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Residue determination of β-cyfluthrin and imidacloprid as mix formulation in/on chickpea (Cicer arietinum) pods and soil and its risk assessment

Residue determination of β-cyfluthrin and imidacloprid as mix formulation in/on chickpea (Cicer... OBJECTIVES: A field experiment was conducted at Agricultural Research Station for irrigated crops at Thasara, Anand Agricultural University, Anand, to study the dissipation and risk assessment of β-cyfluthrin and imidacloprid as combination product in/on chickpea. MATERIALS AND METHODS: Solomon 300 OD comprising 9 per cent β-cyfluthrin and 21 per cent −1 −1 imidacloprid was foliar sprayed at the doses of 18 + 42g a.i. ha (standard dose) and 36 + 84g a.i. ha (double dose). Totally three sprays were made at an interval of 1 week starting from fruiting stage. RESULTS AND DISCUSSIONS: The residues of β-cyfluthrin estimated using gas chromatograph with −1 electron capture detector (GC-ECD) showed an initial deposit of 0.16 and 0.27 μg g in standard and double doses, respectively. The residues for corresponding doses persisted till 7th and 10th −1 day after application and reached below determination level of 0.01μg g on the 10th and 15th day, respectively. Imidacloprid was estimated using high performance liquid chromatography (HPLC) and −1 showed initial deposits of 1.22 and 2.7 μg g in standard and double doses, respectively. Its levels −1 reached below the determination level (0.01 μg g ) on the 15th day in green pods. Statistical analysis of dissipation kinetics showed that β-cyfluthrin followed zero-order kinetics in standard dose with half-life of 7.27 days. In double dose, the dissipation kinetics followed first-order kinetics with half-life of 9 days. Imidacloprid followed first-order kinetics in both the doses with half-life of 6.7 and 7.7 days. CONCLUSIONS: A pre-harvest interval (PHI) of 15 days is suggested. Theoretical risk assessment calculated as hazard quotient was less than 1, rendering the use of combination product as safe- provided proper PHI is followed. Key words: chickpea; β-cyfluthrin; imidacloprid; dissipation; dissipation kinetics; residue; risk assessment; pods. production of chickpea was about 12 million metric tons in 2011 Introduction (www.aicrchickpea.rs.in; accessed on 23 May 2017). India is the Chickpea (Cicer arietinum L.) is the third most important pulse largest producer with about 8 million tons, accounting of about 75 crop, after dry bean and peas in the world and accounts for 20 per cent of total world production. Six countries including India, per cent of the world pulses production. As per the latest available Australia, Turkey, Myanmar, Pakistan, and Ethiopia account for estimates of Food and Agricultural Organization (FAO), the global © The Author(s) 2018. Published by Oxford University Press on behalf of Zhejiang University Press. This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/4.0/), which permits non-commercial re-use, distribution, and reproduction in any medium, provided the original work is properly cited. For commercial re-use, please contact journals.permissions@oup.com Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 2 S. Chawla et al. about 90 per cent of world chickpea production (www.aicrchick- Nowadays, thanks to the awareness among consumers, serious rd pea.rs.in; accessed on 23 May, 2017). In India, it is also known concern is being expressed over the magnitude of pest control chemi- as Bengal gram and accounts for about 45 per cent of total pulses cals found in food stuffs following their use on crops. It is important produced in the country. Chickpea seeds are rich source of protein to ensure that the levels of harvest time residues of pesticides on food (17%–20%), fibre, minerals, and β- carotene. It also fixes the atmos- stuffs do not pose any hazard to consumers. Also with an increase pheric nitrogen (40 kg N/ha), thus reducing the need of nitrogenous in the international trade and to develop awareness in people, there fertilizers and form an important part of vegetarian diet. Chickpea is is a need for admissibility of these pesticides in domestic as well as an important Rabi crop mainly sown in September–November and international trade. harvested in February. Crop duration is 90–120 days, depending on β-Cyfluthrin has been registered in India for use on cotton against the variety and can be grown in heavy soils without and/or with bollworm, and a waiting period of 20 days has been recommended. minimum irrigation. Imidacloprid is registered for use on crops like cotton, rice, okra, There are two varieties of chickpea. Desi varieties are of short sunflower, sorghum, pearl millet, citrus, groundnut, chilly, mustard, duration, whereas Kabuli varieties take relatively a longer period to and sugarcane with waiting periods varying between 3 and 7 days mature. Diseases are the most serious constraints to chickpea produc- (www. cibrc.nic.in). Many combination products of β-cyfluthrin and tivity causing up to 100 per cent losses. Environmental factors and imidacloprid with other pesticides are also registered. However, the intensity of abiotic stresses are known to compound the occurrence combination product of these two pesticides together is still under and severity of the diseases. Although many diseases are reported, only investigation. Present study was undertaken to study the persistence a few such as wilt (Fusarium oxysporum), dry root rot (Rhizoctonia of these two pesticides in combination on chickpea under tropical bataticola), collar rot (Sclerotium rolfsii), wet root rot (Rhizoctonia conditions in Gujarat, India. solani), ascochyta blight (Ascochyta rabiae), botrytis grey mould (Botrytis cinerea), and chickpea stunt may cause major losses and pre- vent farmers from realizing the potential yield of chickpea (www.aicr- Materials and Methods chickpea.rs.in; accessed on 23 May 2017). Estimated losses (%) due to Sampling specific pests in chickpea crops are as follows: Gram pod borer (10%– A field experiment in a randomized block design using three repli- 90%), Gram cutworm (5%–30%), Termites (5%–15%), Semilooper cates for each treatment was conducted at the Agriculture Research (0%–10%), wilt rppt rot (20%–25%), Ascochyta blight (5%–10%), Station for irrigated crops, Anand Agricultural University, Thasara and Botrytis grey mould (5%–10%) (Chandrashekhar et  al., 2014). during Rabi season. Thasara lies in the central region of the Gujarat Annual losses due to insect pests of pulse crops account for 15%– which experience arid and humid weather. Three sprays of Solomon 20% in India. Major pest destroying the chickpea crop is Helicoverpa 300 OD, a combination product of β-cyfluthrin 9 per cent and imi- armigera, causing upto 100 per cent losses in India (Sehgal 1990). The dacloprid 21 per cent, were applied at 18  +  42 and 36  +  84  g a.i. avoidable losses due to insect pests have been estimated to be over US −1 ha at an interval of 1 week on chickpea plants using a Knapsack $14 billion annually (www.icrisat.org). sprayer. First spray was made at the initiation of pod, whereas the A few pesticides such as emamectin benzoate and lambda-cyhalo- last spray coincided with green pod stage. Water was sprayed in the thrin are registered to be used against pod borer in chickpea in India. control plot. Chickpea pods were drawn at 0 (1 h), 1, 3, 5, 7, 10, 15, Nonetheless, wanton usage of the pesticides has raised many prob- and 20 days after the last spray. Pods were at mature stage on the lems such as increased resistance, resurgence of pests, detection of 20th day. Soil samples were also analysed on the 20th day from the residues above safe level, and environmental hazards. As a result, last spray. During the trial, average minimum and maximum tem- there is a need for development of new pesticide combinations so that peratures were 14.17°C and 31.09°C with average humidity 55.65 environmental load can be decreased and there can be a substantial per cent. No rainfall was recorded. delay in development of resistance to these chemicals in pests. A number of combination products have been developed so far. Solomon 300 OD is a combination of β-cyfluthrin and imidacloprid and has been found to be effective. β-Cyfluthrin, cyano(4-fluoro- Green Pods 3-phenoxyphenyl) methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclo- Extraction propanecarboxylate, belonging to pyrethroid group, is a non-systemic A 50  g representative sample of homogenized chickpea pod was insecticide that acts as a contact and stomach poison and is an enriched extracted with 100 ml acetonitrile using a vertical homogenizer for isomeric form of two biologically active diastereomeric pairs of iso- 3 min. The extract was filtered through a Buchner funnel. A 100 ml mers of cyfluthrin (http://www.cdpr.ca.gov/docs/emon/pubs/fatememo/ extract was taken in a glass stopper cylinder. The filtrate was salted cyflthrn.pdf). It has an ether and ester linkage besides dichlorovinyl out with sodium chloride. An aliquot of filtrate representing 12.5 g group attached to a cyclopropane moiety. Presence of a carbon-fluoride of sample (25  ml) was taken for β-cyfluthrin and 10  g of sample bond helps it in overcoming resistance development in insects by the (20 ml) for imidacloprid and was reduced under nitrogen (Turbovap) use of xenobiotic (Naumann, 1998). Imidacloprid, N-[1-[(6-chloro- to 2.0 ml for β-cyfluthrin and to dryness for imidacloprid (Pesticide 3-pyridyl) methyl]-4, 5-dihydroimidazol-2-yl] nitramide, is a broad Analytical Manual, 1999). spectrum systemic insecticide effective against wide range of pests. Bioefficacy studies of these compounds have shown imidacloprid to be effective against thrips in onion (Srinivas et al., 2012) and thrips and Cleanup lace bugs in avocado (Byrne et  al., 2010). Similarly, β-cyfluthrin has β-Cyfluthrin been found to be effective against cruciferous pests such as Brevicoryne Cleanup was done using Florosil column. A  10  ml mixture of brassicae, Pieris brassicae, and Plutella xylostella in cabbage and cau- liflower (Singh et al., 2007). A bioefficacy study using combination of acetone:hexane was used for elution. The eluate was reduced to β-cyfluthrin and imidacloprid has been found effective for the control 2.0  ml under nitrogen and analysed by GLC (Pesticide Analytical of Amrasca biguttla and Leucinales orbonali (Bhargava et al., 2003). Manual, 1999). Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 Residue determination and risk assessment of beta-cyfluthrin and imidacloprid 3 Imidacloprid deviation (RSD), respectively (SANTE 2015). RSD was calculated as follows: The dried fraction was dissolved in acetone: hexane (1:1, v/v) and a pinch of PSA powder was added followed by vortexing for 30 s. RelativeStandardDeviationR () SD = Supernatant was decanted in another tube and brought to dry- Standard deviationS () DM ÷ ean n × 100 () ness under nitrogen. This was then dissolved in acetone: hexane (3:7, v/v) and loaded to 1 g silica column already saturated with As EU maximum residue limits (MRLs) for β-cyfluthrin and imida- acetone. The sample was allowed to pass. The column was then −1 cloprid in pulses are 0.02 and 2.0 μg g , limit of quantitation (LOQ) washed with acetone: hexane (3:7, v/v). This fraction was dis- −1 was taken as 0.01 μg g for both in chickpea. In soil, the LOQs were carded. The sample was then eluted with 10 ml of acetone:hexane −1 taken as 0.025 for β-cyfluthrin and at 0.05 μg g for imidacloprid. (4:6, v/v). Elute was evaporated to dryness under nitrogen and finally dissolved in methanol for analysis (Pesticide Analytical Calculations for analyte concentration, rate of Manual, 1999). reaction, and half-life The residues were calculated by comparing the peak areas of the Soil samples with those of matching standards run under same chroma- tographic conditions. Standards were prepared in linearity range and Extraction used for calculations. β-Cyfluthrin The dissipation kinetics of β-cyfluthrin and imidacloprid at stand- Twenty gram soil was extracted with hexane:acetone (1:1, v/v) for ard and double doses were calculated by plotting graphs between 6 h in Soxhlet. The extract was evaporated to near dryness and the concentration (or some function of concentration) and time. Three final volume was made for GLC analysis (Lang et al., 2005). graphs were made and conclusion about the rate of reaction was made as follows: Imidacloprid 1. C Vs t (best fit, if reaction is zero order); A 20  g representative soil was extracted with 20  ml of acetonitrile:water 2. log C Vs t (best fit, if reaction is first order); and (4:1, v/v) by shaking overnight. After centrifugation and evaporation, 3. 1/ C Vs t (best fit, if reaction is second order), the residues were dissolved in acetonitrile and analysed by high per- formance liquid chromatography (HPLC) (Lang et al., 2005). where C is the concentration at time t (Anonymous, 2016c). Half-life was calculated as described by Fantke and Juraske, 2013 and Hoskins, 1961. Instrumentation β-Cyfluthrin β-Cyfluthrin was determined on Shimadzu GC (Model: GC-2010) Calculations for Dietary Risk Assessment equipped with ECD-Ni . Column used was DB-5, 30 m × 2.5 mm Dietary risk assessment was calculated using hazard quotient (HQ) i.d., 0.25 μm film thickness with a split ratio of 1:5. Injector and (Lozowicka et  al., 2014; Fu et  al., 2016). Estimated daily intake detector temperatures were 210°C and 300°C, respectively. Oven (EDI) was calculated at the proposed pre-harvest interval (PHI) of 7 temperature was programmed from 160°C to 290°C with ramping and 10 days as follows: −1 of 7°C. Carrier gas was nitrogen at the flow rate of 1.5 ml min . At residueat proposed PHId × ailyconsumptionofchickpea this setting, retention time of β-cyfluthrin was 18.3 min. EDI = , bo odyweight () kg Imidacloprid and it was expressed as mg/kg bw/day (Lozowicka et  al., 2014). Imidacloprid was determined on Shimadzu LC-20AT HPLC Daily pulses consumption data were taken from NSSO, 2014. HQ equipped with photodiode array (PDA) detector and RP-18 e column was calculated as follows: (100  ×  4.6  mm i.d). The mobile phase used was water:acetonitrile EDI −1 HQ = , (65:35, v/v) at low pressure gradient with a flow of 0.6 ml min . At ADI 270 nm, absorbance retention time for imidacloprid was observed at where ADI is acceptable daily intake (http://www.fao.org/fao-who- 9.3 min. The residues were calculated by comparing the peak areas codexalimentarius/standards/pestres/pesticides/en/, accessed on 23 of the samples with that of matching standards run under same May 2017). HQ ≤ 1 was considered as safe (Malhat et  al., 2014; HPLC conditions. Ludwicki et al., 2015). Method Validation Results and Discussion To check the response, range, and linearity of these pesticides, cor- Linearity and recovery of β-cyfluthrin and relation coefficient was worked out by running standards at various −1 imidacloprid concentrations, i.e. 0.01, 0.05, 0.1, 0.5, and 1.0 mg kg by plotting linearity curves. Linearity plots for β-cyfluthrin and imidacloprid showed correlation Recovery studies were performed to check the method perfor- coefficient (R ) of 0.9909 and 0.9914, respectively, in the acceptable mance. Recoveries of β-cyfluthrin and imidacloprid were done at range (SANTE, 2015). −1 the level of 0.01 and 0.05 μg g in chickpea green pods and at the Recoveries of β-cyfluthrin and imidacloprid obtained at the level −1 −1 level of 0.025 for β-cyfluthrin and at 0.05  μg g for imidacloprid of 0.01 and 0.05 μg g in chickpea green pods and at the level of −1 in soil. Three replicates were taken at each spiking level. Accuracy 0.025 and 0.05 μg g in soil, respectively, are presented in Table 1. and precision were worked out as % recovery and relative standard The recoveries are in the acceptable range of 70%–120% and RSD Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 4 S. Chawla et al. Table  1. Recovery of β-cyfluthrin and imidacloprid from chickpea varying climatic conditions. β-Cyfluthrin being a contact pesticide pod and soil. is present at the surface; therefore, difference in persistence can be attributed to difference in the nature of commodity and variability −1 S. No. Fortification level (μg g ) Mean recovery (%) ± SD* in climatic conditions. Imidacloprid at standard dose revealed 45.9 per cent loss within Chickpea 24 h of application in chickpea pods, whereas at double dose the loss β-Cyfluthrin Imidacloprid was 19.63 per cent as shown in Table 2. The dissipation continued at relatively higher rate with time and showed 82.78 per cent and 91.85 1 0.01 92.87 ± 19.2 86.76 ± 13.4 per cent loss at standard and double doses by 10  days (Table  2). 2 0.05 82.89 ± 10.8 87.43 ± 14.1 From the 15th day onward, residues reached below determination Soil level at either dose of application. In studies done on mango, okra, and brinjal persisted till 10, 5, 7, and 10  days in different com- β-Cyfluthrin Imidacloprid modities (Mandal et al., 2010; Mohapatra et al., 2011; Sahoo et al., 1 0.025 79.71 ± 3.3 — 2012). Imidacloprid is a systemic pesticide. Once inside the system 2 0.05 — 101.87 ± 8.7 the degradation of pesticide is less influenced by climatic conditions. Hence, the persistence of imidacloprid was similar in most of the *Mean of three replicates. commodities with approximately 10 days in most of the cases. In soil, none of the pesticide was detected above detection limit is less than 20. Thus, based on the recovery study and RSD, the per- on the 20th day. Based on their low volatility and portioning ten- formance of the method adopted in this experiment was considered dency, both β-cyfluthrin and imidacloprid have been shown to have satisfactory for both β-cyfluthrin and imidacloprid (SANTE, 2015). low levels in clay soil (Leslie, 1988; Junior et al., 2004). Dissipation and Harvest Time Residue in Half-life and Pre-harvest Interval Chickpea and Soil Dissipation kinetics for β-cyfluthrin and imidacloprid has been shown Dissipation studies showed the presence of β-cyfluthrin and imida- in Table  3. The results revealed that dissipation of β-cyfluthrin at cloprid residues in the green pods immediately after application. The standard dose followed zero-order kinetics with half-life of 7.27  days initial deposits of β-cyfluthrin residues at standard and double doses (Table  3, Figure  1). This was observed because of almost similar levels −1 were 0.16 and 0.27 μg g , respectively. The corresponding initial of β-cyfluthrin from day 3 to day 7 after application in standard dose. −1 deposits of imidacloprid were 1.22 and 2.7 μg g . Earlier studies on However, in double dose, first-order kinetics gives best fit (Table  3, mango showed initial deposits of β-cyfluthrin of 0.04 and 0.12  μg Figure 1) with half-life of 9 days. Imidacloprid in both the doses showed −1 −1 g at the doses of 75 and 150 g a.i. ha , respectively (Mohapatra first-order kinetics with half-life of 6.7 and 7.7 days (Table 3, Figure 2). et al., 2011). The initial deposits of imidacloprid in the same study Earlier studies on dissipation of β-cyfluthrin and imidacloprid in chickpea −1 were 0.14 and 0.18, and 0.04 and 0.12 μg g at the doses of 75 and by Chahil et  al. (2014) from Punjab location showed half-life of 1.06 −1 150 g a.i. ha , respectively (Mohapatra et al., 2011). and 2.35 days for β-cyfluthrin and 2.07 and 2.31 days for imidacloprid, The difference in the initial deposits between β-cyfluthrin and respectively, at two different doses. Half-life of 2.4 and 2.6 days in mango, imidacloprid apparently reflected in the concentration present in the 0.98 and 0.68 days in okra, 1.83 days and 1.74 and 1.39 days in brinjal in formulation. β-Cyfluthrin being contact poison remains mainly on two doses has been reported in earlier studies (Singh et al., 2007; Mandal the surface of the pods, thereby showing a different dissipation pat- et al., 2010; Mohapatra et al., 2011; Sahoo et al., 2012) for β-cyfluthrin. tern compared with imidacloprid which is systemic in nature and These studies report half-life of 3.06 and 4.16 days in mango, 0.85 and penetrates the pods surface more rapidly. At standard dose, within 0.96 days in okra, 0.19 and 0.36 days in brinjal, and 2.31 and 2.18 days 24  h of application, β-cyfluthrin dissipated from 0.16 to 0.11  μg in brinjal, respectively, in two doses for imidacloprid. Longer half-lives in −1 g , resulting in only 31.25 per cent loss. The corresponding loss at the present study were due to dry weather and high temperature. As no higher dose was 11.11 per cent only. The slow rate of dissipation of rainfall was recorded during the study, there was no possibility of residue β-cyfluthrin in chickpea pods continued with time and reached below wash-off. At the same time, the pods were slightly dry at the later stages determination level on the 10th and 15th day at standard and double leading to longer persistence and longer half-life. doses, respectively. In fact from 3rd day onward, the levels remained On the basis of dissipation and persistence data from the present constant till 7th day as 43.75 per cent. This could be due to very study, a PHI of 15 days is proposed for β-cyfluthrin and imidaclo- low amount of β-cyfluthrin in standard dose (only 9 per cent in the prid, respectively. A  PHI of 8, 7, and 3  days has been reported in formulation). Due to an increase in temperature at the end of winter, mango, okra, and tomato, respectively, in earlier studies (Dikshit an increase in temperature led to little drying in the pods. This drying et al., 2003; Mohapatra et al., 2011; Sahoo et al., 2012). along with low amounts of β-cyfluthrin in initial formulation might have contributed to apparently slower degradation of β-cyfluthrin in standard dose. By 10th day, the residues of β-cyfluthrin were below Risk Assessment −1 determination level of 0.01 µg g in standard dose. At double dose, β-cyfluthrin lost to 55.55 per cent of the initial deposits on the 10th All human health risk situations are a function of hazard and expo- day and reached below determination level (BDL) on the 15th day. sure to it. If the hazard is small and fixed, then the risk will be propor - The studies on different commodities like mango, okra, and brinjal tional to the exposure, which can be reduced to low and occasional showed persistence of β-cyfluthrin varying from 3 to 7 days (Mandal (Bates, 2002). The actual exposure of any consumer to pesticide resi- et al., 2010; Mohapatra et al., 2011; Sahoo et al., 2012). India is a dues can theoretically be determined by the analysis of the consumer’s country with vast diversity of climatic conditions. These trials were total diet. In the present study, dietary risk assessment was done as taken at different locations which lie in different climatic zones with described in Materials and Methods and was expressed as HQ. Data Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 Residue determination and risk assessment of beta-cyfluthrin and imidacloprid 5 Table 2. Dissipation of β-cyfluthrin and imidacloprid in chickpea pod and soil. −1 −1 Days after application Residues (µg g )* of β-cyfluthrin ± SD (%loss) Residues (µg g )* of imidacloprid ± SD (%loss) −1 −1 −1 −1 Standard dose (18 g a.i. ha ) Double dose (36 g a.i. ha ) Standard dose (42 g a.i. ha ) Double dose (84 g a.i. ha ) Chickpea pod 0 0.16 ± 0.04 0.27 ± 0.08 1.22 ± 0.32 2.7 ± 0.29 1 0.11 ± 0.00 (31.25%) 0.24 ± 0.01 (11.11%) 0.66 ± 0.06 (45.9%) 2.17 ± 0.14 (19.63%) 3 0.09 ± 0.01 (43.75%) 0.21 ± 0.03 (22.22%) 0.57 ± 0.08 (53.28%) 0.94 ± 0.16 (65.19%) 5 0.09 ± 0.03 (43.75%) 0.16 ± 0.09 (40.74%) 0.26 ± 0.05 (78.69%) 0.38 ± 0.11 (85.92%) 7 0.09 ± 0.01 (43.75%) 0.14 ± 0.00 (48.15%) 0.23 ± 0.02 (81.15%) 0.25 ± 0.08 (90.74%) 10 BDL** 0.12 ± 0.01 (55.55%) 0.21 ± 0.02 (82.78%) 0.22 ± 0.03 (91.85%) 15 BDL BDL BDL BDL 20 BDL BDL BDL BDL Soil 20 BDL BDL BDL BDL *Average of three replicates. −1 **BDL = Below determination level, i.e. <0.01 µg g . Table 3. Dissipation kinetics: Comparison of zero-order, first-order, and second-order kinetics (values in bold show the best fit). β-Cyfluthrin Standard dose Double dose 2 2 Regression equation R Half-life Regression equation R Half-life Zero order y = −0.011x + 0.142 0.812 7.27 y = 0.015x + 0.256 0.946 9.00 First Order y = −119x + 1.316 0.670 8.85 y = −0.036x + 1.418 0.976 9.12 Second Order y = 15.39x + 25.26 0.562 0.41 y = −0.478x + 3.651 0.988 0.56 Imidacloprid Standard dose Double dose 2 2 Regression equation R Half-life Regression equation R Half-life Zero order y = −0.087x + 0.905 0.725 7.01 y = −0.252x + 2.204 0.792 11.45 First order y = −0.075x + 1.953 0.858 6.69 y = −0120x + 2.363 0.914 7.72 Second Order y = 0.423x + 1.006 0.913 2.88 y = 0.471x + 0.136 0.955 5.74 Figure 1. Dissipation kinetics for β-cyfluthrin at standard and double doses: (a) zero-order kinetics, (b) first-order kinetics, and (c) second-order kinetics (18 and −1 36 g a.i. ha , respectively). for risk assessment are shown in Table  3. No MRLs are available is consumed as pulse as well as flour in various food preparations for β-cyfluthrin and imidacloprid in chickpea. However, MRLs for including snacks, sweets, and in various desserts in India by both rural −1 pulses in EU and codex for imidacloprid are 2.0 µg g and in EU for and urban Indian population. The HQ was less than 1 for both rural −1 β-cyfluthrin is 0.02  µg g . MRLs are neither available for pulses nor and urban population (Table 4), suggesting that the use of combina- for chickpea in India. The levels of imidacloprid are never above MRL tion product of β-cyfluthrin on chickpea pods is safe provided that the in the present study and reached to a significantly low level at PHI. As proper PHI is followed. Earlier studies have also recommended the use MRLs are not available for either of the pesticide in chickpea, theo- of combination product of β-cyfluthrin and imidacloprid in various retical risk was assessed. It was important to assess risk as chickpea commodities provided proper PHI is followed. Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 6 S. Chawla et al. Figure 2. Dissipation kinetics for imidacloprid at standard and double doses: (a) zero-order kinetics, (b) first-order kinetics, and (c) second-order kinetics (18 and −1 36 g a.i. ha , respectively). Table 4. Dietary risk assessment by hazard quotient (HQ) method in chickpea at pre-harvest interval (PHI) of 7 days (for β-cyfluthrin) and 10 days (for imidacloprid; average body weight = 60 kg). −6 −6 Pesticide Dose Residue Dietary intake Dietary intake EDI (× 10 mg/kg EDI (× 10 mg /kg bw/ ADI HQ HQ −1 (mg kg ) (kg) (rural) (kg) (urban) bw/day) (rural) day) (urban) (mg/kg) (rural) (urban) β-Cyfluthrin Standard dose 0.09 0.0261 0.03003 0.000039 0.000045 0.04 0.0010 0.0011 Double dose 0.12 0.0261 0.03003 0.000052 0.000060 0.04 0.0013 0.0015 Imidacloprid Standard dose 0.21 0.0261 0.03003 0.000091 0.000105 0.06 0.0015 0.0018 Double dose 0.22 0.0261 0.03003 0.000096 0.000110 0.06 0.0016 0.0018 Chandrashekhar, K., et al. (2014). Integrated Pest Management for Chickpea, Conclusion pp. 43. The present data show that dissipation kinetics of β-cyfluthrin Dikshit, A. K., Pachauri, D. C., Jindal, T. (2003). Maximum residue limit showed best fit in zero order and first order at standard and dou- and risk assessment of beta-cyfluthrin and imidacloprid on tomato ble doses, respectively. For imidacloprid, first-order kinetics was (Lycopersicon esculentum mill). Bulletin of Environmental Contamination observed at both the doses. The residues reached below deter- and Toxicology, 70: 1143–1150. −1 Fantke, P., Juraske, R. (2013). Variability of pesticide dissipation half-lives in mination level of 0.01 µg g on the 10th day after application of plants. Environmental Science & Technology, 47: 3548–3562. β-cyfluthrin at standard dose and on the 15th day after application Fu, Y., Zheng, Z., Wei, P., Wang, M., Zhu, Z., Liu, Y. (2016). Distribution of in all other cases. HQ is less than 1 in all the cases. Therefore, the thifluzamide, fenoxanil and tebuconazole in rice paddy and dietary risk combination product of β-cyfluthrin and imidacloprid can be used assessment. Toxicological and environmental Chemistry, 98: 118–127 in chickpea safely following a PHI of 15 days. As the residues were Hoskins, W. M. (1961). Mathematical treatment of the rate of loss of pesticide below determination level in soil, it can be concluded that combina- residues. FAO Plant Protection Bulletin, 9: 163–168 tion product does not pose any environmental threat. There are no ICMR. (2010). Indian Council of Medical Research, http://icmr.nic.in/final/ established MRLs for imidacloprid and β-cyfluthrin on chickpea in rda-2010.pdf. India and in codex; hence, present data along with other studies can Júnior, R. P., Smelt, J. H., Boesten, J. J., Hendriks, R. F., van der Zee, S. E. be used for the MRL establishment for these compounds in India. (2004). Preferential flow of bromide, bentazon, and imidacloprid in a Dutch clay soil. Journal of Environmental Quality, 33: 1473–1486. Lang, Y., Cao, Z., Nie, X. (2005). Extraction of organochlorine pesticides in Acknowledgements sediments using soxhlet, ultrasonic and accelerated solvent extraction The authors are thankful to Indian Council of Agricultural Research for finan- techniques. Journal of Ocean University of China, 4: 173. cial assistance and M/s Bayer Cropscience for sponsoring the project. Leslie, W. (1988). Baythroid—residues in field rotational cereal crops. Mobay Chemical Corp. Report No. 98429 References Lozowicka, B., et  al. (2014). Pesticide residues in grain from Kazakhstan Bates, R. (2002). Pesticide residues and risk assessment. Pesticide Outlook, and potential health risks associated with exposure to detected pes- 13:142 ticides. Food and Chemical Toxicology: An International Journal Bhargava, K. K., Bhatnagar, A., Sharma, H. C. (2003). Bioefficacy of imida- Published for the British Industrial Biological Research Association, cloprid and beta-cyfluthrin for the management of insect pests of brinjal. 64: 238–248. Indian Journal of Plant Protection, 31:111–113. Ludwicki, J. K., et  al. (2015) Hazard quotient profiles used as a risk assess- Byrne, F. J., Humeres, E. C., Urena, A. A., Hoddle, M. S., Morse, J. G. (2010). ment tool for PFOS and PFOA serum levels in three distinctive European Field evaluation of systemic imidacloprid for the management of avo- populations. Environment International, 74: 112–118. cado thrips and avocado lace bug in California avocado groves. Pest Malhat, F. M., El Sharkawi, H. M., Loufty, N. M., Ahmed, M. T. (2014) Field Management Science, 66: 1129–1136. dissipation and health hazard assessment of fenhexamid on Egyptian Chahil, G. S., Mandal, K., Sahoo, S. K., Battu, R. S., Singh, B. (2014). Risk grape. Toxicology and Environmental Chemistry, 96: 722–729 assessment of β-cyfluthrin and imidacloprid in chickpea pods and leaves. Mandal, K., Chahil, G. S., Sahoo, S. K., Battu, R. S., Singh, B. (2010). Ecotoxicology and Environmental Safety, 101: 177–183. Dissipation kinetics of beta-cyfluthrin and imidacloprid in brinjal and soil Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 Residue determination and risk assessment of beta-cyfluthrin and imidacloprid 7 under subtropical conditions of Punjab, India. Bulletin of Environmental Health. Part. B, Pesticides, Food Contaminants, and Agricultural Wastes, Contamination and Toxicology, 84: 225–229. 47: 42–50. Mohapatra, S., Deepa, M., Jagadish, G. K. (2011). Behavior of beta cyfluthrin SANTE (2015) European Union Guidance Document on Analytical Quality and imidacloprid in/on mango (mangifera indica L.). Bulletin of Control and Method Validation Procedures for Pesticide Residues Analysis Environmental Contamination and Toxicology, 87: 202–207. in Food and Feed. Document No. SANTE/11945/2015, http://www.eurl- Naumann, K. (1998). Research into fluorinated pyrethroid alcohols an episode pesticides.eu/library/docs/allcrl/AqcGuidance_SANTE_2015_11945.pdf. in the history of pyrethroids discovery. Pesticide Science, 52:3–4. Sehgal, V. K. (1990). Damage yield relationship due to H. armigera larvae NSSO (2014). Household Consumption of Various Goods and Services in chickpea in India. In: Proceeding of the Second International Workshop in India 2011–12, NSS 68th Round. National Sample Survey Office, on  Chickpea Improvement, Chickpea in Nineties, ICARDA/ ICRISAT, Ministry of Statistics and Programme Implementation, Government of 4–8 December 1989. ICRISAT Centre, Patenchery, AP, India. India. Singh, R. R., Patyal, S. K., Thakur, M. (2007) Efficacy of beta-cyfluthrin against Pesticide Analytical Manual (PAM) (1999). Multiclass multiresidue methods, cruciferous pests. Pest Manage. Horticulute and. Ecosystem, 13:146–152. chapter 3, U.S. Food and Drug Administration. Srinivas, P. S., Banerjee, K., Jadhav, M. R., Ghaste, M. S., Lawande, K. E. (2012). Sahoo, S. K., Chahil, G. S., Mandal, K., Battu, R. S., Singh, B. (2012). Bioefficacy, dissipation kinetics and safety evaluation of selected insecti- Estimation of β-cyfluthrin and imidacloprid in okra fruits and soil by cides in allium cepa L. Journal of Environmental Science and Health. Part. chromatography techniques. Journal of Environmental Science and B, Pesticides, Food Contaminants, and Agricultural Wastes, 47: 700–709. Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Food Quality and Safety Oxford University Press

Residue determination of β-cyfluthrin and imidacloprid as mix formulation in/on chickpea (Cicer arietinum) pods and soil and its risk assessment

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Oxford University Press
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Abstract

OBJECTIVES: A field experiment was conducted at Agricultural Research Station for irrigated crops at Thasara, Anand Agricultural University, Anand, to study the dissipation and risk assessment of β-cyfluthrin and imidacloprid as combination product in/on chickpea. MATERIALS AND METHODS: Solomon 300 OD comprising 9 per cent β-cyfluthrin and 21 per cent −1 −1 imidacloprid was foliar sprayed at the doses of 18 + 42g a.i. ha (standard dose) and 36 + 84g a.i. ha (double dose). Totally three sprays were made at an interval of 1 week starting from fruiting stage. RESULTS AND DISCUSSIONS: The residues of β-cyfluthrin estimated using gas chromatograph with −1 electron capture detector (GC-ECD) showed an initial deposit of 0.16 and 0.27 μg g in standard and double doses, respectively. The residues for corresponding doses persisted till 7th and 10th −1 day after application and reached below determination level of 0.01μg g on the 10th and 15th day, respectively. Imidacloprid was estimated using high performance liquid chromatography (HPLC) and −1 showed initial deposits of 1.22 and 2.7 μg g in standard and double doses, respectively. Its levels −1 reached below the determination level (0.01 μg g ) on the 15th day in green pods. Statistical analysis of dissipation kinetics showed that β-cyfluthrin followed zero-order kinetics in standard dose with half-life of 7.27 days. In double dose, the dissipation kinetics followed first-order kinetics with half-life of 9 days. Imidacloprid followed first-order kinetics in both the doses with half-life of 6.7 and 7.7 days. CONCLUSIONS: A pre-harvest interval (PHI) of 15 days is suggested. Theoretical risk assessment calculated as hazard quotient was less than 1, rendering the use of combination product as safe- provided proper PHI is followed. Key words: chickpea; β-cyfluthrin; imidacloprid; dissipation; dissipation kinetics; residue; risk assessment; pods. production of chickpea was about 12 million metric tons in 2011 Introduction (www.aicrchickpea.rs.in; accessed on 23 May 2017). India is the Chickpea (Cicer arietinum L.) is the third most important pulse largest producer with about 8 million tons, accounting of about 75 crop, after dry bean and peas in the world and accounts for 20 per cent of total world production. Six countries including India, per cent of the world pulses production. As per the latest available Australia, Turkey, Myanmar, Pakistan, and Ethiopia account for estimates of Food and Agricultural Organization (FAO), the global © The Author(s) 2018. Published by Oxford University Press on behalf of Zhejiang University Press. This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/4.0/), which permits non-commercial re-use, distribution, and reproduction in any medium, provided the original work is properly cited. For commercial re-use, please contact journals.permissions@oup.com Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 2 S. Chawla et al. about 90 per cent of world chickpea production (www.aicrchick- Nowadays, thanks to the awareness among consumers, serious rd pea.rs.in; accessed on 23 May, 2017). In India, it is also known concern is being expressed over the magnitude of pest control chemi- as Bengal gram and accounts for about 45 per cent of total pulses cals found in food stuffs following their use on crops. It is important produced in the country. Chickpea seeds are rich source of protein to ensure that the levels of harvest time residues of pesticides on food (17%–20%), fibre, minerals, and β- carotene. It also fixes the atmos- stuffs do not pose any hazard to consumers. Also with an increase pheric nitrogen (40 kg N/ha), thus reducing the need of nitrogenous in the international trade and to develop awareness in people, there fertilizers and form an important part of vegetarian diet. Chickpea is is a need for admissibility of these pesticides in domestic as well as an important Rabi crop mainly sown in September–November and international trade. harvested in February. Crop duration is 90–120 days, depending on β-Cyfluthrin has been registered in India for use on cotton against the variety and can be grown in heavy soils without and/or with bollworm, and a waiting period of 20 days has been recommended. minimum irrigation. Imidacloprid is registered for use on crops like cotton, rice, okra, There are two varieties of chickpea. Desi varieties are of short sunflower, sorghum, pearl millet, citrus, groundnut, chilly, mustard, duration, whereas Kabuli varieties take relatively a longer period to and sugarcane with waiting periods varying between 3 and 7 days mature. Diseases are the most serious constraints to chickpea produc- (www. cibrc.nic.in). Many combination products of β-cyfluthrin and tivity causing up to 100 per cent losses. Environmental factors and imidacloprid with other pesticides are also registered. However, the intensity of abiotic stresses are known to compound the occurrence combination product of these two pesticides together is still under and severity of the diseases. Although many diseases are reported, only investigation. Present study was undertaken to study the persistence a few such as wilt (Fusarium oxysporum), dry root rot (Rhizoctonia of these two pesticides in combination on chickpea under tropical bataticola), collar rot (Sclerotium rolfsii), wet root rot (Rhizoctonia conditions in Gujarat, India. solani), ascochyta blight (Ascochyta rabiae), botrytis grey mould (Botrytis cinerea), and chickpea stunt may cause major losses and pre- vent farmers from realizing the potential yield of chickpea (www.aicr- Materials and Methods chickpea.rs.in; accessed on 23 May 2017). Estimated losses (%) due to Sampling specific pests in chickpea crops are as follows: Gram pod borer (10%– A field experiment in a randomized block design using three repli- 90%), Gram cutworm (5%–30%), Termites (5%–15%), Semilooper cates for each treatment was conducted at the Agriculture Research (0%–10%), wilt rppt rot (20%–25%), Ascochyta blight (5%–10%), Station for irrigated crops, Anand Agricultural University, Thasara and Botrytis grey mould (5%–10%) (Chandrashekhar et  al., 2014). during Rabi season. Thasara lies in the central region of the Gujarat Annual losses due to insect pests of pulse crops account for 15%– which experience arid and humid weather. Three sprays of Solomon 20% in India. Major pest destroying the chickpea crop is Helicoverpa 300 OD, a combination product of β-cyfluthrin 9 per cent and imi- armigera, causing upto 100 per cent losses in India (Sehgal 1990). The dacloprid 21 per cent, were applied at 18  +  42 and 36  +  84  g a.i. avoidable losses due to insect pests have been estimated to be over US −1 ha at an interval of 1 week on chickpea plants using a Knapsack $14 billion annually (www.icrisat.org). sprayer. First spray was made at the initiation of pod, whereas the A few pesticides such as emamectin benzoate and lambda-cyhalo- last spray coincided with green pod stage. Water was sprayed in the thrin are registered to be used against pod borer in chickpea in India. control plot. Chickpea pods were drawn at 0 (1 h), 1, 3, 5, 7, 10, 15, Nonetheless, wanton usage of the pesticides has raised many prob- and 20 days after the last spray. Pods were at mature stage on the lems such as increased resistance, resurgence of pests, detection of 20th day. Soil samples were also analysed on the 20th day from the residues above safe level, and environmental hazards. As a result, last spray. During the trial, average minimum and maximum tem- there is a need for development of new pesticide combinations so that peratures were 14.17°C and 31.09°C with average humidity 55.65 environmental load can be decreased and there can be a substantial per cent. No rainfall was recorded. delay in development of resistance to these chemicals in pests. A number of combination products have been developed so far. Solomon 300 OD is a combination of β-cyfluthrin and imidacloprid and has been found to be effective. β-Cyfluthrin, cyano(4-fluoro- Green Pods 3-phenoxyphenyl) methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclo- Extraction propanecarboxylate, belonging to pyrethroid group, is a non-systemic A 50  g representative sample of homogenized chickpea pod was insecticide that acts as a contact and stomach poison and is an enriched extracted with 100 ml acetonitrile using a vertical homogenizer for isomeric form of two biologically active diastereomeric pairs of iso- 3 min. The extract was filtered through a Buchner funnel. A 100 ml mers of cyfluthrin (http://www.cdpr.ca.gov/docs/emon/pubs/fatememo/ extract was taken in a glass stopper cylinder. The filtrate was salted cyflthrn.pdf). It has an ether and ester linkage besides dichlorovinyl out with sodium chloride. An aliquot of filtrate representing 12.5 g group attached to a cyclopropane moiety. Presence of a carbon-fluoride of sample (25  ml) was taken for β-cyfluthrin and 10  g of sample bond helps it in overcoming resistance development in insects by the (20 ml) for imidacloprid and was reduced under nitrogen (Turbovap) use of xenobiotic (Naumann, 1998). Imidacloprid, N-[1-[(6-chloro- to 2.0 ml for β-cyfluthrin and to dryness for imidacloprid (Pesticide 3-pyridyl) methyl]-4, 5-dihydroimidazol-2-yl] nitramide, is a broad Analytical Manual, 1999). spectrum systemic insecticide effective against wide range of pests. Bioefficacy studies of these compounds have shown imidacloprid to be effective against thrips in onion (Srinivas et al., 2012) and thrips and Cleanup lace bugs in avocado (Byrne et  al., 2010). Similarly, β-cyfluthrin has β-Cyfluthrin been found to be effective against cruciferous pests such as Brevicoryne Cleanup was done using Florosil column. A  10  ml mixture of brassicae, Pieris brassicae, and Plutella xylostella in cabbage and cau- liflower (Singh et al., 2007). A bioefficacy study using combination of acetone:hexane was used for elution. The eluate was reduced to β-cyfluthrin and imidacloprid has been found effective for the control 2.0  ml under nitrogen and analysed by GLC (Pesticide Analytical of Amrasca biguttla and Leucinales orbonali (Bhargava et al., 2003). Manual, 1999). Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 Residue determination and risk assessment of beta-cyfluthrin and imidacloprid 3 Imidacloprid deviation (RSD), respectively (SANTE 2015). RSD was calculated as follows: The dried fraction was dissolved in acetone: hexane (1:1, v/v) and a pinch of PSA powder was added followed by vortexing for 30 s. RelativeStandardDeviationR () SD = Supernatant was decanted in another tube and brought to dry- Standard deviationS () DM ÷ ean n × 100 () ness under nitrogen. This was then dissolved in acetone: hexane (3:7, v/v) and loaded to 1 g silica column already saturated with As EU maximum residue limits (MRLs) for β-cyfluthrin and imida- acetone. The sample was allowed to pass. The column was then −1 cloprid in pulses are 0.02 and 2.0 μg g , limit of quantitation (LOQ) washed with acetone: hexane (3:7, v/v). This fraction was dis- −1 was taken as 0.01 μg g for both in chickpea. In soil, the LOQs were carded. The sample was then eluted with 10 ml of acetone:hexane −1 taken as 0.025 for β-cyfluthrin and at 0.05 μg g for imidacloprid. (4:6, v/v). Elute was evaporated to dryness under nitrogen and finally dissolved in methanol for analysis (Pesticide Analytical Calculations for analyte concentration, rate of Manual, 1999). reaction, and half-life The residues were calculated by comparing the peak areas of the Soil samples with those of matching standards run under same chroma- tographic conditions. Standards were prepared in linearity range and Extraction used for calculations. β-Cyfluthrin The dissipation kinetics of β-cyfluthrin and imidacloprid at stand- Twenty gram soil was extracted with hexane:acetone (1:1, v/v) for ard and double doses were calculated by plotting graphs between 6 h in Soxhlet. The extract was evaporated to near dryness and the concentration (or some function of concentration) and time. Three final volume was made for GLC analysis (Lang et al., 2005). graphs were made and conclusion about the rate of reaction was made as follows: Imidacloprid 1. C Vs t (best fit, if reaction is zero order); A 20  g representative soil was extracted with 20  ml of acetonitrile:water 2. log C Vs t (best fit, if reaction is first order); and (4:1, v/v) by shaking overnight. After centrifugation and evaporation, 3. 1/ C Vs t (best fit, if reaction is second order), the residues were dissolved in acetonitrile and analysed by high per- formance liquid chromatography (HPLC) (Lang et al., 2005). where C is the concentration at time t (Anonymous, 2016c). Half-life was calculated as described by Fantke and Juraske, 2013 and Hoskins, 1961. Instrumentation β-Cyfluthrin β-Cyfluthrin was determined on Shimadzu GC (Model: GC-2010) Calculations for Dietary Risk Assessment equipped with ECD-Ni . Column used was DB-5, 30 m × 2.5 mm Dietary risk assessment was calculated using hazard quotient (HQ) i.d., 0.25 μm film thickness with a split ratio of 1:5. Injector and (Lozowicka et  al., 2014; Fu et  al., 2016). Estimated daily intake detector temperatures were 210°C and 300°C, respectively. Oven (EDI) was calculated at the proposed pre-harvest interval (PHI) of 7 temperature was programmed from 160°C to 290°C with ramping and 10 days as follows: −1 of 7°C. Carrier gas was nitrogen at the flow rate of 1.5 ml min . At residueat proposed PHId × ailyconsumptionofchickpea this setting, retention time of β-cyfluthrin was 18.3 min. EDI = , bo odyweight () kg Imidacloprid and it was expressed as mg/kg bw/day (Lozowicka et  al., 2014). Imidacloprid was determined on Shimadzu LC-20AT HPLC Daily pulses consumption data were taken from NSSO, 2014. HQ equipped with photodiode array (PDA) detector and RP-18 e column was calculated as follows: (100  ×  4.6  mm i.d). The mobile phase used was water:acetonitrile EDI −1 HQ = , (65:35, v/v) at low pressure gradient with a flow of 0.6 ml min . At ADI 270 nm, absorbance retention time for imidacloprid was observed at where ADI is acceptable daily intake (http://www.fao.org/fao-who- 9.3 min. The residues were calculated by comparing the peak areas codexalimentarius/standards/pestres/pesticides/en/, accessed on 23 of the samples with that of matching standards run under same May 2017). HQ ≤ 1 was considered as safe (Malhat et  al., 2014; HPLC conditions. Ludwicki et al., 2015). Method Validation Results and Discussion To check the response, range, and linearity of these pesticides, cor- Linearity and recovery of β-cyfluthrin and relation coefficient was worked out by running standards at various −1 imidacloprid concentrations, i.e. 0.01, 0.05, 0.1, 0.5, and 1.0 mg kg by plotting linearity curves. Linearity plots for β-cyfluthrin and imidacloprid showed correlation Recovery studies were performed to check the method perfor- coefficient (R ) of 0.9909 and 0.9914, respectively, in the acceptable mance. Recoveries of β-cyfluthrin and imidacloprid were done at range (SANTE, 2015). −1 the level of 0.01 and 0.05 μg g in chickpea green pods and at the Recoveries of β-cyfluthrin and imidacloprid obtained at the level −1 −1 level of 0.025 for β-cyfluthrin and at 0.05  μg g for imidacloprid of 0.01 and 0.05 μg g in chickpea green pods and at the level of −1 in soil. Three replicates were taken at each spiking level. Accuracy 0.025 and 0.05 μg g in soil, respectively, are presented in Table 1. and precision were worked out as % recovery and relative standard The recoveries are in the acceptable range of 70%–120% and RSD Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 4 S. Chawla et al. Table  1. Recovery of β-cyfluthrin and imidacloprid from chickpea varying climatic conditions. β-Cyfluthrin being a contact pesticide pod and soil. is present at the surface; therefore, difference in persistence can be attributed to difference in the nature of commodity and variability −1 S. No. Fortification level (μg g ) Mean recovery (%) ± SD* in climatic conditions. Imidacloprid at standard dose revealed 45.9 per cent loss within Chickpea 24 h of application in chickpea pods, whereas at double dose the loss β-Cyfluthrin Imidacloprid was 19.63 per cent as shown in Table 2. The dissipation continued at relatively higher rate with time and showed 82.78 per cent and 91.85 1 0.01 92.87 ± 19.2 86.76 ± 13.4 per cent loss at standard and double doses by 10  days (Table  2). 2 0.05 82.89 ± 10.8 87.43 ± 14.1 From the 15th day onward, residues reached below determination Soil level at either dose of application. In studies done on mango, okra, and brinjal persisted till 10, 5, 7, and 10  days in different com- β-Cyfluthrin Imidacloprid modities (Mandal et al., 2010; Mohapatra et al., 2011; Sahoo et al., 1 0.025 79.71 ± 3.3 — 2012). Imidacloprid is a systemic pesticide. Once inside the system 2 0.05 — 101.87 ± 8.7 the degradation of pesticide is less influenced by climatic conditions. Hence, the persistence of imidacloprid was similar in most of the *Mean of three replicates. commodities with approximately 10 days in most of the cases. In soil, none of the pesticide was detected above detection limit is less than 20. Thus, based on the recovery study and RSD, the per- on the 20th day. Based on their low volatility and portioning ten- formance of the method adopted in this experiment was considered dency, both β-cyfluthrin and imidacloprid have been shown to have satisfactory for both β-cyfluthrin and imidacloprid (SANTE, 2015). low levels in clay soil (Leslie, 1988; Junior et al., 2004). Dissipation and Harvest Time Residue in Half-life and Pre-harvest Interval Chickpea and Soil Dissipation kinetics for β-cyfluthrin and imidacloprid has been shown Dissipation studies showed the presence of β-cyfluthrin and imida- in Table  3. The results revealed that dissipation of β-cyfluthrin at cloprid residues in the green pods immediately after application. The standard dose followed zero-order kinetics with half-life of 7.27  days initial deposits of β-cyfluthrin residues at standard and double doses (Table  3, Figure  1). This was observed because of almost similar levels −1 were 0.16 and 0.27 μg g , respectively. The corresponding initial of β-cyfluthrin from day 3 to day 7 after application in standard dose. −1 deposits of imidacloprid were 1.22 and 2.7 μg g . Earlier studies on However, in double dose, first-order kinetics gives best fit (Table  3, mango showed initial deposits of β-cyfluthrin of 0.04 and 0.12  μg Figure 1) with half-life of 9 days. Imidacloprid in both the doses showed −1 −1 g at the doses of 75 and 150 g a.i. ha , respectively (Mohapatra first-order kinetics with half-life of 6.7 and 7.7 days (Table 3, Figure 2). et al., 2011). The initial deposits of imidacloprid in the same study Earlier studies on dissipation of β-cyfluthrin and imidacloprid in chickpea −1 were 0.14 and 0.18, and 0.04 and 0.12 μg g at the doses of 75 and by Chahil et  al. (2014) from Punjab location showed half-life of 1.06 −1 150 g a.i. ha , respectively (Mohapatra et al., 2011). and 2.35 days for β-cyfluthrin and 2.07 and 2.31 days for imidacloprid, The difference in the initial deposits between β-cyfluthrin and respectively, at two different doses. Half-life of 2.4 and 2.6 days in mango, imidacloprid apparently reflected in the concentration present in the 0.98 and 0.68 days in okra, 1.83 days and 1.74 and 1.39 days in brinjal in formulation. β-Cyfluthrin being contact poison remains mainly on two doses has been reported in earlier studies (Singh et al., 2007; Mandal the surface of the pods, thereby showing a different dissipation pat- et al., 2010; Mohapatra et al., 2011; Sahoo et al., 2012) for β-cyfluthrin. tern compared with imidacloprid which is systemic in nature and These studies report half-life of 3.06 and 4.16 days in mango, 0.85 and penetrates the pods surface more rapidly. At standard dose, within 0.96 days in okra, 0.19 and 0.36 days in brinjal, and 2.31 and 2.18 days 24  h of application, β-cyfluthrin dissipated from 0.16 to 0.11  μg in brinjal, respectively, in two doses for imidacloprid. Longer half-lives in −1 g , resulting in only 31.25 per cent loss. The corresponding loss at the present study were due to dry weather and high temperature. As no higher dose was 11.11 per cent only. The slow rate of dissipation of rainfall was recorded during the study, there was no possibility of residue β-cyfluthrin in chickpea pods continued with time and reached below wash-off. At the same time, the pods were slightly dry at the later stages determination level on the 10th and 15th day at standard and double leading to longer persistence and longer half-life. doses, respectively. In fact from 3rd day onward, the levels remained On the basis of dissipation and persistence data from the present constant till 7th day as 43.75 per cent. This could be due to very study, a PHI of 15 days is proposed for β-cyfluthrin and imidaclo- low amount of β-cyfluthrin in standard dose (only 9 per cent in the prid, respectively. A  PHI of 8, 7, and 3  days has been reported in formulation). Due to an increase in temperature at the end of winter, mango, okra, and tomato, respectively, in earlier studies (Dikshit an increase in temperature led to little drying in the pods. This drying et al., 2003; Mohapatra et al., 2011; Sahoo et al., 2012). along with low amounts of β-cyfluthrin in initial formulation might have contributed to apparently slower degradation of β-cyfluthrin in standard dose. By 10th day, the residues of β-cyfluthrin were below Risk Assessment −1 determination level of 0.01 µg g in standard dose. At double dose, β-cyfluthrin lost to 55.55 per cent of the initial deposits on the 10th All human health risk situations are a function of hazard and expo- day and reached below determination level (BDL) on the 15th day. sure to it. If the hazard is small and fixed, then the risk will be propor - The studies on different commodities like mango, okra, and brinjal tional to the exposure, which can be reduced to low and occasional showed persistence of β-cyfluthrin varying from 3 to 7 days (Mandal (Bates, 2002). The actual exposure of any consumer to pesticide resi- et al., 2010; Mohapatra et al., 2011; Sahoo et al., 2012). India is a dues can theoretically be determined by the analysis of the consumer’s country with vast diversity of climatic conditions. These trials were total diet. In the present study, dietary risk assessment was done as taken at different locations which lie in different climatic zones with described in Materials and Methods and was expressed as HQ. Data Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 Residue determination and risk assessment of beta-cyfluthrin and imidacloprid 5 Table 2. Dissipation of β-cyfluthrin and imidacloprid in chickpea pod and soil. −1 −1 Days after application Residues (µg g )* of β-cyfluthrin ± SD (%loss) Residues (µg g )* of imidacloprid ± SD (%loss) −1 −1 −1 −1 Standard dose (18 g a.i. ha ) Double dose (36 g a.i. ha ) Standard dose (42 g a.i. ha ) Double dose (84 g a.i. ha ) Chickpea pod 0 0.16 ± 0.04 0.27 ± 0.08 1.22 ± 0.32 2.7 ± 0.29 1 0.11 ± 0.00 (31.25%) 0.24 ± 0.01 (11.11%) 0.66 ± 0.06 (45.9%) 2.17 ± 0.14 (19.63%) 3 0.09 ± 0.01 (43.75%) 0.21 ± 0.03 (22.22%) 0.57 ± 0.08 (53.28%) 0.94 ± 0.16 (65.19%) 5 0.09 ± 0.03 (43.75%) 0.16 ± 0.09 (40.74%) 0.26 ± 0.05 (78.69%) 0.38 ± 0.11 (85.92%) 7 0.09 ± 0.01 (43.75%) 0.14 ± 0.00 (48.15%) 0.23 ± 0.02 (81.15%) 0.25 ± 0.08 (90.74%) 10 BDL** 0.12 ± 0.01 (55.55%) 0.21 ± 0.02 (82.78%) 0.22 ± 0.03 (91.85%) 15 BDL BDL BDL BDL 20 BDL BDL BDL BDL Soil 20 BDL BDL BDL BDL *Average of three replicates. −1 **BDL = Below determination level, i.e. <0.01 µg g . Table 3. Dissipation kinetics: Comparison of zero-order, first-order, and second-order kinetics (values in bold show the best fit). β-Cyfluthrin Standard dose Double dose 2 2 Regression equation R Half-life Regression equation R Half-life Zero order y = −0.011x + 0.142 0.812 7.27 y = 0.015x + 0.256 0.946 9.00 First Order y = −119x + 1.316 0.670 8.85 y = −0.036x + 1.418 0.976 9.12 Second Order y = 15.39x + 25.26 0.562 0.41 y = −0.478x + 3.651 0.988 0.56 Imidacloprid Standard dose Double dose 2 2 Regression equation R Half-life Regression equation R Half-life Zero order y = −0.087x + 0.905 0.725 7.01 y = −0.252x + 2.204 0.792 11.45 First order y = −0.075x + 1.953 0.858 6.69 y = −0120x + 2.363 0.914 7.72 Second Order y = 0.423x + 1.006 0.913 2.88 y = 0.471x + 0.136 0.955 5.74 Figure 1. Dissipation kinetics for β-cyfluthrin at standard and double doses: (a) zero-order kinetics, (b) first-order kinetics, and (c) second-order kinetics (18 and −1 36 g a.i. ha , respectively). for risk assessment are shown in Table  3. No MRLs are available is consumed as pulse as well as flour in various food preparations for β-cyfluthrin and imidacloprid in chickpea. However, MRLs for including snacks, sweets, and in various desserts in India by both rural −1 pulses in EU and codex for imidacloprid are 2.0 µg g and in EU for and urban Indian population. The HQ was less than 1 for both rural −1 β-cyfluthrin is 0.02  µg g . MRLs are neither available for pulses nor and urban population (Table 4), suggesting that the use of combina- for chickpea in India. The levels of imidacloprid are never above MRL tion product of β-cyfluthrin on chickpea pods is safe provided that the in the present study and reached to a significantly low level at PHI. As proper PHI is followed. Earlier studies have also recommended the use MRLs are not available for either of the pesticide in chickpea, theo- of combination product of β-cyfluthrin and imidacloprid in various retical risk was assessed. It was important to assess risk as chickpea commodities provided proper PHI is followed. Downloaded from https://academic.oup.com/fqs/advance-article-abstract/doi/10.1093/fqs/fyy007/4925843 by Ed 'DeepDyve' Gillespie user on 04 May 2018 6 S. Chawla et al. Figure 2. Dissipation kinetics for imidacloprid at standard and double doses: (a) zero-order kinetics, (b) first-order kinetics, and (c) second-order kinetics (18 and −1 36 g a.i. ha , respectively). Table 4. Dietary risk assessment by hazard quotient (HQ) method in chickpea at pre-harvest interval (PHI) of 7 days (for β-cyfluthrin) and 10 days (for imidacloprid; average body weight = 60 kg). −6 −6 Pesticide Dose Residue Dietary intake Dietary intake EDI (× 10 mg/kg EDI (× 10 mg /kg bw/ ADI HQ HQ −1 (mg kg ) (kg) (rural) (kg) (urban) bw/day) (rural) day) (urban) (mg/kg) (rural) (urban) β-Cyfluthrin Standard dose 0.09 0.0261 0.03003 0.000039 0.000045 0.04 0.0010 0.0011 Double dose 0.12 0.0261 0.03003 0.000052 0.000060 0.04 0.0013 0.0015 Imidacloprid Standard dose 0.21 0.0261 0.03003 0.000091 0.000105 0.06 0.0015 0.0018 Double dose 0.22 0.0261 0.03003 0.000096 0.000110 0.06 0.0016 0.0018 Chandrashekhar, K., et al. (2014). Integrated Pest Management for Chickpea, Conclusion pp. 43. The present data show that dissipation kinetics of β-cyfluthrin Dikshit, A. K., Pachauri, D. C., Jindal, T. (2003). Maximum residue limit showed best fit in zero order and first order at standard and dou- and risk assessment of beta-cyfluthrin and imidacloprid on tomato ble doses, respectively. For imidacloprid, first-order kinetics was (Lycopersicon esculentum mill). Bulletin of Environmental Contamination observed at both the doses. The residues reached below deter- and Toxicology, 70: 1143–1150. −1 Fantke, P., Juraske, R. (2013). Variability of pesticide dissipation half-lives in mination level of 0.01 µg g on the 10th day after application of plants. Environmental Science & Technology, 47: 3548–3562. β-cyfluthrin at standard dose and on the 15th day after application Fu, Y., Zheng, Z., Wei, P., Wang, M., Zhu, Z., Liu, Y. (2016). Distribution of in all other cases. HQ is less than 1 in all the cases. Therefore, the thifluzamide, fenoxanil and tebuconazole in rice paddy and dietary risk combination product of β-cyfluthrin and imidacloprid can be used assessment. Toxicological and environmental Chemistry, 98: 118–127 in chickpea safely following a PHI of 15 days. As the residues were Hoskins, W. M. (1961). Mathematical treatment of the rate of loss of pesticide below determination level in soil, it can be concluded that combina- residues. FAO Plant Protection Bulletin, 9: 163–168 tion product does not pose any environmental threat. There are no ICMR. (2010). Indian Council of Medical Research, http://icmr.nic.in/final/ established MRLs for imidacloprid and β-cyfluthrin on chickpea in rda-2010.pdf. India and in codex; hence, present data along with other studies can Júnior, R. P., Smelt, J. H., Boesten, J. J., Hendriks, R. F., van der Zee, S. E. be used for the MRL establishment for these compounds in India. (2004). Preferential flow of bromide, bentazon, and imidacloprid in a Dutch clay soil. Journal of Environmental Quality, 33: 1473–1486. Lang, Y., Cao, Z., Nie, X. (2005). Extraction of organochlorine pesticides in Acknowledgements sediments using soxhlet, ultrasonic and accelerated solvent extraction The authors are thankful to Indian Council of Agricultural Research for finan- techniques. Journal of Ocean University of China, 4: 173. cial assistance and M/s Bayer Cropscience for sponsoring the project. Leslie, W. (1988). Baythroid—residues in field rotational cereal crops. Mobay Chemical Corp. Report No. 98429 References Lozowicka, B., et  al. (2014). Pesticide residues in grain from Kazakhstan Bates, R. (2002). Pesticide residues and risk assessment. Pesticide Outlook, and potential health risks associated with exposure to detected pes- 13:142 ticides. Food and Chemical Toxicology: An International Journal Bhargava, K. K., Bhatnagar, A., Sharma, H. C. (2003). Bioefficacy of imida- Published for the British Industrial Biological Research Association, cloprid and beta-cyfluthrin for the management of insect pests of brinjal. 64: 238–248. 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