Felix Hernandez*, Juan V. Sancho and Oscar J. PozoAnalytical Chemistry, Experimental Sciences Department, ESTCE, University Jaume I, E-12071 Castellon, Spain

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Figure 2. Negative ion electrospray full-scan mass spectra (bottom) and product ion spectra (top) from (a) DEP, (b) DETP, (c) DEDTP,(d) DMP, and (e) DMTP.

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Figure 3. Proposed fragmentation pathway for dialkylphosphates.

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Figure 4. LC/ESI-MS/MS chromatograms for DMTP, DEP, DETP and DEDTP: (a) 10 g/L standards, (b)urine sample blank and (c) urine sample spiked at 10 g/L.

Table 2. Analytical characteristics of the developed LC/ES-MS/MS method

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Table 3. Validation study of the developed procedure for thedetermination of dialkyl phosphates in spiked urine samples (twosamples at two levels, n = 5 each)

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Figure 5. Evolution of concentration levels of chlorpyrifos metabolites in urine during oneweek of application in citrus orchards obtained for exposed (a and b) and non-exposedfarmers (c).

Figure 6. Chromatograms from urine sample of a farmer exposed to chlorpyrifos (sample a, collected on Thursday): (a) LC/ESI-MS/MS chromatograms for alkyl phosphates and LC/LC/ESI-MS/MS chromatogram for TCP; (b) confirmation of the two dialkylphosphates derivatives found, (Q) quantitation transition; (q) confirmation transition.2 ? @ :# 1 $8; 944*995

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