Ditiyokarbamat Pestisitleri ve Tayin Yöntemleri

Doğada insan, bitki ya da hayvanlara zarar veren varlıkların etkilerini önleme, yok etme, azaltma ya da bu varlıkları geri püskürtme amacıyla kullanılan kimyasal madde veya madde karışımlarına “pestisit” adı verilmektedir. Pestisitler, balık yemleri, dezenfektanlar gibi kullanımlarının yanı sıra tarımda verimi etkileyen zararlı bitki, hayvan ya da mikroorganizmalara karşı savaşta da önemli bir yere sahiptirler. Ancak bu faydalarına rağmen pestisitler insan sağlığına zararlı pek çok etkiye de sahiptirler. Bu nedenle su ve çeşitli gıda ürünlerinde (sebze, meyve vb.) pestisit kalıntılarının duyarlı bir şekilde tayin edilmesi ve bu tayin için amaca uygun ve güvenilir yöntemlerin kullanılması oldukça önemlidir. Bu çalışmada fungusit olarak kullanılan ditiyokarbamat pestisitlerinin (DC) literatürde verilen farklı tayin yöntemleri incelenmiş, yöntemlerin özellikleri ile iyi ve kötü yönleri karşılaştırılarak bu konuda toplu bir bilgi oluşması sağlanmaya çalışılmıştır

Dithiocarbamate Pesticides and Determination Methods

Chemicals or chemical mixtures used to prevent harmful influence of pests on human, animals or plants are called as pesticides. Besides their usage as fish feeds and disinfectants, they are used against various plants, animals or microorganisms that affect yield of agricultural products. However although they are beneficifial for agriculture, they have many harmful effects on human health. For this reason, determination of pesticide residues in water and various food products (vegetables and fruits etc.) by sensitive methods and using reliable and convenient methods is quite important. In this study, different determination methods of dithiocarbamate pesticides (DC) was reviewed and compared with each other

Keywords:

dithiocarbamate pesticides, maneb, zineb, mancozep thiram, ziram,

PDF

___

[1] Ni, Y., Qiu, P. ve Kokot, S.,Simultaneous determination of three organophosphorus pesticides by differential pulse stripping voltammetry and chemometrics, Analytica Chimica Acta, 516, 7–17, (2004).
[2] Kozak, B., Pestisit kullanımı ve sorunları,.www.tarim.gen.tr, (26. 02. 2009).
[3] Delen, N., Durmuşoğlu, E., Güncan, A., Güngör, N., Turgut, C., Burçak, A., Türkiye’de pestisit kullanımı, kalıntı ve organizmalarda duyarlılık azalışı sorunları, Türkiye Ziraat Mühendisliği 6. Teknik Kongre, Ankara, (2005).
[4] EPA,.http://www.epa.gov/pesticides/,(26.02.2009).
[5] Durmuşoğlu, E., Tiryaki, O. ve Canhilal, R.,Türkiye'de pestisit kullanımı, kalıntı ve dayanıklılık sorunları, Ziraat Mühendisliği VII. Teknik Kongresi, Ankara (2010), http://www.zmo.org.tr/yayinlar/kitap_goster.php?kodu=82.
[6] PUS STATS, Pesticide Usage Statistics, (2009), http://pusstats.csl.gov.uk/myindex.cfm, (11. 03. 2010).
[7] National Agricultural Statistics Service, NASS: Agricultural Chemical Use Database, http://www.pestmanagement.info/nass/ ,(11. 05. 2010).
[8] Delen, N., Kınay, P., Yıldız, F., Yıldız, M., Altınok, H. H., Uçkun, Z., Türkiye tarımında kimyasal savaşımın durumu ve entegre savaşım olanakları, Türkiye Ziraat Mühendisliği 7. Teknik Kongre, Ankara , (2010).
http://www.zmo.org.tr/yayinlar/kitap_goster.php?kodu=83.
[9] Extoxnet, Movement of pesticides in the environment, http://extoxnet.orst.edu/tibs/movement.htm, (06. 06. 2009)
[10] Extoxnet, Entry and fate of chemicals in Humans, http://pmep.cce.cornell.edu/profiles/extoxnet/TIB/entry.html, (06..06.. 2009)
[11] EPA, Types of pesticides, http://www.epa.gov/pesticides/about/types.htm, (17. 03 . 2010).
[12] Beyond Pesticides, California’s Pesticide Use Declined, Yet Millions of Pounds of Toxic Pesticides Continue, (2010), http://www.beyondpesticides.org/dailynewsblog/?p=3019, (11. 03. 2010).
[13] Ripley, B. D. ve Cox, D. F., Residues of ethylenebis(dithiocarbamate) and ethylenethiourea in treated tomatoes and commercial tomato products, Journal of Agricultural and Food Chemistry, 26, 1137-1143, (1978).
[14] Guven, K., Deveci, E., Akba, O., A., Onen, Pomerai, D., The accumulation and histological effects of organometallic fungicides Propineb and Maneb in the kidneys of fetus and female rats during pregnancy, Toxicology Letters, 99, 91– 98, (1998).
[15] Belpoggi, F., Soffritti, M., Guariono, M., Lambertini, L., Cevolani, D., Malton, C., Results of long-term experimental studies on the carcinogenicity of ethylene-bisdithiocarbamate (Mancozeb) in rats annals, New York Academy of Sciences, 982, 123–136, (2002).
[16] Extoxnet, Extoxnet-PIP zineb, http://extoxnet.orst.edu/pips/zineb.htm, (06. 06. 2009).
[17] EPA, EPA R.E.D. Facts, http://www.epa.gov/oppsrrd1/REDs/factsheets/0641fact.pdf, (07. 06. 2009).
[18] Nabam, http://sitem.herts.ac.uk/aeru/footprint/en/Reports/479.htm, (07. 06. 2009).
[19] Osaba, L., Rey, M. J., Aguirre, A., Alonso, A., Graf, U., Evaluation of genotoxicity of captan, maneb and zineb in the wing spot test of Drosophila melanogaster: role of nitrosation, Mutation Research, 518, 95–106, (2002) .
[20] Humeres, E., Debacher, N. A. ve Sierra, M.M. de S., Mechanisms of acid decomposition of dithiocarbamates. 2. efficiency of the intramolecular general acid catalysis, Journal of Organic Chemistry, 64, 1807-1813, (1999).
[21] Marshall, W. D. ve Jarvis, W.R., Procedures for the removal of field residues of ethylenebis(dithiocarbamate) (EBDC) fungicide and ethylenethiourea (ETU) from tomatoes prior to processing into juice, Journal of Agricultural and Food Chemistry,27, 4, 766-769, (1979)
[22] Wang, G-J., Yin, C-M., Wang, Y., Kong, Y-H., Wang, G-H., Wu, C-Y., Zhang, LF., Liu, Z-R., The thermal behaviour of ethylene-bis dithiocarbamates maneb, zineb and mancozeb. Part 1. The mechanism of the thermal decomposition, Thermochimica Acta, 220, 213-227, (1993).
[23] Nash, R. G., Uptake of ethylenebis(dithiocarbamate) fungicides and ethylenethiourea by soybeans, Journal of Agricultural and Food Chemistry, 24, 3, 596-601, (1976).
[24] Rhodes, R. C., Studies with manganese [14C]ethylenebis(dithiocarbamate) ([14C]maneb) fungicide and [14C]ethylenethiourea ([14C]ETU) in plants, soil, and water, Journal of Agricultural and Food Chemistry, 25, 3, 528-533, (1977).
[25] Knio, K. M., Dagher, S. ve Saad,A.,The fate and persistence of zineb, maneb, and ethylenethiourea on fresh and processed tomatoes, Food Additives & Contaminants, 17, 5, 393 – 398, (2000).
[26] Marshall W. D., Thermal decomposition of ethylenebis(dithiocarbamate) fungicides to ethylenethiourea in aqueous media, Journal of Agricultural and Food Chemistry, 25, 2, 357-361, (1977).
[27] ECPA, http://www.ecpa.be/website/page.asp?mi=2.
[28] Yıldız, M., Gürkan, M. O., Turgut, C., Kaya, Ü, Ünal, G., Tarımsal savaşımda kullanılan pestisitlerin yol açtığı çevre sorunları, , Türkiye Ziraat Mühendisliği 6. Teknik Kongre, Ankara, (2005).
[29] Chun, O. K. ve Kang, H. G., Estimation of risks of pesticide exposure, by food intake, to Koreans, Food and Chemical Toxicology, 41, 1063-1076, (2003).
[30] CSL, http://www.csl.gov.uk/science/organ/pvm/puskm/pusg.cfm, 2006.
[31] DOAF, http://www.agriculture.gov.ie/publicat/pesticides/PESTICID.PDF, 2006,
[32] RASFF, http://ec.europa.eu/comm/food/food/rapidalert/resources/publications_en.htm, 2006.
[33] Uludağ İhracatçı Birlikleri, http://www.uib.org.tr/haber_v1/devami1.asp?id=310, 2009, (16. 04. 2009).
[34] Clarke, D. G., Baum, H., Stanley, E. l., Hester, W. F., Determination of dithiocarbamates, Analytical Chemistry, 23, 1842-1846, (1951).
[35] Lowen, W. K., Determination of dithiocarbamate residues on food crops, Analytical Chemistry, 23, 12, 1846-1850, (1951).
[36] Malik, A. K., Faubel, W., Capillary electrophoretic determination of zincdimethyldithiocarbamate (Ziram) and zinc ethylenebisdithiocarbamate (Zineb), Talanta, 52, 341-346, (2000)
37] Sastry, C. S. P., Satyanarayana, P., Rao, A. R. M., Singh, N. R., Spectrophotometric determination of thiram, ziram and zineb in formulations, water, grains and vegetables using oxidised hematoxylin, Journal of Food Science and Technology, 25, 377-378, (1988).
[38] Mathew, L., Rao, P., Iyer, C. S. P., Damodaran, A. D., Spectrophotometric determination of ziram (dithiocarbamate fungicide) by thiocyanate and rodamine 6 G method, Talanta, 42, 41-43, (1995).
[39] Malik, A. K. ve Faubel, W., Methods of analysis of dithiocarbamate pesticides: a review, Pesticide Science, 55, 965-970, (1999).
[40] Malik A. K. Sharma, V., Sharma, V. K. ve Rao, A. L. J, Column Preconcentration and Spectrophotometric Determination of Ziram and Zineb in Commercial Samples and Foodstuffs Using (1,2'-Pyridylazo)-2-naphthol (PAN)-Naphthalene as Adsorbate, Journal of Agricultural and Food Chemistry, 52, 26, 7763-7767, (2004).
[41] Malik, A. K., Kapoor, J. ve Rao, A. L. J., Simple and sensitive spectrophotometric determination of ziram, zineb and ferbam in commercial samples and foodstuffs using phenylfuorone, Journal of Environmental Monitoring, 2, 367-371, (2000).
[42] Malik, A. K. ve Rao, A. L. J., Spectrophotometric determination of iron(III) dimethyldithiocarbamate (ferbam), Talanta, 44, 177-183, (1997).
[43]. Walash, M. I., Belal, F., Metwally, M. E., Hefnawy, M. M., Spectrophotometric determination of maneb, zineb and their decomposition products in some vegetables and its application to kinetic studies after greenhoue treatment, Food Chemistry, 47, 4, 411-416, (1993).
[44] Malik, A. K., Kaul, K. N., Lark, B. S., Rao, A. L. J., Simple and sensitive spectrophotometric determination of tetramethylthiuram disulphide (Thiram), Pesticide Science, 53, 104-106, (1998).
[45] Kaur, M., Kaur, V., Malik, A. K., Verma, N., Singh, B., Rao, A. L. J., Development of a derivative spectrophotometric method for the determination of fungicide zinc ethylenebisdithiocarbamate using sodium molybdate, Journal of Brazelian Chemical Society, 20, 993-998, (2009).
[46] Sharma, V. K., Aulakh, J. S. ve Malik, A. K., Thiram: degredation, applications and analytical methods, Journal of Environmental Monitoring, 5, 717-723, (2003).
[47] Sharma, V. K., Aulakh, J. S. ve Malik, A. K., Fourth derivative spectrophotometric determination of fungicide thiram (tetramethyldithiocarbamate) using sodium molybdate and its application, Talanta, 65, 375-379, (2005).
[48] Schwack, W. ve Nyanzi, S., Second-Derivative UV Spectrometric microdetermination of dithiocarbamate residues as methyl xanthate, Journal of AOAC International, 78, 2 , 458-462, (1995).
[49] Kesari, R. ve Gupta, V. K., A sensitive spectrophotometric method for the determination of dithiocarbamate fungicide and its application in environmental samples, Talanta, 45, 1097-1102, (1998).
[50] Dias, M. C., de Queiroz, M. E. L. R., Reis, E. L., Neves, A. A., de Oliveira, T. T., Nagem, T. J., Determination of Maneb residues in tomatoes, by spectrophotometric method of acid hydrolysis, through multivariate calibration, Analytical Letters, 33, 1857-1868, (2000).
[51] Nakazawa, H., Tsuda, Y., Ito, K., Yoshimura, Y., Kubo, H., Homma, H. Determination of dithiocarbamate fungicides by reversed-phase ion pair liquid chromatography with chemiluminescence detection, Journal of Liquid Chromatography &Related Technologies , 27, 4, 705-713, (2005).
[52] Paz, J. L. L. ve Catalá-Icardo, M., Flow injection-photoinducedchemiluminescence determination of ziram and zineb, Analytica Chimica Acta, 625, 173-179, (2008).
[53] Moros, J., Armenta, S., Garrigues, S., de la Guardia, M., Comparision of two vibrational procedures for the direct determination of mancozeb in agrochemicals, Talanta, 72, 72-79, (2007).
[54] Lo, C-C., Ho, M-H. ve Hung, M-D., Use of high performance liquid chromatographic and atomic absorption methods to distinguish propineb, zineb, maneb and mancozeb fungicides, Journal of Agricultural Food Chemistry, 44, 2720-2723, (1996).
[55] Silva, M. del Pilar, Procopio, J. R. ve Hernandez, L., Electrochemical detection in the determination of several dithiocarbamates by reverse-phase liquid chromatography, Journal of Liquid Chromatography and Related Technologies, 22, 3, 463-475, (1999).
[56] Garcinuno, R. M., Fernandez-Hernando, P. ve Camara, C., Simultaneous determination of maneb and its main metabolites in tomatoes by liquid chromatography using diode array ultraviolet absorbance detection, Journal of Chromatography A, 1043, 225-229, (2004).
[57] Hayama, T. ve Takada, M., Simple and rapid method for the determination of ethylenebisdithiocarbamate fungicides in fruits and vegetables using liquid chromatography with tandem mass spectrometry, Annali Bioanalytical Chemistry, 392, 969-976, (2008).
[58] van Lishaut, H. ve Schwack, W., Selective trace determination of dithiocarbamate fungicides in fruits and vegetables by reversed-phase ion-pair liquid chromatography with ultraviolet and electrochemical detection, Journal of AOAC International, 83, 3, 720-727, (2000).
[59] Filipe, O. M. S., Vidal, M. M., Duarte, A. C., Santos, E. B. H., Influence of fulvic acids and copper ions on thiram determination in water, Journal of Agricultural and Food Chemistry, 56, 7347-7354, (2008).
[60]. Kazos, E. A., Constantine, D. S., Nanos, C. G., Konidari, C. N., Determination of dithiocarbamate fungicide propineb and its main metabolite propylenethiourea in airborne samples, Chemosphere, 68, 2104-2110, (2007).
[61] Lawrance, J. F., Iverson, F., Hanekamp, H. B., Bos, P., Frei, R. W., Liquid chromatography with UV absorbance and polarographic detection of ethylenethiourea and related sulfur compunds, Journal of Chromatography, 212, 245-250, (1981).
[62] Garcinuno, R. M., Ramos, L., Fernandez-Hernando, P., Camera, C., Optimization of a matrix solid-phase dispersion method with subsequent clean-up for the determination of ethylenebisdithiocarbamate residues in almond samples, Journal of Chromatography A, 1041, 35-41, (2004).
[63] Kontou, S., Tsipi, D., Oreopoulou, V., Tzia, C., Determination of ETU in tomatoes and tomato products by HPLC-PDA. Evaluation of cleanup procedures, Journal of Agricultural Food Chemistry, 49, 1090-1097, (2001).
[64] Bolzoni, L., Sannino, A. ve Bandini, M., Determination of ethylenethiourea and propylenethiourea in tomato products and in fruit purees, Food chemistry, 47, 299-302, (1993).
[65] Doerge, D. R. ve Yee, A. B. K., Liquid chromatographic determination of ethylenethioruea using pulsed amperometric detection, Journal of Chromatography, 586, 158-160, (1991).
[66] Wang, H., Pacakova, V. ve Stulik, K., Determination of ethylenethiourea in beverages without sample pretreatment using high-performance liquid chromatography and amperometric detection on a copper electrode, Journal of Chromatography, Cilt 457, 398-402, (1988).
[67] Maruyama, M., Residue analysis of ethylenethiourea in vegetables by high performance liquid chromatography with amperometric dedection, Fresenius Journal of Analytical Chemistry, 348, 324-326, (1994).
[68] Sottani, C., Bettinelli, M., Fiorentino, M. L., Minoia, C., Analytical method for the quantitative determination of urinary ethylenethiourea by liquid chromatography/electrospray tandem mass spectrometry, Rapid Communications in Mass Spectrometry, 17, 2253-2259, (2003).
[69] Startin, J. R., Hird, S. J. ve Sykes, M. D., Determination of etyhlenethiourea (ETU) and propylenethiourea (PTU) in foods by high performance liquid chromatography-atmospheric pressure chemical ionisation-medium-resolution mass spectrometry, Food Additives and Contaminants, 22, 3, 245-250, (2005).
[70] Pease, H. L. ve Holt, R. F., Manganese ethylene (bisdithiocarbamate) (maneb)/ethylenethiourea (ETU) residue studies on five crops treated with ethylenebis(dithiocarbamate) (EBDC) fungicides, Journal of Agricultural Food Chemistry , 25, 3, 561-567, (1977)
[71] Dubey, J. K., Heberer, T. ve Stan, H-J., Determination of ethylenethiourea in food commodities by a two step derivatization method and gas chromatography with electron-capture and nitrogen-phosphorus detection, Journal of Chromatography A, Cilt 765, 31-38, 1997.
[72] Vryzas, Z., Papadakis, E. N. ve Papadopoulou-Mourkidou, E., Micro-wave-assisted extraction (MAE)-acid hydrolysis of dithiocarbamates for trace analysis in tobacco and peaches, Journal of Agricultural and Food Chemistry, 50, 8, 2220-2226, (2002).
[73] Gustafsson, K. H. ve Thompson, R A., High-pressure liquid chromatographic determination of fungicidal dithiocarbamates, Journal of Agricultural and Food Chemistry, 29, 4, 729,732, (1981).
[74] Weissmahr, K. W., Houghton, C. L. ve Sedlak, D. L., Analysis of the dithiocarbamate fungicides ziram, maneb and zineb and the flotation agent ethylxanthogenate by ion-pair reversed-phase HPLC, Analytical Chemistry, 70, 22, 4800-4804, (1998).
[75] Mathew, L., Reddy, M. L. P., Rao, T. P., Iyer, C. S. P., Damodaran, A. D., Differential pulse anodic stripping voltammetric determination of Ziram (a dithiocarbamate fungicide), Talanta, 43, 73-76, (1996).
[76] Rao, A. L. J. ve Verma, N., Polarographic determination of zineb and maneb pesticides, Bulletin of Electrochemistry, 6, 4, 439-441, (1990). [77] Malik, A. K. ve Rao, A. L. J., Polarographic determination of zineb and maneb, Journal of Indian Chemical Society, 75, 491-492, (1998).
[78] Lin, M. S., Jan, B. I., Leu, H-J., Lin, J. S., Trace measurement of dithiocarbamate based pesticide by adsorptive stripping voltammetry, Analytica Chimica Acta, 388, 111-117, (1999).
[79] Lin, M. S. ve Wang, J. S., Determination of an ethylene bisdithiocarbamate based pesticide (Nabam) by cobalt phthalocyanine modified carbon ink electrode, Electroanalysis, 16, 11, 904-909, (2004).
[80] Karakoç, Ö., Bazı etilen bis(ditiyokarbamat) pestisitlerinin voltammetrik tayini, Doktora Tezi, Balıkesir Üniversitesi, Fen Bilimleri Enstitüsü, Balıkesir, (2010).