Pesticide dissipation curves in peach,pear and tomato crops in Uruguay*

Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel®. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r²=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r²=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.     

The role of toxicology in the evaluation of new agrochemicals

Abstract

The use of agrochemicals like crop protecting agents, veterinary disinfectants, and wood preservatives may result in (un)intentional exposure of the environment, animals and man. This paper deals with current testing strategies to assess the potential health risks for humans exposed to these chemicals during production or application or via consumption of foods containing pesticide residues.

Principles and procedures for safety assessment of pesticide residues in food as developed by WHO/FAO are described. Different types of toxicity studies in mammalian test animal species are discussed and a strategy is outlined in order to characterize the toxicity profile of a compound and the relationship between applied doses and adverse effects. Safety testing of agrochemicals should be carried out in relation to its intended use, and in particular attention will be paid to toxicity testing of residues of pesticides in food. Extrapolation of results from animal studies to humans and the use of safety factors is discussed.

Besides the use of animal protocol studies for safety testing of agrochemicals, the potential use of in‐vitro models derived from organs and tissues of animals is discussed. Data on the in‐vitro metabolism of thiabendazole, aldicarb and alachlor are discussed in order to demonstrate that such data may complement or partly substitute whole animal experimentation.

Principles and procedures for safety testing of residues of agrochemicals in food as applied during the last three decades, constitute a ‘safety‐first’ approach, providing sufficient safety margins for the consumer of foods which may contain low levels of residues of agrochemicals.     

Dissipation of four forest-use herbicides at high latitudes

Background, aim, and scope  Large-scale deforestation is occurring in subarctic North America following clearing by salvage logging or insect attack. Numerous shrubs, herbs, and deciduous tree species tend to dominate areas on which stands of white spruce have grown. In the absence of economically advantageous mechanical methods, several herbicides have value in efforts to reforest by planting white spruce. Glyphosate, imazapyr, triclopyr, and hexazinone are all capable of selectively removing many competing species, but there is concern about whether they would degrade naturally or persist owing to the frigid climate. Materials and methods  We established test plots with all four herbicides in upland and river bottom sites at 65°N and 58°N latitudes. The northern site has extremely cold winters, with soils that freeze to a depth of 1–2 m, and precipitation of 275 mm/year. The southern site has heavy rain and snowfall, amounting to 2,250 mm/year evenly distributed. Soil seldom freezes deeply. On each test plot, one of the four herbicides was applied at twice the normal operational use rate to facilitate detection. They were applied at the normal timing, with hexazinone, imazapyr, and triclopyr applied in June and glyphosate applied in fall. Soils were sampled immediately after treatment and those samples used as references for dissipation data gathered over the next 11–14 months from soil 0- to 15- and 15- to 45-cm depths. Results  Dissipation rates did not follow first-order rates because freezing conditions slowed most microbial activity. All products dissipated to close to or below detection limits within the time of the study. Dissipation from vegetation was substantially more rapid and depended on the nature of the plants treated as well as the product used. While soil residues dissipated more slowly than in temperate regions, they did display consistent dissipation patterns during above-freezing conditions and also the influence of microbial activity. Mobility was very limited with all products but hexazinone. Discussion  These products dissipate during summer in high latitudes much as they would in temperate climates. Winter changes are small, but are not unlike some changes reported elsewhere under freezing conditions. Unlike many other studies, soil water did not influence dissipation heavily, but the high latitude and semi-arid climate also did not create severely droughty soils. Residues in plants were much higher than those in soils, but denatured the vegetation quickly, leading to unsuitability for forage in any case. Conclusions  Low toxicity of these products and their metabolites combined with consistent dissipation and low mobility suggest that toxic hazard of their use at high latitudes need not be a matter of serious concern to humans, terrestrial wildlife, or aquatic systems. They are safe for use in management and rehabilitation of boreal forests when used properly. Recommendations and perspectives  Dissipation at rates approaching those in warmer climates offer a hypothesis that microflora native to high latitudes may be adapted to destruction of such molecules at lower temperatures than may be indicated by experiments with microflora adapted to warmer climates. Residues pose no observable risk to wildlife or humans in the area of use when products are applied properly. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available for authorized users.     

惠州农业土壤、灌溉水和农产品中有机氯农药的残留

用气相色谱法(GC-ECD)对惠州市51个农业土壤样品、12个灌溉水样品和21个农产品样品中的HCHs和DDTs残留量进行了测定.HCHs平均含量分别为土壤1.66μg/kg、灌溉水5.86ng/L、农产品24.74μg/kg;DDTs平均含量分别为土壤4.98μg/kg、灌溉水2.06ng/L、农产品41.72μg/kg,土壤中有机氯农药通过多种方式进入到水体及农产品中.从HCHs和DDTs异构体组成可以看出,环境中绝大多数农药残留是由于历史上使用造成的,个别地区可能还有新的污染输入.同其它地区相比,惠州农业土壤和灌溉水中的有机氯农药残留水平较低,但农产品尤其是蔬菜中DDTs富集程度较高.     

Herbicide Leaching on a Recharge Area of the Guarany Aquifer in Brazil

Abstract

The region of Ribeirão Preto City, located in Southeast of Brazil, São Paulo State, is an important sugarcane, soybean, and corn producing area with a high level of pesticides utilization. This region is also an important recharge area for groundwater supply of the Guarany aquifer. Since the past ten years atrazine, simazine, ametryn, tebuthiuron, diuron, 2,4-D, picloram, and hexazinone are the main herbicides used in this area. In order to study a possible leaching of some of these herbicides into the aquifer, surface, and groundwater samples were collected in a watershed during the years of 1996 to 2003, from different locations. To detect and quantify the herbicides a GC-MS (gas chromatograph/mass spectrometry) method was used. The response of the herbicides analyzed was linear over the concentration range of 0.02 to 2.0 μg/L. Analysis of groundwater revealed that the herbicides tebuthiuron, diuron, atrazine, simazine, and ametryn were not present in the samples. In the surface water collected in 1997, ametryn was present in two out of nine locations with concentrations ranging from 0.17 and 0.23 μg/L, which is above the allowable 0.1 μg/L according to the European safety level. The leaching potential of tebuthiuron, diuron, atrazine, simazine, 2,4-D, picloram, and hexazinone has been evaluated using CMLS-94, “Chemical Movement in Layered Soil,” as simulation model. No leaching into the depth of the water table at 40 m was found.     

Bioefficacy of Iprodione Against Two Desapers,its Compatibility with T. harzianum and Residues on Cabbage Crop

Iprodione (3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide) bio-assayed against fungi Alternaria brassicicola and Sclerotinia sclerotiorum was found to be highly effective for inhibiting these desapers. Inhibition of A. brassicicola was 100% up to the dose of 75 ppm and for S. sclerotiorum there was 50% inhibition for the same concentration. Formulation of the pesticide was applied @ 500 and 1000 g. a.i./ha on the cabbage crop grown in the fields. Residues in the edible sample of cabbage were analyzed by gas choromatography for the fungicide and its metabolites. The dissipation of residues of the fungicide and its bio-efficacy against two fungi are presented. It dissipated from 3.72 to 0.072 μg/g on cabbage head by 15 days after treatment. The EC₅₀ values of iprodione were found to be 11.5 ppm and 79.4 ppm for A. brassicicola and S. sclerotiorum, respectively. Half-life of iprodione was found to be 3 days for both cabbage head and leaves. The compatibility of the fungicide with a bio agent, T. harzianum was also studied and these two were not found to be compatible.     

Residues of 14C‐γ‐HCH in paddy after dusting,and the fate of γ‐HCH during refining process of rice bran oil

Paddy (rice) plants were dusted with 10% HCH containing ¹⁴C‐Γ‐HCH, at the rate of 2.5 kg a.i./ha and ¹⁴C‐residues were determined in different fractions of rice. Rice bran (0.187 ppm) had more of ¹⁴C‐residues than grain (0.026 ppm) and husk (0.042 ppm). The rice bran oil contained 0.129 ppm HCH residues. While degumming, dewaxing, alkali refining and bleaching had no effect, deodorisation alone eliminated 99.5% of added ¹⁴C‐residues in rice bran the oil during refining process.     

Residues of PCDD,PCDF, and PCBs in some marine organisms in Lake Temsah,Ismailia, Egypt

Residues of PCDDs/F, non-ortho, mono-ortho PCBs, and other PCBs were monitored in the tissues of mullet fish, bolti fish, bivalves and crab taken from Lake Temsah, at Ismailia, Egypt.

Results showed that 2,3,7,8 Tetra CDD and 1,2,3,7,8 Penta CDD were the most frequently detected PCDD congeners. Similarly, 2,3,7,8 Tetra CDF, 1,2,3,7,8 Penta CDF and 2,3,4,7,8 Penta CDF were the most frequently detected PCDF congeners. No relationship was apparent between the concentrations of detected PCDDs congeners and the degree of chlorination, except with crab samples in which an increase in the chlorination coincided with a decrease in the concentrations of the congeners.

In PCDF congeners, detected residues have had a reversed relationship with chlorination increase. In PCDD congeners, Octa CDD had the highest detected concentrations in the two fish species, while in the bivalves and crab, 2,3,7,8 Tetra CDD had the highest concentrations. The mullet fish had the highest total PCDDs concentration, at 0.398?pg/g fresh weight, followed by crab at 0.395?pg/g fresh weight, then bivalves and bolti fish at 0.187 and 0.062?pg/g fresh weight, respectively. In all the examined organisms, the total concentrations of PCDFs were much higher than the total concentrations of the PCDD congeners. The WHO–TEQ values were 11.92, 39.12, 25, and 3.6?pg/g fresh weight, for mullet fish, bolti fish, bivlaves and crab, respectively. The concentration of the mono-ortho congeners CB 118 was the highest detected of all non-ortho and mono-ortho PCBs congeners, with values of 0.382, 0.022, 0.231 and 0.357?ng/g fresh weight, in mullet fish, bolti fish, bivalves and crab, respectively. The WHO–TEQ concentrations were 0.799, 0.003?pg/g fw, 0.05?pg/g fresh weight, 0.676?pg/g, and 0.799?pg/g fresh weight, for the same species, respectively. The total concentration of PCBs 28, 52, 95, 99, 101, 105, 110, 118, 138, 146, 149, 151, 153, 170, 177, 180, 187 were 6.86?ng/g fresh weight for mullet fish, 0.2?ng/g fresh weight, for bolti fish, 2.72?ng/g fresh weight for bivalves and 2.8?ng/g fresh weight for crab, respectively.     

Pyrimethanil Residues on Table Grapes Italia after Field Treatment

Residues of the pyrimidine fungicide pyrimethanil [N-(4,6-dimethylpyrimidin-2yl)aniline] were determined in table grapes “Italia” by gas chromatography nitrogen-phosphorus detector (GC-NPD). Pesticides were extracted from grapes with ethyl acetate and hexane solution (1:1 v/v), and were analyzed without any further clean up. Pyrimethanil was confirmed by high-performance liquid chromatography (HPLC) fitted with a diode array detector (DAD) and electrospray ionization mass spectrometry (ESI-MS) in the select ion-monitoring mode (SIM). The residue of pyrimethanil was under the legal limit immediately after treatment, and showed a half-life time, calculated as a reaction of pseudo first order, of 12 days, with a regression coefficient of 0.9954. Recoveries from fortified grapes ranged between 90 and 113% with a maximum coefficient of variation (CV) of 11%. The calculated limits of detection and quantitation for pyrimethanil were 0.005 and 0.01 mg/kg, respectively.     

Analysis and fate of acephate and its metabolite,methamidophos, in pepper and cucumber

Abstract

Levels of acephate (Orthene^R) and its principle metabolite, methamidophos, in/on greenhouse‐grown pepper and cucumber fruits and leaves in relation to the applied methamidophos were monitored. Dislodgeable and total residues of acephate and methamidophos were determined by gas‐liquid chromatography equipped with a flame ionization detector (GC‐FID) and were confirmed by nitrogen phosphorus detector (GC‐NPD). The dissipation curves of the residues followed first‐order kinetics (R²> 0.96). Initial residues of acephate on fruits varied between pepper (15.12 ppm) and cucumber (2.16 ppm) . Total residues in fruits and leaves determined at intervals following application revealed the greater persistence of acephate on pepper fruits (half‐life [t_1/2] of 6 d) than on cucumber fruits (t_1/2 was 3.7 d) . T_1/2 values for the applied methamidophos were 4.7 and 5.3 d on pepper and cucumber fruits, respectively. Deacety‐lation of acephate (formation of its metabolite) was detectable 1 d following acephate treatment and reached a maximum of 2.05% of initial acephate residues 3 d after application on pepper fruits. On cucumber fruits, acephate metabolite reached a maximum of 2.12% one wk following application. No acephate residues were detected above the limit of detection of 0.001 ppm in pepper fruits 50 d following acephate application while its metabolite was detectable at that time (detectability limit was 0.0001 ppm).