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Degradation of Dicofol and Residues in Kale Plots

P. Danuwat 1/ C. Phatthanawan 2/ T. Hassanai 3/ K. Path 4/ S. Panlop 5/ P. Rimruthai 6/ K. Supranee 7/ T. Phatthanee 8/*

ABSTRACT Degradation of Dicofol and Chlorpyrifos were studied in terms of time for the chemical degraded in organic plots, Good Agricultural Practice (GAP) plots, and controlled plots. Kale was chosen for the reference of annual crop to study the degradation in and Sing Buri for 6 months. Dicofol had degraded within 2-3 months in control plot, 4-5 months in GAP plot and not detected in organic plot. Chlorpyrifos had degraded within 2 months in control plot, 4-5 months in GAP plot and not detected in organic plot. The pH of Kale plots was about Neutral to Slightly Alkaline. Understanding of the fate and behavior of under tropical conditions was important both in agronomical and environmental terms. The results can used as a scientific data base to determine time for appropriated transition periods of conventional agriculture to organic production in .

Key words: Kale, , Dicofol, Chlorpyrifos, transition period, Good Agricultural practice, Organic plant

Introduction The trend towards organic cultivation in Thailand is growing fast since producers and consumers are becoming aware in health and environment (Lombardi et al., 2010). The principal guidelines for organic production are to use materials and practices that enhance the ecological balance of natural systems and that integrate the parts of the

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310 วารสารวิชาการเกษตร ปีที่ 33 ฉบับที่ 3 กันยายน - ธันวาคม 2558 farming system into an ecological whole throughout the transition period at least (Fabian et al., 2012). The organic crop 12 months before the planting of annual production certification standard requires crops and 18 months before the first that land must not have any prohibited harvest of the perennials.” However, the substances applied to it for at least 36 standard of Codex had difference defined, months before harvesting (USDA, 2014). that transition period should be at least The standards are set under the two years for annual crops and three management of the National Bureau of years for perennials. This large difference Agricultural Commodity and Food has affected the acceptance of Thai Standards (ACFS). This organization is agricultural product into the international responsible for determining the standards markets which rely on the standard of and controlling agricultural practices in Codex as a reference limit. The order to compare to the international international markets include The organic standards. However, there is one European Union (EU), Japan, The United issue that is not officially accepted in States of America etc. Thailand; that is the time spent in the Kale (Brassica oleracea L.) is a decay of residual agricultural chemicals. popular and an economic crop in This affects the indication of time from Southeast Asia that belongs to the the start of organic production to Brassicaceae family. It grows well in containing a guarantee on the goods as strong, moist soil that is enriched with being organic, called transition period. organic matter (Oyugi, 2012). However, There are two aspects to the conversion. kale is mostly vulnerable to insect pests First, is the grower skills and experience such as diamondback moth [Plutella in farming and the second is transition of xylostella (Linnaeus)], beet armyworm the land. This period, according to the (Spodoptera exigua (Hübner), common Department of Agriculture and cutworm [Spodoptera litura (Fabricius)], International Federation of Organic cabbage looper (Trichoplusia ni Hübner), Agriculture Movements (IFOAM), is cabbage webworm [Hellula undalis defined as “the provision of the method (Fabricius)], leaf eating beetle (Phyllotreta in organic production that is practiced chontanica Duvivier & P. sinuata Steph.)

Thai Agricultural Research Journal Vol. 33 No. 3 September - December 2015 311 (Kianmeesuk et al., 1999). Tall varieties of and fruit by test in 559 samples kale are transplanted when they are ten (Jarupong et al., 2012). Chinese-Kale has to fifteen centimeters (four to six inches) been reported in commodities of high high. The whole plant can be harvested at ; with 20% of samples once or extend the harvest by picking examined were found to exceed the individual leaves. Kale can be harvested FAO’s allowable maximum residue level at any time as soon as the leaves are (Rerkasem, 2004). Therefore, the main large enough (21-28 days) (Oyugi, 2012). purposes of this work were study the It is mostly vulnerable to insect pests degraded of Dicofol and Chlorpyrifos in such as diamondback moth, beet kale plots for use as reference to indicate armyworm, common cutworm, cabbage an appropriate transition period to organic looper, cabbage webworm and leaf eating production (annual) in Thailand. beetle (Kianmeesuk et al., 1999). Indiscriminate use of pesticides is very Materials and Methods common in this crop culture (Kumar and Experimental sites Moorthy, 2001), which leads to The trial plots to test the degradation destruction of beneficial insects and other of agricultural residual chemicals was non-target organisms, accumulation of selected by considering the landscape toxic residues on produce and human which provided appropriate factors for the poisoning. experiment. Good Agricultural Practice In Thailand, Food and Drug plot, organic plot and chemical spraying Administration of Thailand had found plot in Thumbon Nongyaeng, Amphur Dicofol in the super market by testing in Sansai, , and Kale (FDA, 2012). Moreover, Kale in the Thumbon Srajaeng, Amphur Bangrachan, North market fair, Thailand had detected were chosen as the Chlorpyrifos in all samples about 0.02- trial kale plantations. 0.88 ppm (Kanjanamangsak et al., 2010). According to the study in Northeast Experimental plan Thailand, Chlorpyrifos was the most 42 The experiment were conducted in percent that can detected in vegetable Randomized Complete Block Design

312 วารสารวิชาการเกษตร ปีที่ 33 ฉบับที่ 3 กันยายน - ธันวาคม 2558 (RCBD) with 3 replications. Three magnesium sulfate, 0.1 gm of PSA and treatments were 1. control treatment with 0.05 gm of activated charcoal and shaken spraying Dicofol and Chlorpyrifos only by vortex for 1 min. The mixture was then one time 2. GAP treatment with spraying centrifuged at 2,500 rpm for 10 min. Ten Dicofol and Chlorpyrifos two times and milliliter was pipetted into a new tube and 3. organic treatment with out spraying evaporated by N-Evaporator at 45 ํ°C until by the rule of organic it was almost dried. After that, the volume certification. The details of 3 treatments of the solution was adjusted by 5 ml. of at each trail plot were shown in Table 1, hexane and filtered by Nylon Disc filter 2, 3 and 4. Data was recorded very 0.45 µm into vial for 2 ml. The solution was month for 6 months analyzed by GC-µECD (6890N, Agilent Technology), and the result was ensured Soil sampling and Pesticide analysis by GC/MS (5973 inter, Agilent The soil samples in the trial plots Technology) (AOAC, 2003). The data was of the annual crops in the selected areas, reported until it not detected (LOD lower Chiang Mai and Sing Buri, were sampling than 0.01 mg/kg). by auger equipment under the appropriate depths of kale about 0.6-1.2 Statistical analysis inches (DOA, 2014). The amount of The data was analyzed by SPSS Dicofol and Chlorpyrifos were analyzed by (Statistical Package for the Social AOAC method (2003).Fifty grams of Sciences version 17) in Duncan’s new sampling soils mixed with 100 ml. of multiple range tests. The different result acetonitriles and blended for 1 min. The between the experimental groups was mixture was filtered through paper no.1 considered at a 95% confidence interval. and transferred to a plastic bottle which contained 5 gm of sodium chloride. The Results and Discussion bottles were shaken for 1 min and left it Dicofol until the solution was separated. The The amounts of Dicofol in kale supernatant was transferred to a plot of Chiang Mai and Sing Buri centrifuge tube which contained 0.5 gm of Province were shown in Table 5 and 6,

Thai Agricultural Research Journal Vol. 33 No. 3 September - December 2015 313 Table 1 The activity of kale plot in Chiang Mai for study Dicofol degradation Soil sampling times (months) Treatment 0 1 2 3 4 5 6 Spraying Control - - Harvest - Harvest - Dicofol Spraying Spraying Spraying GAP - Harvest Harvest - Dicofol Dicofol Dicofol Organic - - - Harvest - Harvest -

Table 2 The activity of kale plot in Sing Buri for study Dicofol degradation Soil sampling times (months) Treatment 0 1 2 3 4 5 6 Spraying Control - Harvest - - - Harvest Dicofol Spraying Spraying GAP - Harvest - - Harvest Dicofol Dicofol Organic - - Harvest - - - Harvest

Table 3 The activity of kale plot in Chiang Mai for study Chlopyrifos degradation Soil sampling times (months) Treatment 0 1 2 3 4 5 6 Spraying Control - - Harvest - Harvest - Chlopyrifos Spraying Spraying Spraying GAP - Harvest Harvest - Chlopyrifos Chlopyrifos Chlopyrifos Organic - - - Harvest - Harvest -

Table 4 The activity of kale plot in Sing Buri for study Chlopyrifos degradation Soil sampling times (months) Treatment 0 1 2 3 4 5 6 Spraying Control - Harvest - - - Harvest Chlopyrifos Spraying Spraying GAP - Harvest - - Harvest Chlopyrifos Chlopyrifos Organic - - Harvest - - - Harvest

314 วารสารวิชาการเกษตร ปีที่ 33 ฉบับที่ 3 กันยายน - ธันวาคม 2558 Table 5 Amount of Dicofol (mg/kg) in the kale plot, Chiang Mai Soil sampling times (months) Treatment 0 1 2 3 4 5 6 9.3038 1.0119 Control ND ND ND ND ND ±0.0018ab ±0.0012c 9.3146 14.0243 6.1899 2.1356 GAP ND ND ND ±0.0021ab ±0.0015a ±0.0029b ±0.0011c Organic ND ND ND ND ND ND ND Values were mean ± S.D. (n=3). Mean in the same column, followed by a common letter are not significantly different at 5% level by DMRT or LDS. ND = Not detected (LOD lower than 0.01 ppm).

Table 6 Amount of Dicofol (mg/kg) in the kale plot, Sing Buri Soil sampling times (months) Treatment 0 1 2 3 4 5 6 7.0198 1.0087 0.0217 Control ND ND ND ND ±0.0027a ±0.0024b ±0.0019c 8.1282 1.1101 0.0146 5.4377 1.0023 GAP ND ND ±0.0013a ±0.0016b ±0.0020c ±0.0022a ±0.0014b Organic ND ND ND ND ND ND ND Values were mean ± S.D. (n=3). Mean in the same column, followed by a common letter are not significantly different at 5% level by DMRT or LDS. ND = Not detected (LOD lower than 0.01 ppm).

respectively. Kale plot in Chiang Mai detected after 5 months. Whereas no Province, Amount of detected Dicofol Dicofol was detected in organic treatment in control treatment was decreased from because of no chemical used in this plot. 9.3038 to 1.0119 mg/kg and could not In Sing Buri Province, detected detected after 3 months. Although Dicofol Dicofol was decreased from 7.0198 to was sprayed 3 times in 1st, 2nd and 4th 0.0217 mg/kg and not detected after 3 month in GAP treatment but detected months in control treatment. GAP Dicofol was decreased from 9.3146 to treatment showed decreasing of Dicofol 2.1356 mg/kg in 4 month and not from 8.1282 to 1.0023 mg/kg in 5 months

Thai Agricultural Research Journal Vol. 33 No. 3 September - December 2015 315 and not detected after 6 months even Chlorpyrifos though spraying 2 times in 1st and 4th Detected Chlorpyrifos in kale plot month were done . Similarly to Chiang of Chiang Mai and Sing Buri Province Mai kale plot, no Dicofol or any other was shown in Table 7 and 8 respectively. residual agricultural chemicals was In Chiang Mai Province, decreasing in the detected in the soil. FAO (1992) reported amount of Chlorpyrifos from 18.1281 to that, Dicofol was found to disappear 1.0119 mg/kg in 2 month and not quickly and the half-life was 62 days. detected after 3 months was expressed in Soil acts like an active filter, where kale plot under control treatment . Under chemical compounds are degraded by GAP treatment, detected Chlorpyrifos physical, chemical and biological was decreased from 17.1678 to 1.1904 processes. It is also a selective filter mg/kg in 5 months and not detected after because of its capacity to retain 6 months. chemicals and avoid their seepage into Similar result was also obtained aquifers (Cornejo et al., 2000).. The half- from kale plot in Sing Buri Province. lives of pesticides have been reported to Detected Chlorpyrifos in control increase with decreasing soil water treatment was decreased from 14.5311 to content and temperature (Ou et al., 1983). 0.1871 and not detected after 3 months. Decreasing was also found in GAP

Table 7 Amount of Chlopyrifos (mg/kg) in the kale plot, Chiang Mai Soil sampling times (months) Treatment 0 1 2 3 4 5 6 18.1281 1.0173 Control ND ND ND ND ND ±0.0031a ±0.0025b 17.1678 20.0260 1.2193 16.4025 1.1904 GAP ND ND ±0.0028a ±0.0027a ±0.0019b ±0.0026a ±0.0017b Organic ND ND ND ND ND ND ND Values were mean ± S.D. (n=3). Mean in the same column, followed by a common letter are not significantly different at 5% level by DMRT or LDS. ND = Not detected (LOD lower than 0.01 ppm).

316 วารสารวิชาการเกษตร ปีที่ 33 ฉบับที่ 3 กันยายน - ธันวาคม 2558 Table 8 Amount of Chlopyrifos (mg/kg) in the kale plot, Sing Buri Soil sampling times (months) Treatment 0 1 2 3 4 5 6 14.5311 0.1871 Control ND ND ND ND ND ±0.0012b ±0.0013c 12.0485 0.0485 20.0001 0.0821 GAP ND ND ND ±0.0010b ±0.0017d ±0.0014a ±0.0010cd Organic ND ND ND ND ND ND ND Values were mean ± S.D. (n=3). Mean in the same column, followed by a common letter are not significantly different at 5% level by DMRT or LDS.ND = Not detected (LOD lower than 0.01 ppm). treatment from 12.0485 to 0.0821 mg/kg treatment. GAP treatment, Dicofol and in 4 month and not detected after 5 Chlorpyrifos were not detected after 5 months. Chlorpyrifos was not detected and 6 months. Kale plots cultivated under from Organic plot in Chiang Mai and Sing organic agricultural practice in Chiang Mai Buri Province (2009 ) mentioned and Sing Buri Province were not shown that degradation rate of chlorpyrifos was any detectable Dicofol and Chlorpyrifos or the first order and half-life was significantly any other residual agricultural chemicals extended with increasing chlorpyrifos in the soil. Information on the actual input concentration. It was between 60 and 120 of pesticides into the environment is days but it could range from 2 weeks to crucial for proper risk assessment and the over 1 year depending on the soil type, rational design of risk reduction measures. soil micro-organisms, and climatic Understanding of the fate and behavior of condition (Singh et al., 2002). pesticides under tropical conditions was important both in agronomical and Conclusion environmental terms. Degradation time of Complete degradation of Dicofol the pesticide residues depended on area, and Chlorpyrifos in kale plot were shown pH and temperature.The results of this after 3 months in both Chiang Mai and study can be used as a scientific- Sing Buri Provinces under control supported data base to determine the

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