果酸酶(ME)、苹果酸脱氢酶(MDH)的活性,并对果实中有机酸积累及酶活性的关系进行了分析。研究结果表明:随油桃果实发育,其有机酸含量呈先升高后降低趋势,于盛花后49d达到最高值;苹果酸含量与总有机酸含量变化趋势相似;柠檬酸含量呈逐渐升高趋势,至果实成熟有所降低;果实成熟期苹果酸与柠檬酸含量相近。有机酸相关代谢酶CS活性变化与柠檬酸含量相关性不大;果实发育后期ME活性逐渐升高,促进了苹果酸的降解和转化;MDH活性变化与苹果酸含量显著相关。因此抑制果实发育前期MDH的活性、促进果实发育后期ME的活性可以降低果实酸含量,提高糖酸比。     

Degradation and transformation of a potential natural herbicide in three soils.

The methyl ester of fusaric acid (ME) is one of four toxins produced by the fungus Fusarium nygamai, which could be used as a natural herbicide against Striga hermonthica, a parasitic weed of sorghum and corn in a vast zone of West and Central Africa. A laboratory study was performed to measure the degradation of ME in three soil types and under different temperature and soil moisture conditions, so as to ascertain whether a single ME treatment would protect the crops against this weed during the critical phases of growth. The results show that the persistence in all soils and under all incubation conditions is long enough to protect the crops for the first week of growth, excluding the trial at 30 degrees C in the humic soil, where the half-life of 6 days would require more than one treatment. A degradation product of ME (butylpyridine, BP) was identified by gas chromatography/mass spectrometry and its degradation measured. The sum of ME and BP residues for the first 7 days was almost 100% of the applied compound in all soils and incubation conditions, thus indicating that BP may be the only transformation product of ME at this stage.     

Stability of chlorpyrifos for termiticidal control in six Australian soils.

Chlorpyrifos [O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate] is the most widely used soil-applied termiticide in Australia. It is relatively stable, has low water solubility, is absorbed by organic matter, and has a high affinity for soil with low partitioning potential from soil matter to soil water. The purpose of this degradation study is to determine the effect of soil alkalinity on the longevity of termite protection when chlorpyrifos is applied as a termiticide in a range of Australian soils, particularly high-pH substrates. The study also examines the effects of initial soil concentration on the degradation of chlorpyrifos in the range of soils. At an initial soil concentration of 1000 mg kg(-)(1) for termite control, the degradation rate of chlorpyrifos is very strongly retarded in soils tested when compared with lower soil concentrations of 100 and 10 mg kg(-)(1) in the same soils. The degradation data correlated with a logarithmic model of decay, and it was thus possible to produce half-lives and predict likely periods of termite control. Average half-lives for all soils for the three concentrations were 385, 155, and 41 days, respectively. Soil pH had no effect on the rate of degradation at all concentrations tested.     

Influence of prolonged use of sewage effluent in irrigation on heavy metal accumulation in soils and plants

Total content of Fe, Mn, Zn, Cu, Pb, Cd, Ni and Co in soils irrigated with sewage effluent increased with increasing years of using sewage effluent in irrigation. Iron and Co applied to the soil from sewage effluent were immobilized mainly in unavailable form; Pb, Cd, and Ni in moderately available form; and Mn, Zn, and Cu in highly available form. The concentrations of Fe, Mn, Zn and Cu in tops of alfalfa and leaves of corn grown on these soils increased substantially with increased levels of available metal content of the soil, while those of other metals were little affected. As for orange, continuous increase in leaves metal content with time was found for Fe, Mn, Zn, Co and Cd. The concentrations of Cd, Co, Ni and Pb in corn grains and orange fruits were several times higher than normal, and this reduces their suitability for human consumption.     

Evaluation of chitosan and alginate immobilized Methylobacterium oryzae CBMB20 on tomato plant growth

Methylobacterium oryzae CBMB20, a promising plant growth promoting bacteria (PGPB) and a biocontrol agent, was immobilized in different formulations such as wet chitosan, dry chitosan, wet alginate and dry alginate and were tested for tomato plant growth promotion. Chitosan solution (1.5%) with pH 5.5–6.0 and 90 min contact time was found optimal for immobilization. The chitosan formulations showed better entrapment efficiency and good degradability resistance apart from slow release of cells under prolonged incubation. Survivability of bacteria (80%) was observed in wet chitosan formulation even after 90 days of storage at 4°C. The spermosphere survival of bacteria was high in both dry and wet chitosan formulations applied soils even after 21 days under greenhouse conditions. While the alginate formulation degraded fully, partial degradation of chitosan formulation was observed even after 30 days, indicating its ability to support the survival of M. oryzae CBMB20 in soil. Plants inoculated with wet chitosan formulation registered 1.3 fold increase in the shoot and root length and dry weight compared to other treatments. Hence, chitosan formulation supporting better plant growth compared to alginate will be a better carrier for taking bacteria to the plant rhizosphere and thereby promote plant growth.     

Simultaneous degradation of mixed insecticides by mixed fungal culture isolated from sewage sludge

The degradation of mixed (DDT and chlorpyrifos) insecticides by mixed insecticide enriched cultures was investigated. The mixed fungal population was isolated from mixed insecticide acclimatized sewage sludge over a period of 90 days. Gas chromatography was used to detect the concentration of mixed insecticides and calculate the degradation efficiency. The results showed that the degradation capability of the mixed microbial culture was higher in low concentrations than in high concentrations of the mixed insecticides. After 12 weeks of incubation, mixed pesticide enriched cultures were able to degrade 79.5-94.4% of DDT and 73.6-85.9% of chlorpyrifos in facultative cometabolic conditions. The fungal strains isolated from the mixed microbial consortium were identified as Fusarium sp. isolates GFSM-4 (ITCC 6841) and GFSM-5 (ITCC 6842). The fungal culture GFSM-4 could not utilize mixed insecticides as source of carbon and nitrogen, probably due to high combined toxicity of the mixed insecticides. Liquid media deficient in carbon (1% mannitol) and nitrogen (0.1% sodium nitrate) source increased the degradation efficiency of DDT and chlorpyrifos to 69 and 45%, respectively. The media with normal carbon and deficient nitrogen (0.1% sodium nitrate) sources extensively increased the degradation efficiencies of DDT (94%) and chlorpyrifos (69.2%). Traces of p,p'-dichlorobenzophenone and desdiethylchlorpyrifos were observed in the liquid medium, which did not accumulate probably due to further rapid degradation. This fungal isolate (GFSM-4) was able to degrade simultaneously DDT (26.94%) and chlorpyrifos (24.94%) in sterile contaminated (50 mg of each insecticide kg(-1)) soil in aerobic conditions.     

噻嗪酮在茶园环境中的残留行为研究

参照《农药残留试验准则》,采用田间试验方法,研究在不同地域、不同气候带、不同施药季节条件下杀虫剂噻嗪酮在南京、南宁地区茶园环境中的残留行为,并进行环境影响因素（降水、温度）分析,药剂的作物适用性及区域适用性分析,探讨了不同种植地域MRL值制定的依据。结果表明,噻嗪酮在不同环境条件下的残留行为不同。同季节施药后在两地茶叶上的消解规律相近,统计分析表明两地区的残留消解行为无显著性差异,半衰期为3.97～4.69 d;不同施药季节的降水及气温均可显著影响噻嗪酮在茶叶上的残留状态,降水可明显减少其残留量,而低温则可延长其残留半衰期;在土壤中的残留消解受土壤性质的影响较大,在南京、南宁地区的半衰期相近,但消解过程差异显著,半衰期为10.34～29.96 d。除2008年南京地区外,其他地区与年份不同处理剂量的噻嗪酮药后7 d在茶叶上的残留量均小于10 mg.kg-1,据此并参考国内外噻嗪酮MRL值的制定情况,建议延用国标（GB/T8321.6—2000）的MRL值10 mg.kg-1,建议噻嗪酮在茶叶上使用的安全间隔期为7 d。     

不同污染条件下毒死蜱在蚯蚓体内的蓄积特征及其生长影响

以皮质远盲蚓（Amynthas corticis）为试验生物,采用一次、叠加的污染方式,研究了毒死蜱在土壤中的残留、蚯蚓体内的累积特征及对蚯蚓生长的影响。结果显示:相同实验浓度条件下,以叠加污染方式进入土壤的毒死蜱残留量低于一次污染方式的残留量。当土壤毒死蜱浓度为12 ~ 20 mg kg?1,暴露55 d时,一次污染条件下,蚯蚓体内毒死蜱蓄积量为3.73 ~ 8.84 mg kg?1,生物－土壤蓄积因子（F_BSA）为1.55 ~ 1.70;叠加污染条件下,蚯蚓毒死蜱蓄积量为5.21 ~ 11.04 mg kg?1,F_BSA为2.22 ~ 2.46。相同实验浓度条件下,叠加污染方式进入土壤的毒死蜱对蚯蚓的生长抑制显著高于一次污染处理组。该研究结果可为土壤毒死蜱生物毒性和生态风险评价提供基础数据。     

Der Einfluß von Dicyandiamid und N-Serve in Verbindung mit Ammoniumsulfat als N-Dünger auf die Nitrat- und Oxalsäuregehalte von Spinat (Spinacia oleracea)

Occurence of boron deficiency in Citrus aurantium L. (Bitter orange) at the Caspian Sea (Iran) In a Bitter orange plantation near the Caspian sea over a period of two years different amounts of boron were applied either as borax to the soil or as Solubor to the leaves. Without boron supply the fruits were misshapen, had a rough and thick peel and often brown spots in the pulp. Supply of 5 – 20 g B per tree prevented the occurence of these symptoms and increased both the fruit size and the proportion of the pulp. Without boron supply on fresh weight basis the proportion of pulp/peel was 1 : 1, 6 – 2, 0 as compared to 1 : 0, 6 – 0, 7 with boron supply. The effect of the different boron supply was well reflected in the boron content of the leaves and especially of the fruits. Borax increased the boron content of the plants more than Solubor. Conzidering both the low content of available boron in most of the soils of the Citrus area near the Caspian sea and the special ecological conditions (high pH values and low water content of the soils during fruit development) boron deficiency can be expected. The results of the experiment with Bitter oranges confirm that boron fertilizing is an important factor for plant production in this area.     

Residues of vinclozolin and procymidone after treatment of greenhouse grown lettuce,tomato and cucumber

Residues of the fungicides vinclozolin and procymidone, used to control the Botrytis cinerea disease, were studied in greenhouse grown lettuce, tomato and cucumber. Residue concentrations differed between the species of treated vegetables, and depended mostly on time of picking (harvest), size of fruits and mode of chemical application. The differences in concentration between one and two applications became smaller with time after application. The greatest differences occurred in lettuce. The residue contents in cucumber fruits assigned both for industrial and home processing (pickling) were higher than the legal limit (3 mg/kg). As a result of washing cucumbers, 22–24% of the residue was eliminated, and by peeling them 79–85% of the vinclozolin and procymidone residues were eliminated. Therefore it is reasonable that one or two applications of these fungicides should be used, with a time lapse of 14 days, but only with cucumbers intended for salad consumption. Vinclozolin residues, when used as vaporisation tablets, were in all cases 35–65% lower compared with the wettable powder (WP) formulation; however, the rate of of residue decrease was much slower. When applied in the form of vaporable tablets, the vinclozolin residue concentration was lower in all the sampled fruits in comparison with the WP formulation. The concentration of fungicide residues detected in winter tomato fruits was higher than that of the spring crop. Irrespective of vegetable the detected levels of fungicide residues were lower in ripe and bigger fruits than in green and smaller ones.