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Quantitation of Heterogeneous Formulations of Morpholine-Type Fungicides and Surfactants in Polluted Soils

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Abstract

The paper reports ultraviolet matrix-assisted laser desorption/ionization mass spectroscopy (UVMALDI-MS) protocol for determination of complex heterogeneous emulsion or suspension formulations. The active agents and surfactants are morpholine fungicide fenpropimorph (1), amorolfine (2), tridemorph (mixture of 2,6-dimethyl-4-alkylmorpholins 3–6), 2,6-dimethyl-4-[2-methyl-3-(6-methyl-decahydro-naphthalen-2-yl)-propyl]-morpholine (7), dodemorph (8), main metabolite of 1 fenpropimorph acid (9), sodium dodecyl sulfate (10), and stearate (11). The full method and techniques validation as well as method performance parameters are discussed in terms of their maximal representativeness toward real environmental and foodstuff assay problems. These are additionally complicated by heterogeneous laterally, vertically, and time distribution of pesticide contaminants and their major metabolites in environmental samples. The real environmental heterogeneous distribution is elucidated, studying sterilized soil fractions with particle size 2.0 μm, clay content 11.5 %, silt 23.0 %, sand 8.1 %, and pH ∈ 6.0–8.1. A statistical sampling cluster approach is used. The method performance parameters are concentration LODs of 0.026 mg kg−1 (res. LOQs 0.08666 mg kg−1). Concentration linear dynamic ranges are ∈ 0.025–7.3 mg kg−1 (r 2 = 0.99822 and 0.99421) and ∈ 2.3–7.4 mg kg−1 (level of confidence of 99.331 %) for complex spiked heterogeneous soil samples. The data illustrates the great capability of method and its promising application for environmental contamination monitoring and controlling programs for assessment.

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Abbreviations

APCI:

atmospheric pressure chemical ionization (mass spectrometric method)

EI:

electron impact (mass spectrometric method)

GC:

gas chromatography

HPLC:

high-performance liquid chromatography

LC:

liquid chromatography

ESI:

electrospray ionization (mass spectrometric method)

LODs:

(concentration) limits of detection (method)

LOQs:

(concentration) limits of quantitation (method)

MALDI:

matrix-assisted laser desorption/ionization (mass spectrometric method)

MDL:

method detection limit (instrumental)

MS/MS:

tandem mass spectrometry

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Acknowledgments

The authors thank Deutscher Akademischer Austausch Dienst, Deutsche Forschungsgemeinschaft, the central instrumental laboratories for structural analysis at Dortmund University (Federal State Nordrhein-Westfalen, Germany), and the analytical and computational laboratory clusters at the Institute of Environmental Research at same University.

Conflict of Interests

Michael Spiteller has received research grants (Deutsche Forschungsgemeinschaft, 255/22-1 and 1315); Bojidarka Ivanova has received research grant (Deutsche Forschungsgemeinschaft, 255/22-1).

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Correspondence to Bojidarka Ivanova.

Electronic supplementary material

Chemical diagrams (Scheme S1) of the analytes 1–9; Thermodynamics (Table S1); Optimized molecular structures of the ionic adducts of 10 and 11 observed in the gas phase; Solvent accessible surfaces, the hydrogen and coordinative bonds (Scheme S2); UV-MALDI-MS spectrum of 10 (Fig. S1).

Scheme S1

(DOC 57 kb)

Table S1

(DOC 44 kb)

Scheme S2

(DOC 531 kb)

Figure S1

(DOC 37 kb)

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Ivanova, B., Spiteller, M. Quantitation of Heterogeneous Formulations of Morpholine-Type Fungicides and Surfactants in Polluted Soils. Water Air Soil Pollut 225, 1918 (2014). https://doi.org/10.1007/s11270-014-1918-9

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