Phosphine estimation in fumigated food grains using gas chromatography equipped with FPD detector.

Phosphine, as per several reports, is considered to be an ideal and effective alternative to methyl bromide (MB) fumigant, phased out globally honouring 'Montreal Protocol'. The food grains fumigated with phosphine are perceived to be residue-free; however, estimation of its residues is imperative. In the present study, the phosphine residues were estimated in grains of wheat, rice, green gram, chickpea and yellow pea fumigated with different formulations of phosphine under 7 and 10 days exposure periods at various locations in India. For efficacy studies, the conventional aluminium phosphide (AlP) tablet (56% @2 and 3 tablet/MT) and granular AlP (77.5% @1.0 and 1.5 g phosphine/m3) formulations were applied. Each treatment including untreated control was replicated thrice. The concentration was monitored every 24 h until the end of exposure periods. Food grain samples were drawn before and post fumigation following a certain waiting period for estimation of phosphine residues using gas chromatography equipped with FPD detector. Residues in fumigated food grains were observed in traces in all the experimental stacks, but below the MRL (0.1 ppm), fixed by Codex Alimentarius Commission (CAC). Phosphine can be considered safe for use as an alternate fumigant in quarantine and long-term storage of food grains leaving residues below MRL.

Mixture toxicity assessment of selected insecticides to silver perch fingerling, Bidyanus bidyanus.

The organophosphorus (OP) and carbamate (CB) insecticides are responsible for inhibition of the Acetylcholinesterase (AChE) enzyme. The AChE activity, therefore, has been demonstrated to be a potent biomarker for these insecticides in terrestrial and aquatic environments. The objective of this study was to investigate the response of AChE in the brain of four-week old fingerlings of silver perch, Bidyanus bidyanus exposed to OP and CB insecticides. The fish fingeling were exposed to three OPs and one CB insecticide as individual and their binary mixtures for 48 h. The OP insecticides with oxon (PO) as well as thion (PS) group gets oxidized to oxon analogs in biological systems. The 50% AChE inhibition (48 h EC50) in fingerling exposed to chlorpyrifos (CPF) and triazophos (TRZ) was evident at 2.3 and 6.7 µg/L, respectively. The toxicological interaction of three OPs and one CB insecticide was evaluated using the toxic unit method. A strong synergism was observed for binary combination of CPF with profenofos (PRF), and CPF with TAZ. In contrast, the mixture of TAZ with PRF and carbofuran (CBF) with CPF and PRF showed antagonistic behavior. Although OP and CB insecticides can break down rapidly in the environment, this study suggests that non-target aquatic biota may be exposed to mixtures of ChE-inhibiting insecticides for a period of several months, in agricultural regions where insecticides are applied for extended periods of the year. And at environmentally relevant concentrations such mixtures may lead to deleterious effects in non-target organisms.

Rice pest management with reduced risk pesticides in India.

Sitapur district in the Uttar Pradesh (U.P.) state of northern India has been observed to consume large amounts of WHO classified "extremely" and "highly hazardous" pesticides, in rice crop, posing significant health and environmental threats. Keeping in view this problem, integrated pest management (IPM) modules were synthesized for rice crop and then compared with non-IPM/farmer's practice (NIPM). This study assisted in identifying pesticides with reduced risk to the environment. To measure and compare risks, environmental impact quotient (EIQ) has been used as a pesticide risk indicator model, between IPM and NIPM programs. Using this model, the field EIQ values (EIQ field use rating or EIQ-FUR), for 32 commonly used pesticides in the region, were evaluated based on dosage, frequency, and percent active ingredients present in the pesticide formulations. The results conclude that copper oxychloride (CuOCl2) (50 WP at 1.25 kg/ha) and mancozeb (75 WP at 1.25 kg/ha) were the most detrimental to arthropod parasitoids and were the highest contributors to environmental risk (13-16%), in rice crop. This is based on the comparison of total dosage and active ingredients of pesticides applied under IPM and NIPM, with the total field EIQ values. The IPM modules were observed to have least impact on natural enemies with 30-40% increase in population, while keeping the weed population below 10%. NIPM, on the other hand, had resulted in 20% reduction in crop yields, 50% reduction in biodiversity, and about 150% increase in weed population, relative to the control (untreated) rice fields. Moreover, NIPM practices had been observed to pose 56% greater risk as per the total field EIQ values (62 for IPM and 141 for NIPM). The observations concluded that the EIQ model is a useful tool and can be easily used by the pesticide managers for assessing the risk against NIPM.

Binary combinations of organophosphorus and synthetic pyrethroids are more potent acetylcholinesterase inhibitors than organophosphorus and carbamate mixtures: An in vitro assessment.

Anticholinesterase insecticides such as organophosphorous (OP) and carbamates pesticides (CB); and synthetic pyrethroids (SP) pesticides commonly co-occur in the environment. This raises the possibility of antagonistic, additive, or synergistic neurotoxicity in exposed organisms. Acetylcholinesterase (AChE) inhibition has been demonstrated to be useful as a biomarker for exposure to OP and CBs in many environments. This study investigated the response of housefly (Musca domestica) head AChE (HF-AChE) exposed to five OPs; chlorpyrifos (CPF), malathion (MLT), triazophos (TRZ), monocrotophos (MCP) and profenofos (PRF) and two CBs; carbaryl (CRB) and carbofuran (CBF) as individual compounds and as binary mixtures of OPs and CBs under in vitro conditions. In addition, the selected OPs and CBs were evaluated for their toxicity in binary combinations with two SPs; deltamethrin (DLT) and cypermethrin (CYP) at fixed concentrations of 0.1 and 10µg/L. The toxicological interaction of five OPs with two CBs pesticides was evaluated under oxidised and un-oxidised conditions using a toxic unit (TU) approach and a concentration addition (CA) model. Pyrethroid combinations were assessed only under oxidised conditions. Since OPs and CBs act by a similar mechanism of inhibition of AChE, a dose additive effect was expected, but not conclusively found. TRZ with either CBF or CRB exhibited synergism under oxidised and un-oxidised conditions but the degree of synergism was stronger under un-oxidised conditions. Additivity was exhibited by CBF+MCP, CRB+MCP, CRB+MLT and CBF+MCP under un-oxidised conditions and CRB+MCP and CRB+CPF under oxidised conditions. Pyrethorids in combination with OPs (TRZ, MLT and CPF) were highly synergistic. In the present study, we used pure housefly head AChE without any interference of monooxygenase and/or esterase enzyme activities. Therefore these other enzymes were not producing the observed deviations from concentration-addition in the binary combinations between OPs, CBs and SPs. The mechanisms of OP, CB and SP interactions in pesticide mixtures requires further investigation.

Binary combinations of organophosphorus pesticides exhibit differential toxicity under oxidised and un-oxidised conditions.

Acetylcholinesterase (AChE) inhibition has been demonstrated to be useful as a biomarker for exposure to organophosphorus (OP) insecticides in many environments. The objective of this study was to investigate the response of housefly (Musca domestica) head AChE (HF-AChE) exposed to five OPs as individual compounds and their binary mixtures under in vitro conditions. To examine the effects of oxidation on OP potency in the HF-AChE system, bromine water was used as an oxidisng agent. With oxidation, the sensitivity of HF-AChE to chlorpyrifos (CPF), malathion (MLT) and triazophos (TRZ) increased significantly. Monocrotophos (MCP) and profenofos (PRF) did not exhibit any significant differences in toxicity under oxidised and un-oxidised conditions. The toxicological interaction of five organophosphorus pesticides was evaluated using the concentration addition model, the combination index-isobologram equation and the toxic unit approach. All three models provided similar predictions for the 10 binary combinations of OPs under oxidised and un-oxidised conditions. In the present study, the antagonistic effects of the binary combination of OPs (CPF+PRF, CPF+MLT, MCP+MLT, PRF+MLT, MLT+TRZ and PRF+TRZ) were observed under oxidised conditions. This may be due to dispositional and/or receptor antagonism. Most of the binary combinations assayed under un-oxidised conditions exhibited synergistic responses. Triazophos showed very strong synergism in binary combinations with CPF, MCP and PRF un-oxidised conditions. In contrast, under oxidised conditions, only CPF+TRZ exhibited synergism. The results obtained indicate differential toxicity of binary combinations of OPs under oxidised and un-oxidised conditions. This information could be a valuable tool in understanding the mechanisms of OPs interactions and the interpretation of future in vivo studies with mixtures of OP insecticides.

Pesticide residue analysis of soil, water, and grain of IPM basmati rice.

The main aim of the present investigations was to compare the pesticide load in integrated pest management (IPM) with non-IPM crops of rice fields. The harvest samples of Basmati rice grain, soil, and irrigation water, from IPM and non-IPM field trials, at villages in northern India, were analyzed using multi-pesticide residue method. The field experiments were conducted for three consecutive years (2008-2011) for the successful validation of the modules, synthesized for Basmati rice, at these locations. Residues of tricyclazole, propiconazole, hexconazole, lambda cyhalothrin, pretilachlor chlorpyrifos, DDVP, carbendazim, and imidacloprid were analyzed from two locations, Dudhli village of Dehradun, Uttrakhand and Saboli and Aterna village of Sonepat, Haryana. The pesticide residues were observed below detectable limit (BDL) (<0.001-0.05 µg/g) in all 24 samples of rice grains and soil under IPM and non-IPM trials. Residues were below detection level (<0.001-0.05 µg/L) in irrigation water samples (2008-09). Residues of tricyclazole and carbendazim, analyzed from same locations, revealed pesticide residues as BDL (<0.001-0.05 µg/g) in all 40 samples of Basmati rice grains and soil. It was also observed as BDL (<0.001-0.05 µg/L) for 12 water samples (2009-2010). The residues of tricyclazole, propioconazole, chlorpyrifos, hexaconazole, pretilachlor, and λ-cyhalothrin were also found as BDL (<0.001-0.05 µg/g) in 40 samples of Basmati rice grains and soil and 12 water samples (<0.001-0.05 µg/L) (2010-2011).

Comparative assessment of pesticide residues in grain, soil, and water from IPM and non-IPM trials of basmati rice.

The integrated pest management (IPM) modules of pesticide schedule on Basmati rice were validated at field experiments conducted in Northern India for consecutive 3 years (2005-2008). The pesticide residues were found below the detectable limit (<0.01-0.001 mg/kg) in soil and irrigation water samples of Kaithal region. In Dehra Dun region of Uttrakhand, the residues of carbendazim in rice grains and soil were detected below <0.01 mg/kg level. In second year experiments (2006-2007), only four non-IPM soil samples indicated the presence of chlorpyrifos and endosulfan in the range of ND <0.001 to 0.07 mg/kg, out of 45 samples analyzed. Carbendazim applied as seed treatment at Dehradun and Kaithal field trials was found below detectable limit in both IPM and non-IPM rice grains (<0.01 mg/kg) and irrigation water (0.01 µl/ml). Chlorpyrifos was detected in five water samples from Kaithal and one from Pant Nagar in the range of 0.003-0.006 µl/L, α- and ß-isomer of endosulfan in the range of 0.005-0.03, and 0.005-0.02 µl/ml, respectively, in one sample from Pant Nagar and two from Kaithal, out of a total of 22 samples. In the region of Uttrakhand and Uttar Pradesh during 2007-2008, four non-IPM samples of soil indicated trace levels of endosulfan, out of 16 samples analyzed. The residues were detected below detection limit for carbendazim (<0.01 mg/kg) in soil samples of Dehradun IPM fields and for endosulfan and carbendazim (0.001-0.01 µl/L) in water samples each from IPM and non-IPM fields of Uttar Pradesh. The results of 3-year trials of IPM module indicated basmati rice as safe and economical with pesticide residue-free rice grains.

Impact analysis of IPM programs in Basmati rice by estimation of pesticide residues.

Samples of Basmati rice grain, soil and water were collected, from IPM and non-IPM field trials conducted at four regions of Haryana, Uttar Pradesh and Uttarakhand in India, for pesticide residue analysis. Out of 45 soil samples collected, only four non-IPM samples indicated the presence of chlorpyrifos and endosulfan in the range of ND (<0.001) to 0.05 mg/kg. Carbendazim used at two locations of Dehradun and Kaithal was found below detectable limit (<0.05 mg/kg) in both IPM and non-IPM trials. Out of total 22 samples of water analyzed, chlorpyriphos was detected in samples from Kaithal and Pant Nagar in the range 0.003-0.006 µL/L, alpha -endosulfan isomer was detected in the range 0.005-0.03 µL/L and the beta-isomer in the range 0.005-0.02 µL/L in sample from Pant Nagar and Kaithal. The residues in all the grain sample of paddy were below detectable limit (<0.001-0.05 mg/kg). The insecticides applied in IPM as well as non-IPM trials were found to be below maximum residue level (MRL).

Analysis of insecticides in okra and brinjal from IPM and non-IPM fields.

Samples of okra and brinjal fruits, collected from non-integrated pest management (Non-IPM) and IPM fields in village Raispur, Ghaziabad District (U.P.), were analyzed for pesticide residues. The residues of chlorpyrifos in soil were 4.219 and 1.135 microg/g at harvest time in non-IPM and IPM fields of summer okra crop from initial value of 0.407 microg/g before sowing, while in brinjal crop, it was not detected in soils of any trials. During first year of study, the residues of chlorpyrifos and cypermethrin in okra fruit were observed to be 5.75 and 0.625 microg/g, respectively, for non-IPM fields; and 0.104 microg/g of chlorpyrifos for IPM trials. The pesticide residues were found to be 0.77, 1.39, 0.4 and 0.32 microg/g for cypermethrin, chlorpyrifos, monocrotophos and dimethoate, respectively, for non-IPM okra fruits in second year. For brinjal fruit, residues of cypermethrin and imidacloprid were not detected in IPM trials while it was found to be 0.28 and 0.78 microg/g for cypermethrin and chlorpyrifos respectively, for non-IPM trials.

Determination of pesticide residue in soil, water and grain from IPM and non-IPM field trials of rice.

Soil, water and rice grain samples from field trials conducted under the IPM and non-IPM modules in Kaithal (Haryana) region were analyzed for pendimethalin, atrazine, lindane and chlorpyriphos, and in Dehradun (Uttarakhand) region, samples were analyzed for carbendazim only. The pesticide residues were found below the detectable limit in the soil and water samples of the Kaithal region. From Dehradun region the residues of carbendazim in rice grains were detected at 0.001 mg/kg level, and in soil they were in the range of 0.03-0.001 mg/kg. The insecticides applied in IPM as well as non-IPM trials in both regions were observed to be below the prescribed maximum residue level.

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 microg/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.