Oxamyl

Oxamyl (Vydate) 0.2 0.2 Slight nervous system effects Runoff/leaching from insecticide used on apples, potatoes, and tomatoes... 

Figure 13.15 Chromatograms obtained by on-line ti ace enrichment of 50 ml of Ebro river water with and without the addition of different volumes of 10% Na2S03 solution for every 100 ml of sample (a) blank with the addition of 1000 p.1 of sulfite (b) spiked with 4 p.g 1 of the analytes and 1000 p.1 of sulfite (c) spiked with 4 p.g 1 of the analytes and 500 p.1 of sulfite (d) spiked with 4 p.g 1 of the analytes without sulfite. Peak identification is as follows 1, oxamyl 2, methomyl 3, phenol 4, 4-niti ophenol 5, 2,4-dinitrophenol 6, 2-chlorophenol 7, bentazone 8, simazine 9, MCPA 10, atrazine. Reprinted from Journal of Chromatography, A 803, N. Masque et ai, New chemically modified polymeric resin for solid-phase extraction of pesticides and phenolic compounds from water , pp. 147-155, copyright 1998, with permission from Elsevier Science.

Apart from these two Vertex compounds, only one other caspase inhibitor, BDN-6556, has been used in clinical trials. This compound belongs to the class of oxamyl dipeptides and was originally developed by Idun Pharmaceuticals (taken over by Pfizer). It is the only pan-caspase inhibitor that has been evaluated in humans. BDN-6556 displays inhibitory activity against all tested human caspases. It is also an irreversible, caspase-specific inhibitor that does not inhibit other major classes of proteases, or other enzymes or receptors. The therapeutic potential of BDN-6556 was first evaluated in several animal models of liver disease because numerous publications suggested that apoptosis contributes substantially to the development of some hepatic diseases, such as alcoholic hepatitis, hepatitis B and C (HBV, HCV), non-alcoholic steato-hepatitis (NASH), and ischemia/reperfusion injury associated with liver transplant. Accordingly, BDN-6556 was tested in a phase I study. The drug was safe and... 

Organotin compounds la 399 lb 21, 319 Ornithine la 235 Orthosipon leaf extract lb 216,217 Oryzalin lb 110-112 Ovalbumin lb 401 Over pressure layer chromatography (OPLC) lb4 Oxacillin lb 84,188,301 Oxaflozan lb 268,358 Oxalic acid la 45,171,426 Oxamyl lb 332... 

In the case of aldicarb, oxamyl, and 3-hydroxycatbofuran, the ion transitions go from [M + NH4]+ —> product ions. 

Figure 1 was taken from an unpublished report, DuPont Study No. AMR 4392-97, Dissipation of Dislodgeable Foliar and Soil Residues of Oxamyl Following Application of Vydate L Insecticide to Tomatoes in the USA - Season 1997-1998 . This study has been submitted to the EPA and the data were used to establish and verify re-entry intervals. Data from this study will be used to provide an example of the topics discussed throughout this article. 

In the oxamyl tomato study, the DFR samples were obtained using a 5-cm Birkestrand sampler (10-cm disk size using the upper and lower surfaces). The sample consisted of 40 leaf disks or 400 cm from each subplot. The samples were collected impartially or in a nondirected approach from the middle two rows. The plot was four rows wide and the tractor came into contact with the first and fourth rows as the application was made. The middle two rows should be undisturbed by this movement and should therefore provide a more representative sample. 

Field recovery samples are an important part of the quality control in DFR studies. Field fortifications allow the experimental data to be corrected for losses at all phases of the study from collection through sample transport and storage. Fresh laboratory fortifications monitor losses due to the analytical phase. This section details how the field recovery process was handled in the oxamyl tomato DFR study. 

Fresh oxamyl standards were prepared for each fortification event. Concentrations of 50 and 400 qg mL analytical-grade oxamyl were prepared in a 20% acetonitrile-80% FIPLC-grade water solution. The solutions were tranferred in 1-mL aliquots into uniquely identified vials so that each vial contained the correct volume of oxamyl standard to fortify one quality control sample. The vials were shipped as needed during the course of the study to each field site. 

Six control sample jars of 0.01% Aerosol OT detergent in distilled water solution (200 mL each) were prepared at each site on sampling days 1,14 and 28 by dislodging leaf disks taken from the untreated control area. Triplicate samples were fortified at each of two concentrations. Fortification levels were 50 and 400 qg of oxamyl per sample. 

A 25-g sample of <150- o.m control soil was placed into each of six jars for fortification. Three samples were fortified at each of two concentrations of oxamyl. Soil samples were fortified on the same days and at the same levels as the foliar... 

To calculate the safe re-entry interval (REI), the margin of exposure (MOE) must be considered. Worker risk is measured as a margin of exposure and is related to how closely the occupational exposure comes to the no observed adverse effect level (NOAEL, for oxamyl 50 mg kg day ). MOE is defined as... 

For oxamyl, an MOE of > 100 must be achieved in order to establish an REI which does not exceed the regulatory agency s risk concern. Dose is calculated by the following equation ... 

A nonlinear fit weights the initial data points more heavily and gives a better description of the decline in oxamyl residues during the critical period when the residues are a concern in the evaluation of worker safety. The nonlinear curve fitting approach has been accepted by regulatory agencies for the determination of pesticide half-life determinations in soil when the decline data do not fit a linear first-order curve. 

Table 3 HPLC/MS/MS conditions for the determination of oxamyl in drinking...

Crops, food, and feed. The first recommended method is based on the Dutch Multiresidue Method 2 for A-methylcarbamates, which was originally developed by de Kok et The method has recently been validated by DuPont Crop Protection and Batelle, Geneva Research Centres, for the analysis of methomyl and oxamyl in dry, high-water, high-fat, and high-acid content crops and in various grape processed products. The limit of detection for each analyte is 0.003-0.005 mg kg . ... 

The first recommended soil method for oxime carbamates is the method of Honing et al. by HPLC/MS. The LOQ of the method, specifically for aldicarb, methomyl, and oxamyl, is 0.05mgkg. Soil (lOg) is Soxhlet extracted for 16h with acetone-dichloromethane (1 1) using double-thickness cellulose extraction thimbles (80 X 22-mm i.d.). Prior to extraction, the Soxhlet system and the thimbles are cleaned for 14 h by refluxing with methanol. The extracts are removed and concentrated nearly to dryness in a rotary evaporator operating at 35 °C evaporation to dryness... 

The European drinking water guidelines set a maximum admissible concentration of 0.10 pgL for individual pesticides and their related compounds in drinking water. The recommended methods for oxime carbamates and their metabolites in groundwater and surface water are suitable for detection limits below 0.10 pgL. The first method is the HPLC/lluorescence multiresidue method of de Kok et al The second method is an HPLC/MS/MS method of DuPont Crop Protection which is specific for oxamyl and may be applicable for the analysis of other oxime carbamates in heavily polluted waters. 

A sensitive and selective method, which is specific for oxamyl and may be applicable to other oxime carbamates and their metabolites in heavily polluted waters, involves the use of HPLC/MS/MS. A 75-mL reservoir is attached on top of a Bond-Elut SAX (l-g/6-mL) (Varian), which is connected to an Oasis HLB (l-g/20-mL)... 

---