Evaluation of headspace solid-phase microextraction for analysis of phosphine residues in wheat.

In headspace (HS) analysis, a fumigant is released from a commodity into a gas-tight container by grinding, heating, or microwaves. A new technique uses HS-solid-phase microextraction (SPME) for additional preconcentration of fumigant. HS-SPME was tested for detection of phosphine (PH3), chosen for examination because of its wide use on stored commodities. PH3 was applied to 50 g wheat in separate 250 mL sealed flasks, which were equipped either with a septum for conventional HS analysis or with one of four HS-SPME fibers [100 microm polydimethylsiloxane (PDMS), 85 microm carboxen (CAR)/PDMS, 75 microm CAR/PDMS, and 65 pm PDMS/divinylbenzene (DVB)]. The wheat was heated at 45 degrees C for 20 min. In conventional HS analysis, a gaseous aliquot (80 pL) was taken from the HS and injected into the GC instrument. In the HS-SPME procedure, the fiber was removed from the HS and exposed in the heated injection port of the GC instrument. In all cases, PH3 was determined under the same chromatographic conditions with a GC pulsed flame photometric detector. In a comparison of the efficacy of the fibers, the bipolar fibers (CAR/PDMS and PDMS/DVB) contained more PH3 than the aliquot in the conventional HS analysis; larger size bipolar fibers extracted PH3 more efficiently than smaller fibers (e.g., 85 > 75 > 65 microm). The nonpolar fiber (PDMS) contained no PH3. Four fortification levels of PH3 on wheat were tested: 0.01, 0.05, 0.1, and 0.3 microg/g. The response of each bipolar fiber increased with the fortification levels, but the conventional HS analysis detected no fumigant at the lowest fortification level of 0.01 mg/g. Under the conditions of the validation study, the LOD was in the range of 0.005-0.01 ng PH3/g wheat.

Toxicity of cyanogen to insects of stored grain.

Range-finding studies on the toxicity of cyanogen to all stages of five species of stored product Coleoptera are reported. The species were Rhyzopertha dominica (F), Sitophilus granarius (L), Sitophilus Oryzae (L), Tribolium castaneum (Herbst), Tribolium confusum Jacquelin du Val and Ephestia cautella (Walker). Exposures for 24 h to cyanogen at 1.3 mg litre(-1) controlled all external stages. Control of internal stages of Sitophilus species was achieved by a 5-day exposure to initial concentrations between 13.7 and 27.4 mg litre(-1), whereas R. dominica was controlled at 13.7 mg litre(-1). Cyanogen showed similar toxicity to all tested external stages and, in this respect, was more similar to methyl bromide than to phosphine. Its toxicity to insects increased with both relative humidity and concentration of carbon dioxide. Cyanogen was toxic to insects whether applied as a gas or in an aqueous solution.