Transport of the insecticides chlorpyrifos,chlorfenvinphos, carbofuran,carbosulfan, and furathiocarb from soil into the foliage of cauliflower and Brussels sprouts plants grown in the field

In several field assays made in different locations in 1988 and 1989, cauliflower and Brussels sprouts plants were treated some days after plantation by pouring onto soil around the stem of the plant one of the insecticides chlorpyrifos, chlorfenvinphos, carbofuran, carbosulfan, or furathiocarb, for protection against the root fly. During plant growth, each of the insecticides (and their soil metabolites) was transported from soil into the plant foliage, where it could give—during a certain period of time—a secondary plant protection against the foliage insects. The foliage concentrations of the non systemic chlorpyrifos and chlorfenvinphos were equal or greater than 1 mg/kg fresh weight during a period of about 44 days after soil treatment in Brussels sprouts crops, and 35 days in cauliflower crops. Comparison of 1988 and 1989 however showed that these periods of time changed according to the weather conditions, especially rainfall. These periods of time were greater when the insecticide soil concentrations were greater—and thus when the rates of insecticide soil metabolism were smaller— and when the rainfall were greater—water transporting the insecticides from soil to the foliage. Similar relationships were observed with the systemic insecticides carbofuran, carbosulfan and furathiocarb; the weights per plant of insecticide compounds transported from soil into the foliage however were greater with these systemic insecticides than they were with the non systemic chlorpyrifos and chlorfenvinphos. The extreme values observed for the periods of time of insecticide foliage concentrations equal or greater than 1 mg/kg fresh weight thus were: 1. in cauliflower crops: 21 to 36 days for chlorpyrifos, and 23 to 39 days for chlorpyrifos + oxon; 24 to 37 days for chlorfenvinphos; 20 to 48 days for carbofuran; 2. in Brussels sprouts crops: 43 to 49 days for chlorpyrifos; 47 to 53 days for chlorpyrifos + oxon; 41 to 45 days for chlorfenvinphos; between 2 to 3 months for carbofuran, carbofuran + carbosulfan, and carbofuran + furathiocarb in the fields treated respectively with either carbofuran, carbosulfan, or furathiocarb. Moreover, in the spring and summer cauliflower crops made on fields onto which continuous cauliflower crops—with their soil insecticide treatments—had been made since a greater number of years (greater soil “history”), the insecticide compounds soil and foliage concentrations generally were lower.     

Photodegradation of the organophosphorus pesticides chlorpyrifos,fenamiphos and vamidothion in water

The photodegradation of the pesticides chlorpyrifos, fenamiphos and vamidothion in water containing 2–4% methanol was examined. Acetone (5%) was added as photosensitizer in the photolysis of vamidothion. A suntest apparatus equipped with a xenon arc lamp which exhibits a radiation very close to natural sunlight was employed. Analyses were performed by direct injection of the water samples containing the photoproducts into a liquid chromatograph with diode array and thermospray mass spectrometric detection. The major photodegradation products were identified by matching their diode‐array spectra with the corresponding spectra of the authentic standards, their retention times and the spectra obtained using positive and/or negative thermospray mass spectrometry. 3,5,6‐trichloro‐2‐pyridinol, fenamiphos sulfoxide and vamidothion sulfoxide were the major photodegradation products from chlorpyrifos, fenamiphos and vamidothion, respectively.     

Chlorpyrifos insecticide uptake by plantain from polluted water and soil

Chlorpyrifos is a common organophosphorus insecticide used for crop protection. Chlorpyrifos use has induced heath issues and water pollution. Such issues may be solved by phytoremediation, which is the use of plants for the cleanup of pollutants. Here, we tested Plantago major L. to clean water and soils under laboratory conditions. Results show that the concentration of chlorpyrifos residues after 5 days exposure reached 36.86 μg/g in roots and 13.93 μg/g in upper plant tissues. Gas chromatography–mass spectrometry (GC–MS) analysis of chlorpyrifos metabolites suggests the formation of 3, 5, 6-trichloro-2-pyridinol (TCP) and diethyl 3,5,6-trichloropyridin-2-yl phosphate (chlorpyrifos-oxon). Chlorpyrifos-oxon was detected in the roots and the leaves after 2 h of testing. After 24 h of testing, the degradation product chlorpyrifos-oxon increased in the roots and the leaves then decreased gradually until the end of testing. TCP levels increased gradually to 192 h then decreased until the end of testing.     

European starling nestling response to chlorpyrifos exposure in a corn agroecosystem

European starling (Sturnus vulgaris) nestlings were used as a surrogate to study the effect of chlorpyrifos application to a corn agroecosystem on songbird reproduction. Chlorpyrifos was applied in a T‐band at 1.3 kg AI/ha, and residues were measured in soil, earthworms, ground‐dwelling insects, and diet items collected from the crop of starling nestlings. Chlorpyrifos levels in soil peaked at 34.2 μg/g, 4 days post‐application, and dissipated to trace levels by 64 days post‐application. Concentrations of chlorpyrifos in earthworms and ground‐dwelling insects reached 0.9 and 0.7 ug/g, respectively. Starling nestling diet items included invertebrates from eight orders with chlorpyrifos concentrations ranging from trace levels to 10.6 μg/g in earthworms. Nestling brain and plasma cholinesterase (ChE) activity and body mass measurements were taken at 3, 8, and 13 days post‐hatch (DPH). Adult starling fecundity was also measured. Body mass differences between treatment and reference site nestlings at 3 and 13 DPH were not significant at α = 0.05. However, 8 DPH nestlings from the Treatment Site had a transient reduction in weight (p = 0.03) when compared with 8 DPH reference nestlings. There were no significant differences in brain or plasma ChE activities of 3, 8, or 13 DPH nestlings. Further, multiple measures of fecundity (i.e., clutch size, hatching percentage, and fledging percentage) indicated that chlorpyrifos application did not affect starling nestling survival to fledging, as the values from the Treatment and Reference Site were nearly identical. This screening‐level study suggests that although one age group of starling nestlings from the Treatment Site weighed less than their Reference Site counterparts, a single T‐band application of chlorpyrifos did not impair starling nesting success.     

哒嗪硫磷水解与土壤降解研究

采用室内模拟方法,研究了哒嗪硫磷在东北黑土、江西红壤和南京黄棕壤3种不同类型土壤中的降解特性及pH、温度和表面活性剂（SDS）浓度对水解的影响。结果表明,哒嗪硫磷水解速率随pH值与温度的升高而显著加快,在15℃、pH 5缓冲溶液中水解半衰期为216.56 d,在35℃、pH 9缓冲溶液中半衰期为3.47 d,平均温度效应系数为2.98。SDS能显著抑制哒嗪硫磷水解,且随着浓度的增大抑制作用增强。哒嗪硫磷在3种土壤中的降解速率依次为南京黄棕壤〉东北黑土〉江西红壤,半衰期分别为10.27、78.75、105.00 d,降解速率随土壤pH值的增大而增大。灭菌处理下,哒嗪硫磷在3种土壤中半衰期显著延长,其中在南京黄棕壤中半衰期延长近10倍,哒嗪硫磷在土壤中降解主要为微生物降解。     

Hydrolytic biodegradation of chlorothalonil in the soil and in cabbage crops

Broccoli and Chinese cabbage crops were treated at planting by pouring an emulsion of the fungicide chlorothalonil around the stem of the plant. During culture, chlorothalonil was biodegraded in soil into l,3‐dicarbamoyl‐2,4,5,6‐tetrachlorobenzene (compound 1), l,3‐dicyano‐4‐hydroxy‐2,5,6‐trichlorobenzene (compound 2), and l‐carbamoyl‐3‐cyano‐4‐hydroxy‐2,5,6‐trichlorobenzene (compound 3). Compounds 1 and 2 were the major metabolites in soil. In the harvested broccoli (in the flower) and Chinese cabbages (the leaves), the concentrations of chlorothalonil and of compounds 1 and 2 were lower respectively than 0.1, 0.1 and 0.5mg/kg fresh weight.     

Bioactivity,adsorption and persistence of pretilachlor in paddy field soils

The effects of environmental factors on bioactivity, adsorption and persistence of pretilachlor were studied in the laboratory and greenhouse using cucumber (Cucumis sativus L.) as the bioassay species. The three soils studied viz. Bernam, Selangor and Sabrang series were chosen for their different characteristics. The half‐life of pretilachlor decreased from 10.24 to 4.90 days as temperature increased from 25°C to 35°C in the Selangor Series soil and from 10.86 to 7.63 days in the Bernam Series soil at 60% field capacity. At the same moisture level, an increase of temperature from 25°C to 35°C also reduced the half‐life of pretilachlor in Sabrang soil from 8.87 to 2.59 days. The half‐life of pretilachlor also decreased with increasing moisture levels in Selangor and Sabrang series but not in Bernam series soils. The greatest adsorption of pretilachlor was observed in Bernam series, followed by Selangor and Sabrang series. No phytotoxic residue of pretilachlor was detected in the supernatant after 10 h incubation. Since the residue was strongly adsorbed in Bernam series, its biological activity was less than in the other soils studied.     

毒死蜱对紫金山森林土壤酶活力及微生物毒性影响研究

毒死蜱是有机磷类农药,对乙酰胆碱酯酶具有抑制作用,在农业虫害防治中应用广泛。为掌握毒死蜱对森林土壤酶活力和土壤微生物生态效应,选择紫金山森林土作为受试土壤,采用室内培养法,研究了毒死蜱对土壤蔗糖酶、脲酶、酸性磷酸酶和过氧化氢酶,以及土壤呼吸强度和氮素硝化作用的影响。结果表明:试验期间,1.25 mg a.i.·kg-1、12.5 mg a.i.·kg-1和125 mg a.i.·kg-1毒死蜱对土壤脲酶、酸性磷酸酶总体表现为抑制作用;对土壤蔗糖酶和过氧化氢酶的影响与暴露剂量和暴露时间有关,在60 d时,Z1低剂量处理组(1.25 mg a.i.·kg-1)蔗糖酶和过氧化氢酶可恢复,Z100高剂量处理组(125 mg a.i.·kg-1)抑制作用不能解除。试验初期,毒死蜱对土壤呼吸强度有一定刺激作用随后逐渐恢复;对土壤氮硝化作用影响表现为先促进后抑制,且抑制作用有长期影响。由此可知,毒死蜱使用对紫金山森林土的土壤酶活性和土壤微生物产生毒性效应,具有一定生态风险。     

Feasibility of using salivary biomarkers to assess human exposure to chlorpyrifos

The objective of this study was to determine the feasibility of using salivary biomarkers to assess chlorpyrifos exposure using data collected from laboratory controlled animal study, as well as from farmers in Thailand and Nicaragua who applied chlorpyrifos in the field. Time-matched saliva and arterial blood samples were collected from rats and adult agricultural workers, while spot saliva samples were collected from children. Specimen samples were analyzed for chlorpyrifos using a commercially available enzyme-linked immunosorbent assay. The results from both animal and farmer studies show that chlorpyrifos is excreted into saliva. Nevertheless, salivary excretion of chlorpyrifos seems to differ from other pesticides, as evidenced by the lack of correspondence of chlorpyrifos levels between saliva and plasma samples. The lower chlorpyrifos concentrations in saliva collected from rats, and from farmers and their children, may have resulted from the rapid hydrolysis of chlorpyrifos during the intracellular passive diffusion in the salivary gland. In conclusion, chlorpyrifos is excreted into saliva; however, the majority of chlorpyrifos that is excreted in saliva may have been metabolized due to base-dependent hydrolysis. Because of this finding, it was hypothesized that it would be ideal to measure its metabolite, 3,5,6-trichloropyridinol, in saliva as the biomarker for chlorpyrifos exposure.     

Dissipation of the triketone mesotrione herbicide in the soil of corn crops grown on different soil types

The new triketone herbicide mesotrione corresponds to the older sulcotrione in which the 2‐chloro benzoyl substituent is replaced by a nitro group, generating an herbicide of greater efficiency and a broader spectrum of activity. Mesotrione has been applied within the same 15 days period pre‐emergence at the rate of 150gha^‐1 to four corn crops made at different sites located 40 km apart in Belgium and of soils of different textures, but similar pH and organic matter (old humus) contents. The mesotrione soil half‐life in the 0–10 cm surface soil layer (which contained more than 90% of the residue) was 50 days in loam soil (at Zarlardinge), 41 days in sandy loam soil (at Melle) and in clay soil (at Koksijde), and 34 days in sandy soil (at Zingem). The cumulative effects of the recent organic fertilizer treatments and of the soil texture could explain the differences between the soil half‐lives. The time for the 90% dissipation of mesotrione was between 3.6 (in the sandy soil) to 4.7 months (in the sandy loam, loam and clay soils). The low mesotrione soil residues remaining after the corn harvest should disappear with the usual heavy rains in autumn, and the tilling which precedes the following crop and dilutes the mesotrione soil residue. These low mesotrione soil residues thus should have no phytotoxicity toward the following crop, especially at the lower application dose of 100 g mesotrione ha^‐1 used in practice.     

毒死蜱对土壤蔗糖酶活性的影响

采用模拟方法探讨了毒死蜱污染土壤酶活性的变化规律。结果表明，有机质含量高的土壤，毒死蜱对土壤蔗糖酶具有明显的抑制作用，在酸性和中性条件下，酶活性的抑制幅度较大，在试验所设的培养时间内，毒死蜱对蔗糖酶活性的抑制总的变化趋势呈现先激活后抑制。建议对于有机质含量较高的土壤，采用蔗糖酶活性作为表征土壤毒死蜱污染程度的监测指标。     

阿特拉津在土壤中的降解途径及其对持留性的影响

通过田间和实验室试验，研究了除草剂阿特拉津在土壤中的降解代谢规律及其与土壤特性的关系。试验表明，阿特拉津施用后、在作物生长期内可降解９０％以上，土壤酸碱度对阿特拉津在土壤中的代谢有显著影响。在碱性土壤中阿特拉津主要经过微生物代谢而被降解；在酸性土壤中化学水解占优势地位。阿特拉津在强酸性土壤中的持留性（半衰期为６３ｄ）低于弱酸性土壤中的持留性（半衰期为８４ｄ），而在碱性土壤中由于较强的微生物降解作用，其持留性（半衰期为５１ｄ）最低。     

降解毒死蜱曲霉Y的分离和降解效能测定

毒死蜱在灭菌土壤、施用过和未施用过毒死蜱的土壤中的降解速率测定表明：土壤中的微生物在毒死蜱的降解中起着重要的作用。同时，毒死蜱在连续使用后，降解速度大大加快，说明毒死蜱可诱发降解菌的产生，从连续使用毒死蜱的土壤中分离了1株可降解毒死蝗的真菌曲霉Y。测定了曲霉Y在不同接菌量、不同温度、不同毒死蜱浓度及不同碳源浓度下对毒死蜱的降解能力，同时，还测定了曲霉Y其他杀虫剂的降解能力。图6参13。     

Persistence and dissipation of dazomet in soil and tomato (lycopersicon esculentum mill) seedlings

The persistence and dissipation pattern of dazomet residues in nursery bed soil and tomato seedlings under field condition and in submerged soil and surface water under laboratory condition was studied. In nursery bed soil the half life (t _1/2) of dazomet ranged from 1.85 to 3.09 days indicating very rapid dissipation. No residues existed in tomato seedlings sown on the treated plots 3 weeks after application and the seedlings were healthy and devoid of any deformation. Under submerged condition dissipation was much faster both in soil and surface water, t_1/2 being 0.82–0.84 days only in water.     

Phytotoxicity and uptake of chlorpyrifos in cabbage

Chinese cabbage, Brassica chinensis L., and cabbage, Brassica oleracea L. var. capitata, are the main daily foliar vegetables of the vast majority of the population of eastern and southern China. Cabbages are also planted and consumed widely in other countries. The insecticide and acaricide chlorpyrifos is registered in many countries. Chlorpyrifos controls a variety of insects in plants and soils, and chlorpyrifos is extensively used in the Chinese market. Food poisoning due to the presence of organophosphorus pesticide residues in vegetables has been reported in China provinces. Plant uptake of pesticide residues in air, water, and soil is a source of pesticide residues in vegetables. Here, phytotoxicity and uptake of chlorpyrifos by Chinese cabbage and cabbage were studied in the laboratory using the batch technique. From 0 to 16 days after chlorpyrifos treatment, vegetables roots, stems, leaves, and culture water samples were collected, and the residues of chlorpyrifos in culture water, plant tissues were analyzed using GC-FPD. The results demonstrate that culture solutions with chlorpyrifos had no significant inhibitory effects on vegetable plant height. However, at 1.0 mg/l, it had significant inhibitory effects on the root length and fresh weight of Chinese cabbage. Then, at 10.0 mg/l, it had only significant inhibitory effects on the root length and fresh weight of cabbage compared to the control treatment. The disappearance rates of chlorpyrifos in solutions were in sequence as: nutrition solution with Chinese cabbage, nutrition solution with cabbage, pond water, nutrition solution. The results showed also that chlorpyrifos can be taken up by roots of Chinese cabbage and cabbage from water and subsequently translocated as a function of time. Uptake dynamics of chlorpyrifos from culture solutions by the two cabbage plants were similar.     

Sub-lethal effect of chlorpyrifos on protein metabolism of the food fish Clarias batrachus and monitoring of recovery

The effect of sub-lethal concentrations of chlorpyrifos on protein metabolism in physiological important tissues, namely gills, kidney, liver, and muscle of the freshwater fish, Clarias batrachus, was studied. Fish were exposed to 1/20th and 1/10th of 96?h LC₅₀ concentrations for 7, 14, 21, and 28 days. After 28 days of exposure, fish were released into fresh water and kept in the same for 21 days in order to study the recovery. Fish were sacrificed at the stipulated periods and gills, kidney, liver, and muscle tissues were used for the estimation of total protein, amino acids, ammonia, urea, glutamine, protease, transaminases, and phosphatases. Total protein, amino acid, and ammonia contents were decreased in all tissues for 28 days and recovery was observed during the recovery period. Urea and glutamine levels were elevated, except in kidneys, and recovered at the end of the recovery period. The activities of protease, alanine, and aspartate aminotransferases, and acid and alkaline phosphatases were elevated in the tissues for 28 days exposure at both concentrations. Recovery of these enzymes activities was noticed during depuration.     

杀虫剂对土壤温室气体排放的影响

在室内培养条件下,研究了在施用尿素的土壤（有效氮质量分数为200 mg·kg^-1）中分别添加不同剂量（在5、10和50 mg·kg^-1）的吡虫啉和毒死蜱2种杀虫剂时,杀虫剂对土壤温室气体CO2、N2O和CH4排放过程的影响。结果表明：和空白相比,施用尿素明显地增加了土壤中温室气体N2O和CO2的排放量,但对CH4的排放无明显影响。当施用5 mg·kg^-1吡虫啉时,土壤中N2O和CO2排放总量和尿素处理相比无明显差异,但吡虫啉用量上升至10和50 mg·kg^-1时则显著降低了温室气体N2O和CO2的排放量（P〈0.05）,N2O排放量分别降低了26.89%和53.10%,CO2排放量分别降低15.14%和13.79%。毒死蜱在5、10和50 mg·kg^-1三种用量时土壤的N2O排放量与尿素处理相比均无明显差异。毒死蜱在5和10 mg·kg^-1用量时则明显抑制了土壤CO2的排放（p〈0.05）,分别比尿素处理降低了19.88%和19.02%;用量上升到50 mg·kg^-1用量时,土壤的CO2排放量与尿素处理相比无差异。吡虫啉和毒死蜱对CH4排放量均没有明显影响。可见,杀虫剂施用明显影响到土壤温室气体的排放,但不同杀虫剂品种及其用量的效应也存在明显差异。     

海藻多糖稀土配合物对蔬菜有机磷农药残留的降解作用

以小白菜、甘蓝、芹菜为试验材料,采用大田试验研究了海藻多糖稀土配合物对蔬菜中有机磷农药残留的影响.试验结果表明,叶面喷施海藻多糖稀土配合物对小白菜、甘蓝、芹菜中毒死蜱、氧化乐果、敌敌畏等有机磷农药残留具有明显的降解作用;对甘蓝中毒死蜱和氧化乐果的降解效果优于小白菜,但对芹菜中毒死蜱的降解效果远不及甘蓝和小白菜,表现出一定的作物选择性.叶面喷施海藻多糖稀土配合物对敌敌畏等磷酸酯类有机磷农药的降解作用比毒死蜱、氧化乐果等硫代磷酸酯类有机磷农药的降解强烈,表现出一定的农药选择性;另外,喷水对叶片表面残存农药具有一定的冲洗作用,可减少叶面农药的残留量;叶面喷施海藻多糖稀土配合物对甘蓝和小白菜中有机磷农药的降解率远高于叶面喷水.以上结果表明海藻多糖稀土配合物确实具有降解有机磷农药残留的作用.在蔬菜生产中将海藻多糖稀土配合物作为农药残留降解制剂是可行的,有利于蔬菜安全生产和提高蔬菜产品的食用安全性。     

Herbicides interactions with cow manure and field soil organic matter

The direct interaction of the herbicide metazachlor ‐chosen as an example‐ with the soil organic matter has been studied by laboratory incubation of old and young cow manures containing metazachlor. The extraction efficiencies of solvents of increasing polarities indicated the formation of association compounds by bonds weaker than covalent between metazachlor and the organic matter: electron donor‐acceptor complexes, hydrogen bonding complexes, and complexes by both bonding types. Laboratory incubation of metazachlor in soil of low organic matter content indicated that the soil mineral part only had a diluting effect on the soil organic matter capacity to adsorb metazachlor. Similar association compounds were observed in the soil of a cauliflower field crop. Their concentrations were greater in the plots treated with organic fertilizers than in the organic fertilizers untreated plots. The free‐ unbound metazachlor was faster metabolized than the one bound to the soil organic matter, explaining why the organic fertilizer treatments slow down the herbicide soil biodegradation during the main first crop period. Inclusion of metazachlor in the field soil humic acids lattice ‐another kind of herbicide association compound with the soil organic matter‐ occurred at crop end when most of the metazachlor was metabolized; the soil concentrations of this kind of association compound thus was low, so that the release after crop of metazachlor in the environment has no practical significance.     

Metsulfuron‐methyl soil persistence and mobility in winter wheat and following green manure crops

A procedure has been developed for the analysis of metsulfuron‐methyl in the soil of field crops. The soil extracts are cleaned by repeated TLC, and metsulfuron‐methyl is simultaneously separated from its soil metabolites. Metsulfuron‐methyl is transformed by diazomethane into its N,N ‘‐dimethyl derivative which in the GC (electron capture detection) and GC‐MS apparatus is transformed into a benzisothiazole compound which is measured with great sensitivity. The sensitivity limit is 0.3 μg metsulfuron‐methyl kg^‐1 dry soil. The results of the chemical analyses are confirmed by bioassays using sugar beet as test plant. Metsulfuron‐methyl was measured in the soil of two winter wheat crops after post‐emergence application in the spring of 6 g metsulfuron‐methyl ha^‐1. In the 0–8 cm surface soil layer, the metsulfuron‐methyl soil half‐life was 78 days in 1997, and 67 days in 1998. During crop, metsulfuron‐methyl remained in the 0–8 cm surface soil layer. There, it was at a maximum concentration and herbicide efficiency in a 2 cm‐thick soil layer. This maximum concentration soil layer progressively moved down during crop, attaining the 4–6 cm surface soil layer at crop end. After the winter wheat harvest at the end of July, and the rotary‐tilling of the 0–10 cm surface soil layer before sowing of the green manures, 27% of the metsulfuron‐methyl initial dose still remained in the 0–10 cm surface soil layer. This residue progressively disappeared, and was no more detected at the middle of November. It had no, or only very low inhibiting effect on the growth of the green manures. Thus there is no concern about the possible phytotoxicity of persistent metsulfuron‐methyl soil residues towards the following crops, when metsulfuron‐methyl is applied at the rate of 6 g a.i.ha^‐1.