Persistence of fipronil and its metabolites in soil under field conditions

Fipronil belongs to phenylpyrazole class of chemical compounds. Degradation of fipronil in sandy loam soil was investigated under field conditions by applying fipronil (Regent 5 % SC) at 50 (T ₁) and 100 g a.i. ha^?1 (T ₂) in field. Samples were drawn periodically in triplicate on 0 (1 h after treatment), 1, 3, 7, 10, 15, 30, 60, and 90 days after treatment and analyzed on GC-ECD system equipped with capillary column. The residues of fipronil in both the doses dissipated in the range of 93.33–100 % in 90 days. Limit of detection (LOD) and limit of determination (LODe/LOQ) were 0.0003 and 0.001 mg kg^?1, respectively. Dissipation followed a biphasic first-order kinetics with half-life values of 10.81 and 9.97 days for fipronil alone and 8.14 and 13.05 days for fipronil along with metabolites in soil at (T ₁) and (T ₂) treatments, respectively.     

Simultaneous determination of insecticide fipronil and its metabolites in maize and soil by gas chromatography with electron capture detection

An integrated method for the simultaneous determination of insecticide fipronil and its three metabolites, desulfinyl, sulfide, and sulfone, in maize grain, maize stem, and soil was developed. This three-step method uses liquid–solid extraction with ultrasound or mechanical grinding, followed by liquid–liquid partitioning and florisil solid-phase extraction (SPE) for cleanup. The quantification was conducted by gas chromatography–electron capture detection in triplicate for each sample. The method was validated with five replicates at three fortification concentrations, 0.002, 0.01, and 0.1 mg kg^?1, in each matrix and gave mean recoveries from 83 to 106 % with relative standard deviation ≤8.9 %. The limits of quantification (LOQ) were 0.002 mg kg^?1 for the compounds in all matrixes. In the field study in Beijing and Shandong 2012, fipronil-coated maize seeds were planted and the proposed method was applied for checking the possible existence of four compounds in maize and soil samples, but none of them contained residues higher than the LOQs in both application rates. Moreover, the dissipation of fipronil in soil fits first-order kinetics with half-lives 9.90 and 10.34 days in Beijing and Shandong, respectively. Combined with an adequate sample treatment, this technique offers good sensitivity and selectivity in the three complex matrixes. The results could provide guidance for the further research on pesticide distribution and safe use of fipronil as seed coat in cereals.     

Persistence and vertical distribution of termiticide fipronil in modified ground board test

Fipronil termiticide belongs to phenyl-pyrazole class of chemical compounds. It has broad-spectrum activity particularly against house hold pests such as cockroaches, mosquitoes, locusts, ticks, and fleas at both larval and adult stages. At high dosage it can be used to control subterranean termites in building foundations. To evaluate long term efficacy against termites the persistence and vertical distribution of fipronil was studied under natural weather conditions of Dehradun, India. Fipronil was applied at four concentrations i.e. 0.05, 0.1, 0.25 and 0.5% a.i ha⁻¹ by drenching 17 × 17 in.² plot prepared as per modified ground board test. Soil samples were collected after 22, 38 and 56 months of treatment up to the depth of 75 cm. The soil core was cut into five distinct sections i.e. 0–15, 15–30, 30–45, 45–60 and 60–75 cm depth. The residues were extracted by shaking 20 g soil sample with acetone. The acetone extract was concentrated and cleaned-up over florisil column. Fipronil residues were estimated on GLC at 220, 260, and 300°C oven, injector and detector temperature respectively. Fipronil was found to persist beyond 56 months after application. Two metabolites viz. desulfinyl and sulfide-fipronil were detected in sampling after 22 months of application that also dissipated with time. Fipronil residues were found up to 60 cm depth. The residues in deeper layers dissipate slowly with time and after 56 months of treatment residues were detected only up to 30 cm depth.     

Persistence and bioaccumulation of oxyfluorfen residues in onion

A field study was conducted to determine persistence and bioaccumulation of oxyflorfen residues in onion crop at two growth stages. Oxyfluorfen (23.5% EC) was sprayed at 250 and 500 g ai/ha on the crop (variety, N53). Mature onion and soil samples were collected at harvest. Green onion were collected at 55 days from each treated and control plot and analyzed for oxyfluorfen residues by a validated high-performance liquid chromatography method with an accepted recovery of 78–92% at the minimum detectable concentration of 0.003 μg g^???1. Analysis showed 0.015 and 0.005 μg g^???1 residues of oxyfluorfen at 250 g a.i. ha^???1 rate in green and mature onion samples, respectively; however, at 500 g a.i.ha^???1 rates, 0.025 and 0.011 μg g^???1 of oxyfluorfen residues were detected in green and mature onion samples, respectively. Soil samples collected at harvest showed 0.003 and 0.003 μg g^???1 of oxyfluorfen residues at the doses 250 and 500 g a.i. ha^???1, respectively. From the study, a pre-harvest interval of 118 days for onion crop after the herbicide application is suggested.     

Persistence and effect of processing on reduction of fipronil and its metabolites in chilli pepper (Capsicum annum L.) fruits

A single laboratory UPLC-MS/MS method was developed and validated for the estimation of fipronil and its metabolites in fresh and dry chilli pepper fruits. Dissipation of fipronil on chilli fruits was studied following the application of fipronil (Jump 80 WG) at 40 and 80 g active ingredient (a.i.) ha^?1 in the fruiting stage of the crop. The initial deposits of total fipronil on fresh chilli fruits at single and double dose application were 0.69 and 1.43 μg g^?1, respectively, and were dissipated to below quantitation level at 27 days after application. The half-life of fipronil at single and double dose in fresh chilli pepper was 4.22 and 4.32 days and the waiting period was 25.9 and 30.6 days, respectively. Processing factor due to sun drying was calculated by measuring fipronil residues in dry chilli fruits, and it ranged from 2.96 to 3.50 during 0 to 21st day after application. Among the metabolites of fipronil, fipronil desulfenyl and fipronil sulfone had maximum residues in fresh and dried chilli, respectively, followed by fipronil sulfide. Dipping in solutions of tamarind, turmeric, vinegar and slaked lime and wet scrubbing could remove more than 90 % of fipronil residues in fruits.     

Organochlorine insecticide residues in agricultural soils of the indo-gangetic plain

Multiple residues of organochlorine insecticides were monitored in the agricultural fields near Farrukhabad in the vicinity of the River Ganga in northern India for one year (1991–1992). Almost all soil samples were found to be contaminated with residues of hexachlorocylohexane (HCH) and dichlorodiphenyl-trichloroethane (DDT). Residues of aldrin and endosulfan were also detected in a large number of samples. Heptachlor residues were scarcely detected. Alpha-HCH, pp-DDT and alpha-endosulfan were found to dominate over the other isomers/metabolites of HCH, DDT and endosulfan, respectively. The average concentration of dieldrin was more than that of aldrin. The concentrations of residues progressively increased up to a depth of 1 m.     

A sampling method to determine insecticide residues on surfaces and its application to food-handling establishments

Known amounts of acephate, chlorpyrifos, and diazinon were applied to Formica, unfinished plywood, stainless steel, and vinyl tile. Cotton-ball and dental wick materials were dipped in 2-propanol and swiped over the treated surface area two time. More acephate was found on the second swipe compared to the first from vinyl tile, similar amounts on both swipes from plywood, and less on the second swipe from formica and stainless steel. The ratio of chlorpyrifos on Swipe 1 compared to Swipe 2 found with cotton-ball on both formica and stainless steel surfaces was equivalent (6:1), but a considerable difference was seen when two dental wick swipes were used. Residues of diazinon removed from formica and stainless steel were equivalent, regardless of the swiping material used. Residues of chlorpyrifos were detected by taking swipes of surfaces in two restaurants and a supermarket up to 6 mo after a prescribed application by a commercial pest control firm. The data show that measurable amounts of chloropyrifos can be detected on surfaces not treated with the insecticide for at least 6 mo.     

水溶液中盐的浓度与其电导率的关系研究

采用电导法研究了水溶液中盐的浓度与其电导率的关系。结果表明 ,在低浓度范围内电导率与浓度的平方根呈线性关系 ;在较高的浓度范围内 ,首次发现浓度与电导率的关系和 Langmuir吸附等温式中的压力与吸附量之间的关系类似。利用浓度与电导率间的定量关系确定水溶液中盐的浓度 ,比传统的重量法和滴定法快速且准确。     

Organochlorine insecticide residues in drinking and ground water in and around Delhi

A multiresidue method was developed for the estimation of 15organochlorine pesticides in water. 50 samples of drinking watersupplied by the Municipal Corporation to the residential areasof Delhi and 20 ground water samples from nearby villages usedfor irrigation were monitored for the presence of organochlorineinsecticides by the method developed. Although, organochlorinepesticides were detected in the ground water and irrigationwater samples, the levels of pesticides were below the MaximumContaminant Level as prescribed by WHO. No organochlorineinsecticides were detected in any of the drinking water samples.     

Persistence of dicofol residues in cotton lint seed, and soil

A supervised field trial was conducted at the CCS Haryana Agricultural University, Hisar to assess the residues of dicofol on cotton, during Kharif season, 2008. Dicofol (Kelthane 18.5EC) was applied at 500 g a.i./ha (T(1)) and 1,000 g a.i./ha T(2)) after 105 days of sowing of cotton crop (Varity Cotton/H-1226). Soil samples were collected on 0 (1 h after treatment), 3, 7, 10, 15, 30, and 60 days after spray and cotton samples were collected at harvest. Samples were processed and residues were quantified by GC-ECD system equipped with capillary column. Limit of detection and limit of quantification (LOQ) were 0.001 and 0.010 mg kg(?-1), respectively, for soil and LOQ for cotton lint and seed was 0.020 mg kg(?-1). Initial residues of 0.588 and 1.182 mg kg(?-1) in soil reached below detectable level (BDL) of 0.010 mg kg(?-1) in T(1) and to the level of BDL (0.010 mg kg(?-1)) in T(2) at harvest (60 days after treatment). In 60 days, residues dissipated almost completely (100 and >99%) in both the treatments. Half-life period was calculated as 8.57 days at single dose and 8.69 days at double dose in soil. Residues of dicofol were detected in cotton lint to the levels of 0.292 and 0.653 mg kg(?-1) and in seed 0.051 and 0.090 mg kg(?-1) in T(1) and T(2) doses, respectively at harvest. Residues in cotton seed were below MRL value of 0.01 mg kg(?-1) in both the doses.     

Ground water contamination by organochlorine insecticide residues in a rural area in the indo-gangetic plain

Residues of several organochlorine insecticides were monitored in the ground water from a rural area near Farrukhabad in the vicinity of the Ganga River in northern India for one year (1991–1992). Almost all the samples were found to be contaminated with residues of Hexachlorocyclohexane (HCH) and Dichloro-diphenyl-trichloroethane (DDT). Residues of Aldrin, endosulfan and heptachlor were also detected in a large number of samples. The concentrations of aldrin residues greatly exceeded the WHO guideline value for drinking water, concentrations of heptachlor and DDT residues also occasionally exceeded the specified limits. Migration of pollutants through ground water recharge with polluted Ganga River water and monsoon rains carrying undergraded residues downwards from the soil surface are throught to be important sources of insecticide contamination of ground water in the region.     

Persistence and effect of processing on reduction of chlorantraniliprole residues on brinjal and okra fruits

Dissipation and decontamination of chlorantraniliprole (Coragen 18.5 SC) in brinjal and okra fruits were studied following field application at single and double doses of 30 and 60 g ai ha^?1, and the residues of the insecticide was estimated using LC-MS/MS. Initial residues of chlorantraniliprole at single and double doses on the fruits of brinjal were 0.72 and 1.48 mg kg^?1, while on okra fruits, the residues were 0.48 and 0.91 mg kg^?1, respectively. The residues reached below detectable level of 0.01 mg kg^?1 on the 10th day. Half-life of chlorantraniliprole at 30 and 60 g ai ha^?1 on brinjal was 1.58 and 1.80 days with the calculated waiting period of 0.69 and 2.38 days, whereas on okra, the values were 1.60 and 1.70 and 0 and 1.20 days, respectively. The extent of removal of chlorantraniliprole using simple decontaminating techniques at 2 h and 3 days after spraying was 40.99–91.37 % and 29.85–89.12 %, respectively, from brinjal fruits and 47.78–86.10 % and 41.77–86.48 %, respectively, from okra fruits.     

Persistence behaviour of imidacloprid and its metabolites in soil under sugarcane

The persistence and metabolism of imidacloprid in soil under sugarcane were studied following application of imidacloprid at 20 and 80 g active ingredient (a.i.) ha^?1. Soil samples were collected at different time intervals (7, 15, 30, 45, 60 and 90 days after application), and the residues of imidacloprid and its metabolites (6-chloronicotinic acid, nitrosimine, imidacloprid-NTG, olefin, urea and 5-hydroxy) were quantified by high-performance liquid chromatography. In soil, the total imidacloprid residues were mainly constituted by the parent compound followed by 6-chloronicotinic acid, nitrosimine and imidacloprid-NTG metabolites. Maximum residues of imidacloprid and its metabolites were 4.29 and 7.81 mg kg^?1 in soil samples collected 7 days after the application of imidacloprid at 20 and 80 g a.i. ha^?1, respectively. At both doses, these residues declined to below the detectable limit in soil after 90 days of application. Olefin, urea and 5-hydroxy metabolites were not detected in soil. Dissipation of total imidacloprid residues did not follow the first-order kinetics with a coefficient of determination value of 0.883 and 0.838 for the recommended dose and four times the recommended dose, respectively. The half-life (T _1/2) value of total imidacloprid was observed to be 10.64 and 10.10 days for the recommended dose and four times the recommended dose, respectively.     

Monitoring of methoxychlor residues in the Athabasca River system in northern Alberta after treatment for control of black fly larval populations

Methoxychlor (2,2-bis(p-methoxyphenyl)-1,1,1-trichloroethane) was used in the Athabasca River in northern Alberta for the control of black fly larvae, Simulium arcticum, during May to July of 1981 to 1987. Samples of river water and sediment were analyzed for methoxychlor residues each year as part of Alberta Environment's program to assess environmental impact and monitor compliance with issued permits. During 1985 fish samples were also collected at various sites downstream and upstream of the point of application of methoxychlor. This paper summarizes the residue data obtained by analysing these fish, sediment and water samples collected from the Athabasca River system during the years 1981 to 1987.     

Development of a new method for the determination of residues of the neonicotinoid insecticide imidacloprid in juvenile chinook (Oncorhynchus tshawytscha) using ELISA detection

The neonicotinoid insecticide imidacloprid (IMI) has been proposed as an alternative to carbaryl for controlling indigenous burrowing shrimp on commercial oyster beds in Willapa Bay and Grays Harbor, Washington. A focus of concern over the use of this insecticide in an aquatic environment is the potential for adverse effects from exposure to non-target species residing in the Bay, such as juvenile Chinook (Oncorhynchus tshawytscha) and cutthroat trout (O. clarki). Federal registration and State permiting approval for the use of IMI will require confirmation that the compound does not adversely impact these salmonids following field applications. This will necessitate an environmental monitoring program for evaluating exposure in salmonids following the treatment of beds. Quantification of IMI residues in tissue can be used for determining salmonid exposure to the insecticide. Refinement of an existing protocol using liquid-chromatography mass spectrometry (LC-MS) detection would provide the low limits of quantification, given the relatively small tissue sample sizes, necessary for determining exposure in individual fish. Such an approach would not be viable for the environmental monitoring effort in Willapa Bay and Grays Harbor due to the high costs associated with running multiple analyses, however. A new sample preparation protocol was developed for use with a commercially available enzyme-linked immunosorbent assay (ELISA) for the quantification of IMI, thereby providing a low-cost alternative to LC-MS for environmental monitoring in Willapa Bay and Grays Harbor. Extraction of the analyte from the salmonid brain tissue was achieved by Dounce homogenization in 4.0 mL of 20.0 mM Triton X-100, followed by a 6 h incubation at 50-55 °C. Centrifugal ultrafiltration and reversed phase solid phase extraction were used for sample cleanup. The limit of quantification for an average 77.0 mg whole brain sample was calculated at 18.2 μg kg(-1) (ppb) with an average recovery of 79%. This relatively low limit of quantification allows for the analysis of individual fish. Using controlled laboratory studies, a curvelinear relationship was found between the measured IMI residue concentrations in brain tissue and exposure concentrations in seawater. Additonally, a range of IMI brain residue concentrations was associated with an overt effect; illustrating the utility of the IMI tissue residue quantification approach for linking exposure with defined effects.     

Persistence of white spot syndrome virus in shrimp ponds and surrounding areas after an outbreak

White Spot Syndrome Virus (WSSV) is the major and most serious pathogen in shrimp aquaculture industries. By using a sensitive PCR-based detection technique followed by sequencing multiple PCR products for confirmation, we address to the question of whether WSSV can persist in shrimp ponds and surrounding areas after an outbreak. The seawater samples were taken from two shrimp ponds and surrounding canals in a coastal area in northern Vietnam, Quang Ninh Province where the shrimps cultured in the two ponds had been killed due to a WSSV outbreak in April 2001 and the ponds were thereafter abandoned. A total of 480 seawater samples (30 samples each for July and December of 2001 and 2002) were subjected to WSSV genome detection. Although the detection rates of WSSV genome were generally gradually declined in seawater environments of both diseased shrimp ponds and surrounding canals, WSSV was still detected with rates of more than 10% in the diseased ponds and lower in surrounding canals in December 2002, 20 months after the WSSV outbreak.     

Pesticide residues in river Yamuna and its canals in Haryana and Delhi, India

Yamuna, a prominent river of India covers an extensive area of 345,843 km(2) from Yamunotri glacier through six Indian states. Residues of organochlorine pesticides (OCPs) namely, isomers of HCH and endosulfan, DDT and its metabolites, aldrin, dieldrin, were analysed in water of river Yamuna along its 346 km stretch passing through Haryana-Delhi-Haryana and the canals originating from it. beta-HCH, p.p'-DDT, p.p'-DDE and p.p'-DDD had maximum traceability in test samples (95-100%) followed by gamma-HCH, alpha-HCH and o.p'-DDD (60-84%) and o.p'-DDT, delta-HCH and o.p'-DDE (7-30%) while aldrin, dieldrin, alpha and beta endosulfan remained below detection limits (BDL). The concentration of SigmaHCH and SigmaDDT at different sites of the river ranged between 12.76-593.49 ng/l (with a mean of 310.25 ng/l) and 66.17-722.94 ng/l (with a mean of 387.9 ng/l), respectively. In canals the values were found between 12.38-571.98 ng/l and 109.12-1572.22 ng/l for SigmaHCH and SigmaDDT, respectively. Water of Gurgaon canal and Western Yamuna canal contained maximum and minimum concentration, respectively both of SigmaHCH and SigmaDDT residues. Sources of these pesticides and suggested measures to check pesticide pollution of this major Indian river, keeping in view its vital link with life, are discussed in this paper.     

Persistence and dissipation of flubendiamide and its risk assessment on gherkin (Cucumis anguria L.)

A supervised open field trial was conducted to evaluate the dissipation pattern and risk assessment of flubendiamide in gherkin fruits following foliar application of Fame 480 SC at 60 and 120 g a.i.?ha^?1. Samples of gherkin fruits were drawn at different time intervals and quantified by HPLC-DAD. The maximum initial deposits of flubendiamide on gherkin were found to be 0.79 and 1.52 mg kg^?1, respectively, at recommended and double the recommended doses. The dissipation pattern of flubendiamide followed a first-order kinetics with half-lives of 1.87 to 2.16 days at 60 and 120 g a.i.?ha^?1, respectively. The limit of quantification of flubendiamide and desiodo flubendiamide was observed to be 0.01 mg kg^?1 for gherkin fruit and soil substrates. Theoretical maximum residue contribution (TMRC) for flubendiamide was calculated and found to be well below the maximum permissible intake (MPI) on gherkin fruits. Thus, the application of flubendiamide at the recommended dose on gherkin fruits presents no human health risks and safe to consumers.