Abstract
Dithiocarbamate fungicides (DTFs) are widely used to control various fungal diseases in crops and ornamental plants. Maximum residual limits in the order of ppb-ppm are currently imposed by legislation to prevent toxicity problems associated with excessive use of DTFs. The specific analytical determination of DTFs is complicated by their low solubility in water and organic solvents. This review summarizes the current analytical procedures used for the analysis of DTF, including chromatography, spectroscopy, and sensor-based methods and discusses the challenges related to selectivity, sensitivity, and sample preparation. Biosensors based on enzymatic inhibition demonstrated potential as analytical tools for DTFs and warrant further research, considering novel enzymes from extremophilic sources. Meanwhile, Raman spectroscopy and various sensors appear very promising, provided the selectivity issues are solved.
Highlights
Dithiocarbamate fungicides (DTFs) are non-systemic pesticides that have been used since the 1940s to control a number of fungal diseases in various crops and ornamental plants
The results revealed that while there is a clear differentiation between the two DTFs based on principal component analysis (PCA) when analyzing individual spectra, it was not possible to distinguish between them when present in mixtures
Despite the large use of DTFs in agriculture, research in the field of analytical methods dedicated to these fungicides has been very limited compared to other classes of pesticides
Summary
Dithiocarbamate fungicides (DTFs) are non-systemic pesticides that have been used since the 1940s to control a number of fungal diseases in various crops and ornamental plants. The DTFs from different groups have different toxicity, resulting in variances in the risk assessment for exposure to specific fungicides Due to their toxicity, fungicides like zineb were banned in many countries around the globe, including the US and the EU, while in countries where it is currently allowed for use, maximum residue limits in the range of ppm are imposed by various organizations worldwide, for various food and agricultural products. The compounds were extracted as water-soluble sodium salts with cysteine and ethylenediaminetetraacetic acid (EDTA) and were derivatized by methylation This strategy enables differentiation between the DTFs from different groups, i.e., thiram, ziram, ferbam, zineb, maneb, mancozeb, milneb, metiram, propineb, nickel bis(dithiocarbamate), and polycarbamate. An LC-MS method was described for the analysis of 10 DTFs in beer, fruit juice, and malt samples, based on the common strategy of transforming the fungicides in water soluble salts and derivatizing them with methyl iodide [8]. Despite general progress in the development of cleaning cartridges, QuEChERS extraction methods and analytical instrumentation for chromatography and MS, there was not a huge advancement in the last years regarding the determination of DTFs
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