Dissipation of spiromesifen and spiromesifen-enol on ...

Environ Sci Pollut Res DOI 10.1007/s11356-017-9954-9

RESEARCH ARTICLE

Dissipation of spiromesifen and spiromesifen-enol on tomato fruit, tomato leaf, and soil under field and controlled environmental conditions Lekha Siddamallaiah 1,2 & Soudamini Mohapatra 1 & Radhika Buddidathi 1 & Shibara Shankara Hebbar 3

Received: 6 February 2017 / Accepted: 11 August 2017 # Springer-Verlag GmbH Germany 2017

Abstract Dissipation of spiromesifen and its metabolite, spiromesifen-enol, on tomato fruit, tomato leaf, and soil was studied in the open field and controlled environmental conditions. Sample preparation was carried out by QuEChERS method and analysis using LC-MS/MS. Method validation for analysis of the compounds was carried out as per Bsingle laboratory method validation guidelines.^ Method validation studies gave satisfactory recoveries for spiromesifen and spiromesifen-enol (71.59–105.3%) with relative standard deviation (RSD) < 20%. LOD and LOQ of the method were 0.0015 μg mL−1 and 0.005 mg kg−1, respectively. Spiromesifen residues on tomato fruits were 0.855 and 1.545 mg kg−1 in open field and 0.976 and 1.670 mg kg−1 under polyhouse condition, from treatments at the standard and double doses of 125 and 250 g a.i. ha−1, respectively. On tomato leaves, the residues were 5.64 and 8.226 mg kg−1 in open field and 6.874 and 10.187 mg kg−1 in the polyhouse. In soil, the residues were 0.532 and 1.032 mg kg−1 and 0.486 and 0.925 mg kg−1 under open field and polyhouse conditions, respectively. The half-life of degradation of spiromesifen on tomato fruit was 6–6.5 days in the open field and 8.1–9.3 days in the polyhouse. On tomato Responsible editor: Philippe Garrigues * Soudamini Mohapatra [email protected]

1

Pesticide Residue Laboratory, ICAR-Indian Institute of Horticultural Research, Hesaraghatta Lake P.O., Bangalore, Karnataka 560089, India

2

Center for Postgraduate Studies (Jain University), 18/3, 9th Main, 3rd Block, Jayanagar, Bangalore 560011, India

3

Division of Vegetable Crops, Indian Institute of Horticultural Research, Hesaraghatta Lake P.O., Bangalore, Karnataka 560089, India

leaves, it was 7–7.6 and 17.6–18.4 days and in soil 5.6–7.4 and 8.4–9.5 days, respectively. Metabolite, spiromesifen-enol, was not detected in any of the sample throughout the study period. Photodegradation could be the major route for dissipation of spiromesifen in the tomato leaves, whereas in the fruits, it may be the combination of photodegradation and dilution due to fruit growth. The results of the study can be utilized for application of spiromesifen in plant protection of tomato crop under protected environmental conditions. Keywords Half-life . Limit of detection (LOD) . Limit of quantification (LOQ) . Method validation . QuEChERS method . Spiromesifen

Introduction Tomato is the most widely grown vegetable in the world with an annual production of 170.75 million tonnes during 2014 (http://www.fao.org/faostat/en/#data/QC). India occupies the second rank in the area and production of tomato after China with a production of 18.73 million tonnes during that period. Tomato is consumed in many ways: as raw vegetable in salads and as ingredient in many dishes, sauces, and drinks. Tomato and tomato products have numerous health benefits (Rao et al. 1998). It is rich in vitamins A, C, and E (Beecher 1998). It contains lycopene, antioxidant, α-tomatine, calcium, and niacin, thus plays a major role in human health by reducing the risk of cancer and chronic degenerative diseases (Shi and Manguer 2000; Sies et al. 1992; Friedman 2013; Olaniyi et al. 2010; Suarez et al. 2007). Tomato cultivation can be done throughout the year (Tumwine 1999). It is grown both under open field and controlled environmental conditions. Cultivation of the crop under the controlled environmental conditions is carried out in polyhouses. Polyhouse protects the

Environ Sci Pollut Res

crop against pests and diseases, enables the crop to grow throughout the year irrespective of the season, improves the fruit quality, and increases the production and productivity per unit area (Singh et al. 2012). The cultivation of vegetable crops under polyhouse produced better yield in more than 50 countries throughout the world (Kanthaswamy et al. 2000; Ganesan 2002a, b, c; Srivastava et al. 2002). Tomato is a warm-season crop. The average monthly temperature that is required for the tomato crop is 21 to 23 °C (http://agropedia. iitk.ac.in/content/climatic-and-temperature-requirementtomato). The fruit setting is at night temperature in the range of 15–20 °C (Lekshmi and Celine 2015). Polyhouse cultivation of tomato plants resulted in earlier flowering and fruit setting by 3 and 8 days compared to the open field (Ganesan 2002b). The production of tomato and income generated was more under polyhouse condition compared to that of the open field condition (Singh et al. 2012). The cultivation of crops under the open field is more commonly affected by pests and diseases, thus lowering the yield and quality of the crop. Tomato is most commonly affected by aphids (Myzus persicae), thrips (Frankliniella spp.), fruit worms (Helicoverpa armigera), mites (Tetranychus evansi), and diseases such as early blight (Alternaria solani), bacterial wilt (Ralstonia solanacearum), and late blight (Phytophthora infestans), thus leads to yield losses (Akemn et al. 2000; Anastacia et al. 2011; Ssekyewa 2006). Tomato crop under the polyhouse is also affected by the glasshouse whitefly Trialeurodes vaporariorum (Daniel et al. 2016). Spiromesifen is used for control of the important pests of vegetables such as tetranychid mites and whiteflies (Roffeni et al. 2008). Spiromesifen (3-mesityl-2-oxo-1-oxaspiro [4.4] non-3-en4-yl 3, 3-dimethylbutyrate) is a miticide/insecticide which belongs to the chemical class of spirocyclic phenyl substituted tetronic acid. It is a lipid biosynthesis inhibitor, acts by inhibiting lipid metabolism enzyme acetyl CoA-carboxylase, and causes significant decrease in the fat lipids (Kontsedalov et al. 2008). Spiromesifen is active against the tetranychid spider mite species (Tetranychus spp.) and whiteflies (Bemisia spp. and Trialeurodes spp.) (Nauen et al. 2002; Nauen and Konanz 2005). Spiromesifen can be used for the control of red spider mite and whitefly population effectively (Alam et al. 2014; Tekam et al. 2013). It controls insect pests which are resistant to the commonly used neonicotinoids and has currently no known cross-resistance (Prabhaker and Toscano 2008). Spiromesifen-enol [1-oxaspiro [4.4] non3-en-2-one, 4-hydroxy-3-(2, 4, 6-trimethylphenyl)] is the major metabolite of spiromesifen, which is formed by hydrolysis of the parent compound. The residue definition for food of plant origin is the sum of spiromesifen and spiromesifen-enol, expressed as spiromesifen, for monitoring and risk assessment purposes (European Food Safety Authority 2012).

Environmental conditions vary in the open field and controlled condition (Anonymous 2011). In open field, the crop is susceptible to the changes in environmental conditions such as humidity, temperature, light intensity, wind, and rainfall. Polyhouse provides the favorable environment for the growth of plants. It is used to protect the plants from environmental conditions such as cold weather, excessive temperature and radiation, and wind (Yadav et al. 2014). Polyhouse provides a better microclimatic condition for the growth of crops. Temperature plays a major role in the development of the plants and productivity (Parvej et al. 2010). The cultivation of the crop under the controlled environmental conditions can lead to the buildup of pesticides, whereas rainfall in the open field can facilitate the leaching of pesticides to the soil. Pesticides dissipate faster from crops but slowly from soil (Juraske et al. 2008; Fantke et al. 2013). Soil residues are the major source for the entry of large number of pesticides into the food chain (Ghosh and Singh 2009). The difference in the environmental condition will also be responsible for the variation in the dissipation pattern of pesticide in the open field and polyhouse. Volatilization due to elevated temperatures, high moisture content, and direct exposure to sunlight accelerate degradation of pesticides in the environment (Fantke and Juraske 2013; Delcour et al. 2015). Sunlight-induced photodegradation plays an important role in the degradation of pesticides (Katagi 2004). Tricyclazole when used as foliar spray for the control of pest, it undergoes both hydrolysis and photolysis reactions (Phong et al. 2009a; Phong et al. 2009b). Spiromesifen degraded faster under UV light conditions than under sunlight (Mate et al. 2015). Pesticides persisted longer on cucumber, peppers, tomato, and capsicum in polyhouse compared to open field (Fang et al. 2006; Buddidathi et al. 2015; Sharma et al. 2012). The persistence of spiromesifen on tomato fruit has been reported earlier (Sharma et al. 2014). However, no information is available on its behavior under different environmental conditions. This study was undertaken to study the behavior of spiromesifen on tomato fruit, tomato leaf, and field soil under open field and controlled environmental conditions.

Materials and methods Chemicals and reagents Spiromesifen (purity 99%), spiromesifen-enol (purity 99.5%) (Fig. 1), LC-MS/MS grade acetonitrile, acetic acid, methanol, ammonium formate (NH4HCO2), and formic acid (CH2O2) were purchased from Sigma-Aldrich, India Pvt. Ltd. Oberon 240 SC formulation was obtained from the M/S Bayer Crop Sciences, India Pvt. Ltd. Analytical grade magnesium sulfate (MgSO4), sodium sulfate (Na2SO4), and sodium acetate (C 2 H 3 NaO 2 ) were purchased from Rankem Avantor


stored at − 20 °C. The loss of solvents due to evaporation was adjusted gravimetrically before use. Field experiment

Fig. 1 Chemical structure of a spiromesifen and b spiromesifen-enol

Performance Materials, India Ltd. (Bangalore, India). MgSO4 was activated in a muffle furnace for 5 h at 600 °C and kept in desiccators until used. Primary secondary amine (PSA) of mesh size of 40 μm, and graphite carbon bulk sorbent (GCB) was procured from Agilent Technologies (Bangalore, India). The water from Millipore Water Purification System (ELIX, Merck Millipore, India Pvt. Ltd.) was used for the mobile phase. Membrane filter of 0.2 μm used for filtration of samples was purchased from Phenomenex (Bangalore, India). The soil characteristics were as follows: sandy loam, pH 6.6, EC 0.2 dS m−1, CEC 6.9 meq 100 g−1, organic carbon 0.4%, sand 70.6%, silt 7.4%, and clay 10.3%, which was the same in the open field and polyhouse.

Preparation of standard solutions Spiromesifen and spiromesifen-enol standard solution (1000 μg mL−1) was prepared by weighing 10 ± 0.1 mg of spiromesifen and spiromesifen-enol in 10-mL volumetric flasks and dissolving in 10-mL LC-MS/MS grade acetonitrile. Working solutions of appropriate concentrations were prepared by dilution of the stock solutions. Calibration standards prepared were at 0.0015, 0.0025, 0.005, 0.01, 0.025, 0.05, and 0.1 μg mL−1. For the residue analysis, purpose matrix-matched standards were found to be more prominent. For preparation of matrix matched standards, control sample (1 mL) was concentrated in a TurboVap® LV concentrator (Caliper Life Sciences, USA), and suitable aliquots of the standards were added to make up the volume to 1 mL. All standard solutions are Table 1

a

Sample preparation Tomato samples were cut into small pieces and homogenized in a high-volume Robot Coupe Homogenizer (Blixer® 6 V.V.,

Recovery (%) and RSD (%) of spiromesifen and spiromesifen-enol from tomato fruit, tomato leaf, and soil at different spiked levels

Spiked level (mg kg−1)

0.005 0.010 0.025 0.050 0.100

The field study was carried out at the experimental field of Indian Institute of Horticultural Research (IIHR), Bangalore, India (latitude, 13.13° N; longitude, 77.49° E) during May– August 2016. The field soil was sandy loam type (Typic Haplustalf), and the soil pH was 6.6 and organic carbon 0.4%. In line with good data reporting practice, we also report (average) temperature, humidity, (total) rainfall, and wind speed (Fantke et al. 2016) (Table 1). The experimental study was carried out at randomized block designs as per good agricultural practices (GAP) following the OECD guidelines (2016). The study was carried out in a similar manner in the polyhouse at the same time. Tomato (variety Arka Rakshak) was grown in the polyhouse and experimental field without application of pesticides. Five plots (5 M × 5 M) were selected for each treatment and each treatment was replicated thrice. At the fruit formation stage (2 months after transplanting) of tomato crop (open field and polyhouse), spiromesifen (Oberon 240 SC) spray applications were given at the standard and double doses of 125 and 250 g a.i. ha−1 twice at 10-day intervals using a knapsack sprayer. Untreated plants were kept as control. Tomato fruit samples were collected on 0 (2 h), 1, 3, 5, 7, 10, 15, 20, 25, and 30 days (harvest) after the second spray. Tomato fruit (2 kg) and leaf (500 g) samples from the treated field were brought to the laboratory in plastic bags and stored at 4 °C. The samples were analyzed within 24 h. Soil samples of about 5 kg were collected from the treated field (at 1–15-cm depth) and air dried in the shade at room temperature (25 ± 2 °C). The samples were powdered and sieved (2 mm) before use. Tomato leaf and soil samples were collected on 0, 5, 10, 15, 20, 25, and 30 days after the second spray.

Tomato fruit

Tomato leaf

Soil

Spiromesifen

Spiromesifen-enol

Spiromesifen

Spiromesifen-enol

Spiromesifen

Spiromesifen-enol

96.00 ± 8.4 100.90 ± 7.8 102.24 ± 5.7 104.16 ± 4.6 105.27 ± 3.7

74.50 ± 6.7 78.30 ± 6.3 82.60 ± 5.3 83.60 ± 5.2 85.45 ± 4.8

87.32 ± 9.3 90.44 ± 8.0 92.78 ± 5.7 95.38 ± 5.2 96.66 ± 4.3

72.45 ± 6.9 76.24 ± 6.5 80.48 ± 5.4 81.56 ± 4.5 83.58 ± 3.2

89.25 ± 8.1 91.58 ± 7.2 95.68 ± 6.9 100.12 ± 6.2 102.34 ± 5.8

71.59 ± 6.5 75.48 ± 5.3 80.65 ± 4.5 84.56 ± 4.1 87.58 ± 3.8

Average of six replicate analyses ± SD


Fig. 2 LC-MS/MS extracted ion chromatogram of matrix match standards of a spiromesifen, 0.1 μg mL−1 and b spiromesifen-enol, 0.1 μg mL−1

France). A subsample of (250 g) was further homogenized with a silent crusher M (Heidolph Instruments, Germany). Leaf samples were mixed in a Waring blender. Extraction and purification of tomato fruit and leaf samples were carried out by QuEChERS method. Fifteen grams of the Table 2

Residues of spiromesifen in tomato fruits

Days after treatment

Residues of spiromesifen in tomato fruits ± SDa (mg kg−1) Untreated control

0 1 3 5 7 10 15 20 25 30 a

homogenized sample in triplicate was taken in 50-mL polypropylene centrifuge tubes and treated with 15 mL of 1% acetic acid in acetonitrile and vortexed for 1 min. Anhydrous MgSO4 (6 g) and C2H3NaO2 (1.5 g) were added to the tubes and vortexed for 2 min. Centrifugation was carried out at

ND ND ND ND ND ND ND ND ND ND

Open field

Polyhouse

Application at 125 g a.i. ha−1




0.855 ± 0.080 0.749 ± 0.091 (12.4) 0.642 ± 0.107 (24.9) 0.550 ± 0.033 (35.7) 0.420 ± 0.030 (50.9) 0.300 ± 0.026 (64.9) 0.176 ± 0.010 (79.4) 0.115 ± 0.012 (86.5) 0.042 ± 0.010 (95.1) < LOQ

1.545 ± 0.079 1.329 ± 0.077 (14.0) 1.168 ± 0.035 (24.4) 0.956 ± 0.106 (38.1) 0.820 ± 0.009 (46.9) 0.562 ± 0.119 (63.6) 0.306 ± 0.028 (80.2) 0.180 ± 0.035 (88.3) 0.105 ± 0.024 (93.2) 0.068 ± 0.015 (95.6)

0.976 ± 0.022 0.882 ± 0.031 (9.6) 0.742 ± 0.013 (23.9) 0.651 ± 0.03 (33.3) 0.590 ± 0.057 (39.5) 0.470 ± 0.045 (51.8) 0.300 ± 0.054 (69.3) 0.158 ± 0.016 (83.8) 0.112 ± 0.015 (88.5) 0.081 ± 0.017 (91.7)

1.670 ± 0.074 1.493 ± 0.080 (10.6) 1.275 ± 0.052 (23.6) 1.11 ± 0.069 (33.5) 0.945 ± 0.025 (43.4) 0760 ± 0.048 (54.5) 0.552 ± 0.033 (66.9) 0.432 ± 0.059 (74.1) 0.265 ± 0.017 (84.1) 0.152 ± 0.025 (90.9)

Average of three replicate analyses ± SD

ND not detected Figures in the parenthesis are the percent dissipation of residues


Agilent LC system coupled with 6460 triple quad mass spectrometer (Agilent technologies, Palo Alto, CA, USA) used to analyze spiromesifen and spiromesifen-enol in tomato fruit, leaf, and soil. The separation of the analytes was performed using a Zorbax Eclipse Plus C18 column (2.1 × 100-mm i.d., 3.5-μm particle size). The mobile phase was composed of (A) 0.1% ammonium formate (5 mM) and 0.01% formic acid, v v−1 in water, and (B) 0.1% ammonium formate (5 mM) and 0.01% formic acid, v v−1 in methanol. The column was maintained at a constant temperature of 40 ± 0.8 °C and the column flow rate was 0.4 mL min−1. The gradient mobile phase established with 15% acetonitrile at 0–1 min, 50% at 6 min, 95% at 12 min, and returns to initial concentration by 18 min. The samples were transferred to 1.5-mL vials, and 2 μL was injected using an auto-sampler. For the determination of spiromesifen residues, electrospray ionization (ESI) probe was operated in positive mode and for spiromesifen-enol in negative mode, using multiple reaction monitoring (MRM) method. Instrument parameters were optimized for determination of spiromesifen and spiromesifen-enol residues. The MS/MS was monitored for the two most abundant MS/MS precursor and product transition ion: one for quantification and another for confirmation (quantifier and qualifier). Under the above operating conditions, the retention time of spiromesifen-enol was 4.5 min and that of the spiromesifen is 12.3 min. The extracted ion chromatograms of spiromesifen and spiromesifen-enol are presented in Fig. 2.

2 Field- tomato fruits at 125 g a.i./ha Field- tomato fruits at 250 g a.i./ha Polyhouse- tomato fruits at 125 g a.i./ha Polyhouse- tomato fruits at 250 g a.i./ha

Concentration

1.5

y = -0.0478x + 1.4193 R² = 0.923 y = -0.0484x + 1.2652 R² = 0.8878

1

y = -0.0298x + 0.8421 R² = 0.9294

0.5

y = -0.0317x + 0.7308 R² = 0.9158

0 0

5

10

-0.5

b

15

20

25

30

35


3.5 y = -0.0324x + 3.2148 R² = 0.9909

3

Log Concentration × 1000

LC-MS/MS analysis

a

y = -0.0463x + 3.1989 R² = 0.9979

2.5 2 1.5

Field- tomato fruits at 125 g a.i./ha y = -0.0371x + 3.0017 Field- tomato fruits at 250 g a.i./ha R² = 0.9918 Polyhouse- tomato fruits at 125 g a.i./ha Polyhouse- tomato fruits at 250 g a.i./ha y = -0.0505x + 2.9629 R² = 0.9913

1 0.5 0 0

c

5

10

15 20 Days after treatment

25

30

35

30 Field- tomato fruits at 125 g a.i./ha Field- tomato fruits at 250 g a.i./ha Polyhouse- tomato fruits at 125 g a.i./ha Polyhouse- tomato fruits at 250 g a.i./ha

25 20 1/ Concentration

4100 rpm for 10 min using a Q-Sep 3000 centrifuge (Bellefonte, PA, USA). The upper acetonitrile layer (3 mL) was transferred to 15-mL centrifuge tubes containing 450-mg MgSO4 and 150-mg PSA. For the leaf samples, 50 mg mL−1 of GCB was added to remove the chlorophyll content. The tubes were vortexed for 2 min and centrifuged at 4100 rpm for 10 min. The acetonitrile phase was filtered through a 0.2-μm PTFE membrane filter. An aliquot of 1 mL was taken for LCMS/MS analysis. A representative 20-g soil sample in three replicates was taken in 100-mL polypropylene centrifuge tubes; 30-mL acetonitrile:water (2:1, v v−1) was added and vortexed for 2 min. The contents in the tubes were centrifuged at 10,000 rpm for 10 min using an R-24 Remi centrifuge (Remi Instruments, India). The solvent layer was transferred to a 50-mL measuring cylinder with stopper containing 10 mL of saturated NaCl solution and mixed thoroughly. Three milliliters of the upper acetonitrile layer (3 mL) was subjected to clean-up using MgSO4 and PSA as described above. One milliliter of aliquot was filtered through 0.2-μm PTFE membrane filter for analysis by LC-MS/MS.

y = 0.4227x - 0.9677 R² = 0.8781 y = 0.1654x + 0.0617 R² = 0.8449

15

y = 0.7246x - 1.394 R² = 0.7569

10 5

y = 0.3586x - 0.1799 R² = 0.9159

0 0 -5

5

10

15

20

25

30

35


Fig. 3 Dissipation of spiromesifen in tomato fruits; a Zero order kinetics. b First-order kinetics. c Second-order kinetics

Rate of reaction and half-life The dissipation pattern of spiromesifen in tomato fruits, tomato leaves, and soil was determined by plotting graphs between the concentrations (C) of spiromesifen versus time (t). Graphs are plotted for zero order reaction (C versus t),


first-order reaction (ln C versus t) and second-order reaction (1/[C] versus t) (http://www.chem.purdue.edu/gchelp/ howtosolveit/Kinetics/IntegratedRateLaws.html). A linear graph with correlation coefficient, r2 ≥ 0.99, indicated the correct rate of reaction. The half-life (t1/2) was obtained from the dissipation rate constant, k value using the formula,t 1=2 ¼ lnðk2Þ Pre-harvest interval (PHI) was calculated by statistical analysis as per Hoskins (1961). Method validation QuEChERS analytical method used for analysis of spiromesifen and spiromesifen-enol in tomato fruit, tomato leaf, and soil was validated as per SANTE (2015). The parameters of the method validation studied were accuracy and precision, limit of detection (LOD), limit of quantification (LOQ), linearity, range, selectivity, and measurement uncertainty. Accuracy and precision of the analytical method were carried out by conducting the recovery experiments. Control samples of tomato fruit, tomato leaf, and soil were used for the recovery studies. Recovery was carried out for spiromesifen and spiromesifen-enol at five concentration levels of 0.005, 0.01, 0.025, 0.05, and 0.1 mg kg−1 for tomato fruit, tomato leaves, and soil. LOD is the lowest concentration of analyte in a sample that can be detected with signal to noise ratio of 3:1. It is determined by injecting the standards prepared in the range of 0.0015–0.1 μg mL−1. LOQ is the concentration at which the chromatographic peak is clearly identified with signal of 10 and noise ratio of 1. Linearity of the method was studied by Table 3 Residues of spiromesifen in tomato leaves


injecting the standards of spiromesifen and spiromesifen-enol in the range of 0.0015–0.1 μg mL−1. The selectivity of the method was studied by analyzing the blank and spiked samples from low to high concentrations. The uncertainty of the analytical method was calculated by taking into consideration various factors contributing towards it. The factors were recovery, concentration of sample, volume measure of sample, temperature, reference standard purity, reference standard mass, volume of standard solution prepared, stock solution dilution, and sample mass. Combined uncertainty was calculated with coverage factor, K = 2 at 95% confidence level.

Results and discussion Method validation The analytical method validated for analysis of spiromesifen and spiromesifen-enol in tomato fruit, tomato leaves, and soil was found to be suitable as satisfactory results were obtained for all the parameters studied according to SANTE (2015). The calibration curve was linear in the range of 0.0015– 0.1 μg mL−1 with the correlation coefficient of 0.99. The LOD of the method was 0.0015 μg mL−1. The LOQ of the method was 0.005 mg kg−1 where satisfactory recoveries were obtained for all the matrices studied. The recoveries of spiromesifen from tomato fruits were 96–105.27%, with RSD between 3.6 and 8.7%. The recoveries from tomato leaves were 87.32–96.66%, with RSD between 4.4 and 10.7%, and soil, 89.25 and 102.34%, with RSD between 5.7

Residues of spiromesifen in tomato leaves ± SDa (mg kg−1) Untreated control

0 5

ND ND

10

ND

15

ND

20

ND

25

ND

30

ND

a

Open field

Polyhouse





5.640 ± 0.214 4.250 ± 0.016 (31.4) 2.750 ± 0.276 (60.5) 1.884 ± 0.126 (78.2) 1.022 ± 0.068 (89.5) 0.630 ± 0.089 (95.3) 0.3 ± 0.089 (94.7)

8.226 ± 0.305 6.582 ± 0.189 (30.0) 4.300 ± 0.320 (43.8) 2.474 ± 0.279 (63.4) 1.767 ± 0.071 (81.1) 1.063 ± 0.137 (89.9) 0.514 ± 0.029 (93.4)

6.874 ± 0.273 5.770 ± 0.318 (16.1) 4.537 ± 0.214 (33.9) 3.543 ± 0.308 (48.5) 2.96 ± 0.227 (56.9) 2.567 ± 0.091 (62.7) 2.185 ± 0.169 (68.2)

10.187 ± 0.256 9.242 ± 0.133 (9.3) 7.263 ± 0.159 (28.7) 6.058 ± 0.070 (40.5) 4.860 ± 0.131 (52.3) 4.165 ± 160 (59.1) 3.42 ± 0.111 (66.4)


ND not detected Figures in the parenthesis are the percent dissipation of residue


Spiromesifen residues in/on tomato fruit

a

12

Field- tomato leaves at 125 g a.i./ha y = -0.2347x + 9.9771 R² = 0.9761 Field- tomato leaves at 250 g a.i./ha Polyhouse- tomato leaves at 125 g a.i./ha Polyhouse- tomato leaves at 250 g a.i./ha y = -0.2625x + 7.4963 R² = 0.9375

10 8

Concentration

and 8.9%. Spiromesifen-enol recoveries from tomato fruit were 74.50–85.45% (RSD 5.7–9.0%), from tomato leaves 72.45–83.58% (RSD 3.8–9.5%), and soil 71.59–87.58% (RSD between 4.3 and 9.1%) (Table 1). The method was highly selective for both the analytes studied in all the matrices. MU of the method for analysis of tomato fruit, tomato leaf, and soil was in the range of 4.8–12.55%.

y = -0.1575x + 6.4247 R² = 0.9492 6 y = -0.1785x + 5.0314 R² = 0.9396 4 2 0 0

5

10

-2

b

15

20

25

30

35


4.5 y = -0.0164x + 4.0249 R² = 0.995

4


3.5 3 2.5 2 Field- tomato leaves at 125 g a.i./ha Field- tomato leaves at 250 g a.i./ha Polyhouse- tomato leaves at 125 g a.i./ha Polyhouse- tomato leaves at 250 g a.i./ha

1.5 1

y = -0.017x + 3.8302 R² = 0.9915 y = -0.0402x + 3.9805 R² = 0.9907 y = -0.0417x + 3.8156 R² = 0.9903

0.5 0 0

5

10

15

20

25

30

35


c

4 Field- tomato leaves at 125 g a.i./ha

3.5

y = 0.0539x - 0.1775 R² = 0.7607

Field- tomato leaves at 250 g a.i./ha 3

Polyhouse- tomato leaves at 125 g a.i./ha y = 0.0065x + 0.0802 R² = 0.9714 Polyhouse- tomato leaves at 250 g a.i./ha

2.5 1/ Concentration

Residues of spiromesifen on tomato as initial deposits were 0.855 and 1.545 mg kg−1 in the open field and 0.976 and 1.670 mg kg−1 under polyhouse conditions at standard and double doses of 125 and 250 g a.i. ha −1 , respectively (Table 2). Spiromesifen residues were detected on tomato fruits for 25 days in the open field and 30 days in the polyhouse from treatment doses. When the treatment was doubled, the residues were detected up to 30 days in the open field and polyhouse, but the levels were much higher in the polyhouse tomatoes. Spiromesifen dissipation was faster from tomato fruits in the open field compared to the polyhouse. In the initial stages, this difference was marginal. From the tenth day onwards, it was more evident when the residue dissipation was about 65% in the open field compared to about 52% in the polyhouse. After 15 days, spiromesifen residue levels on tomato were 0.176 and 0.306 mg kg−1 in the open field, whereas it was 0.3 and 0.552 mg kg−1 under polyhouse conditions at standard and double doses, respectively. After 30 days, spiromesifen residues on field grown tomatoes had reached below the LOQ of 0.005 mg kg−1 at standard dose treatment whereas in polyhouse grown tomatoes, it was 0.081 mg kg−1. From double dose treatments, the residues were 0.068 and 0.152 mg kg−1 in field and polyhouse grown tomatoes. Higher initial residue deposits in polyhouse grown tomatoes could be attributed to spray drift caused by wind speed (Nuyttens et al. 2006; Wang and Rautmann 2008). The wind speed was in the range of 4.9–6.4 km h−1 during the study period, and this could have caused spray drift reducing spray deposits on the tomato plants. The higher initial residues compounded by slow dissipation resulted in higher residue levels in polyhouse grown tomatoes, which was almost double compared to field grown tomatoes by the 25th day. The difference in dissipation pattern could be correlated with the difference in the environmental parameters in the field and polyhouse. The average temperature (highest) in the open field was within 28–29.2 °C and in the polyhouse, 30.4–33 °C. The average humidity (highest) in the open field was within 76– 79% and in the polyhouse, 77–83%. The cumulative rainfall between the field treatment of spiromesifen to tomato crop and the last sample analysis (30 day) was 174.2 mm. High atmospheric temperature in Indian cities can volatilize pesticides from soil (Chakraborty et al. 2015). Increase in the moisture can further increase the volatilization of pesticides (Wolters

2 y = 0.0918x - 0.3446 R² = 0.7591

1.5 1 0.5 0 0

5

10

15

20

25

30

35

-0.5 -1


y = 0.0106x + 0.1274 R² = 0.9909

Fig. 4 Dissipation of spiromesifen in tomato leaves. a Zero-order kinetics. b First-order kinetics. c Second-order kinetics

et al. 2003). Temperature was marginally higher in the polyhouse, but the rainfall (174.2 mm) and volatilization caused by wind speed (4.9–6.4 km h−1) could be the factors for faster dissipation of spiromesifen in field grown tomato fruits (Chai et al. 2009; Lester et al. 2017).


In earlier studies, it was reported that in the polyhouse, the temperature and humidity were higher compared to the open field, but light intensity is higher in the open field (Dhandare et al. 2008; Klopffer 1992). Inside the polyhouse, the photosynthetically active radiation was 40% less than the open field conditions (Parvej et al. 2010). Light intensity plays a major role in degradation of organic compounds in the environment (Ahmed et al. 2011). The photochemical reaction that undergoes in the presence of light leads to the abiotic degradation of pesticides and other organic chemicals (Holland and Sinclair 2004). Photochemical degradation contributes to the fate of many pesticides in the environment (Remucal 2014; Kiss and Virag 2009). As light intensity is reduced in the polyhouse, so is the photodegradation. This factor could have contributed in a major way to the slow dissipation of spiromesifen in the polyhouse compared to the open field even though the temperature and humidity were higher in the polyhouse. The fruit growth was similar in the polyhouse and open field, so dilution factor due to fruit growth would be same under both conditions. Flubendiamide and acephate degraded faster under field conditions compared to the polyhouse (Buddidathi et al. 2015; Sharma et al. 2012). It is also reported by other researchers that pesticide residues were detected more often in crops grown in protected environments compared to that in open field conditions (Allen et al. 2015). The metabolite spiromesifen-enol was not detected in any tomato fruit throughout the study period. In supervised field studies conducted on various crops Table 4 Residues of spiromesifen in soil


such as apple, chili, cotton, and cabbage, spiromesifenenol was never detected (Sharma et al. 2005; Sharma et al. 2007; Siddamallaiah and Mohapatra 2016). Spiromesifen degradation in tomato fruits followed first-order rate kinetics with the correlation coefficient r2 ≥ 0.99. Its dissipation in field and polyhouse grown tomato fruits is presented in Fig. 3. It degraded at the half-life of 6.1–6.5 days in the open field and 8.1– 9.3 days in the polyhouse from treatment at the standard and double doses. The half-life of degradation of flubendiamide and acephate on capsicum was longer in the polyhouse compared to that of the open field (Buddidathi et al. 2015; Sharma et al. 2012). The initial residue deposits of spiromesifen on tomato were less than the maximum residue limit of 1 mg kg − 1 (European Food Safety Authority 2012) from standard dose treatment in polyhouse and open field. Therefore, 1-day PHI was recommended for this treatment. With doubling the treatment dosage, the required PHI was 4 days in the open field and 7 days in the polyhouse. The reported half-life and PHI were longer in the polyhouse compared to the open field for flubendiamide on capsicum (Buddidathi et al. 2015). Spiromesifen residues in/on tomato leaf Residues of spiromesifen in tomato leaves were 5.640 and 8.226 mg kg−1 in the open field and 6.874 and 10.187 mg kg−1 in the polyhouse from treatment at the standard and double doses of 125 and 250 g a.i. ha−1, respectively (Table 3).

Residues (mg kg−1) of spiromesifen in soil mean ± SDa Untreated control

0 5

ND ND

10

ND

15

ND

20

ND

25

ND

30

ND

a

Field

Polyhouse





0.532 ± 0.094 0.365 ± 0.049 (31.4) 0.210 ± 0.054 (60.5) 0.116 ± 0.020 (78.2) 0.056 ± 0.007 (89.5) 0.025 ± 0.003 (95.3) < LOQ

1.032 ± 0.083 0.723 ± 0.059 (30.0) 0.580 ± 0.051 (43.8) 0.316 ± 0.044 (63.4) 0.195 ± 0.035 (81.1) 0.104 ± 0.021 (89.9) 0.068 ± 0.003 (93.4)

0.486 ± 0.040 0.380 ± 0.036 (21.8) 0.286 ± 0.029 (41.2) 0.176 ± 0.040 (63.8) 0.103 ± 0.037 (78.8) 0.066 ± 0.012 (86.4) < LOQ

0.925 ± 0.093 0.738 ± 0.128 (20.2) 0.502 ± 0.096 (45.7) 0.370 ± 0.069 (60.0) 0.260 ± 0.031 (71.9) 0.155 ± 0.039 (83.2) 0.11 ± 0.034 (88.1)


ND not detected Figures in the parenthesis are the percent dissipation of residue


a

1.2 Field- soil at 250 g a.i./ha


Polyhouse- soil at 125 g a.i./ha

y = -0.0174x + 0.4667 R² = 0.9798

0.6

y = -0.0203x + 0.4713 R² = 0.9304

0.4

0.2

0 0

5

10

-0.2

15

20

25

30

35


b 3.5 y = -0.0315x + 3.0088 R² = 0.9916


3

y = -0.0404x + 3.0677 R² = 0.9907

2.5

2

1.5 Field- soil at 125 g a.i./ha y = -0.0354x + 2.7324 Field- soil at 250 g a.i./ha R² = 0.99 Polyhouse- soil at 125 g a.i./ha Polyhouse- soil at 250 g a.i./ha y = -0.0536x + 2.7921

1

0.5

R² = 0.991

0 0

5

10

15

20

25

30

35


c

45 40

y = 0.2577x - 0.0769 R² = 0.8792

Field- soil at 125 g a.i./ha

35

Field- soil at 250 g a.i./ha 30

y = 1.3704x - 4.4863 R² = 0.7694


25


y = 0.4363x - 1.3021 R² = 0.8404

20 15 10

y = 0.5079x + 0.1056 R² = 0.8714

5 0 5

10

15

20

25

30

35

-5 -10

The residues of spiromesifen in soil on the initial day were 0.532 and 1.032 mg kg−1 and 0.486 and 0.925 mg kg−1 under open field and polyhouse conditions at standard and double doses, respectively (Table 4). Contrary to the initial residue deposits on tomato fruit and tomato leaves, the residue levels in the soil were slightly higher in the open field compared to the polyhouse. The spray drift caused by wind speed (4.9–6.4 km h−1) would have resulted in the deposit of spiromesifen in field soil. In spite of this difference, residue levels in the polyhouse soil were

y = -0.0322x + 0.9145 R² = 0.9377


0.8

0

Spiromesifen residues in soil

y = -0.0275x + 0.85 R² = 0.9549

Field- soil at 125 g a.i./ha 1


Dissipation of spiromesifen on the tomato leaves was much faster under open field conditions compared to the polyhouse. Within 5 days, about 30% residue loss was observed from the leaves in the field compared to 9.3–16.1% loss in the polyhouse. This difference increased with time and after 20 days, the residue loss was 81.1–89.5% in the field and 52.3–57% in polyhouse. The higher initial residues and slow dissipation resulted in a situation where the residue levels on the leaves in the polyhouse were nearly three times higher than that in the field after 20 days. After 30 days (last analysis), spiromesifen residues on the leaves in the open field were 0.3 and 0.514 mg kg−1 in the open field and 2.185 and 3.42 mg kg−1 in the polyhouse. The vegetative growth of the tomato plant was significantly higher in the polyhouse compared to the open field. In the field, the height of the tomato plants was 2.5–3 ft whereas in the polyhouse, it was about 6 ft during fruit growth. Dilution of residues due to growth of leaves is a major route for dissipation of pesticides (Jacobsen et al. 2015; Xia et al. 1992; Zongmao and Haibin 1988). In the current study, it was observed that even though the growth of tomato plant was vigorous in the polyhouse, it did not contribute the dissipation of spiromesifen residues from the leaves. Evaporation of pesticide residues from leaves caused by wind speed is an important factor under most environmental conditions (Lester et al. 2017). The effect of reduced exposure to environmental factors, such as wind speed, rainfall, and sunlight, could have resulted in higher spiromesifen residues on polyhouse grown tomato leaves (van den et al. 2008). The photosynthetically active radiation is significantly reduced in polyhouse which would have reduced the degradation of spiromesifen on tomato leaves (Parvej et al. 2010). Spiromesifen degradation in tomato leaves followed first-order rate kinetics (Fig. 4). The half-life of spiromesifen on tomato leaves in the polyhouse was much longer (17.6–18.4 days) compared to the open field (7–7.6 days). Half-life of degradation of acetamiprid was longer in the polyhouse grown tobacco leaves compared to that of the open field ones (Chen et al. 2016). The metabolite spiromesifen-enol was not detected in the tomato leaves during the study period.


Fig. 5 Dissipation of spiromesifen in soil. a Zero-order kinetics. b Firstorder kinetics. c Second-order kinetics

higher from fifth day onwards. However, this difference was comparatively less than that of tomato fruits and tomato leaves. Residues of spiromesifen in soil persisted for 25–30 days under field and polyhouse conditions. From standard dose treatments, the residue levels reached < LOQ under field as well as polyhouse conditions. From


double dose treatments, the residues were 0.068 and 0.11 mg kg−1, respectively. Spiromesifen degradation in soils followed first-order rate kinetics (Fig. 4). Residues of spiromesifen degraded at the half-life of 5.6–7.4 days in the field and 8.4–9.5 days in the polyhouse. The results of this study are in line with other reported studies where half-life of acetamiprid was longer in the green house compared to that of the open field (Chen et al. 2016). Pesticide degradation in soil is dependent on the physical and chemical properties of the soil, pH, and microbial community, etc. (Shahgholi and Ahangar 2014; Rao et al. 1983). The soil characteristics in the field and polyhouse were similar in the current study, so their effect on spiromesifen degradation would be same in both conditions. The lack of photodegradation in the polyhouse would have affected the persistence of spiromesifen in soil; however, this effect was not as evident as it was on tomato fruits and tomato leaves. The soil under tomato plant was covered by the thick foliage of tomato leaves which would have reduced the effect of photodegradation. Therefore, the predominant factor on soil degradation of spiromesifen would be soil characteristics. The pesticides applied to the soil may be taken up by the roots and the possible uptake by the plant is via the roots (Hwang et al. 2017). But spiromesifen exhibits a very low mobility in plants (Weber 2005). The residue from the field soil is unlikely to be translocated to the tomato fruits and leaves (Fig. 5).

Conclusions Cultivation of tomato in polyhouse can be used for increased growth, yield and benefit to farmers, and the ease of growing throughout the year. The dissipation pattern of spiromesifen under open field and controlled environmental conditions was compared in this study. The method used for analysis of spiromesifen and spiromesifen-enol in tomato fruit, tomato leaves, and soil was fit for the purpose. Spiromesifen residues persisted longer on tomato fruits, tomato leaves, and soil under polyhouse conditions compared to the open field. Photodegradation, volatilization (evaporation caused by wind speed), and dissipation due to rainfall were considered the major factors for faster dissipation of spiromesifen in the open field. This difference was most evident on tomato leaves and least in the soil. The residue levels on tomato leaves in the polyhouse after 20 days were 2.96 and 4.86 mg kg−1, which was nearly three times that of the field (1.02 and 1.767 mg kg−1) from treatment at the standard and double doses. After 25 days, the residues on tomato leaves in the polyhouse were about four times that of the field residues. In the soil, the residue levels did not vary much and reached < LOQ after 30 days both in field and polyhouse. Since residues did not accumulate in the soil, the

carryover of spiromesifen to subsequent crops would be ruled out. Even though the residue levels reached < LOQ in the polyhouse soil at harvest in the tomato leaves, it was 2.185 mg kg−1 from standard dose treatment. These results indicate that discretion should be taken to use this chemical in the polyhouse for control of white flies and mites. Acknowledgements The author thanks the Director, ICAR-IIHR, Bangalore and Indian Council of Agricultural Research (ICAR), New Delhi for sponsoring the study.

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