Analytical Sciences

LC/MS Studies on Characterization andDetermination of N,N'-Ethylenebisdithiocarbamate Fungicidesin Environmental Water Samples

Yoshifumi HANADA,*¹Tiezi TANIZAKI,*¹ Minoru KOGA,*²Hiroaki SHIRAISHI,*³ and MitsuyukiSOMA*⁴

*1 Kitakyushu City Institute ofEnvironmental Sciences, 1-2-1 Shin-ike, Tobata, Kitakyushu 804-0082,Japan
*2 Prefectural University of Kumamoto, 3-1-100 Tukide, Kumamoto862-8502, Japan
*3 The National Institute for Environmental Studies,16-2 Onogawa, Tsukuba, Ibaraki 305-8506, Japan
*4 University ofShizuoka, 52-1 Yada, Shizuoka 422-8526, Japan

Liquid chromatography/mass spectrometry(LC/MS) has been applied to analyze N,N'-ethylenebisdithioarbamatefungicides (EBDCs: manzeb, maneb and zineb) in environmental water samples.The EBDCs that are zinc and/or manganese salts are transformed into readilywater-soluble sodium salts by adding an alkaline EDTA solution. TheN,N'-ethylenebisdithiocarbamate anion is extracted intochloroform-hexane (3:1) as an ion pair with tetrabutylammonium, and thenS-alkylated with methyl iodide. The extraction and derivatizationare carried out at room temperature. The derivatizedethylenebisdithiocarbamic acid dimethyl ester is introduced into an LC/MSequipped with a negative ion electrospray ionization interface.Identification of the compound is performed with the specificquasi-molecular ion, and the quantitative analyses are carried out usingthe peak areas. The average recoveries and coefficients of variation ofEBDCs at sub-ppb level are 79.1% and 29.3% (n = 6), respectively.The limit of detection based on standard deviation of 0.043 ug/L for manzebis achieved.

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