Preparation and characterization of porous silica-coated multifibers for solid-phase microextraction.

C18-bonded silica-coated multifibers were prepared and studied as a stationary phase for solid-phase microextraction (SPME). The porous multifiber SPME provided larger absorption capacity and higher absorption rate compared to a polymer-coated single fiber. Its absorption rate was 10 times higher than that of a commercial 100-microm poly(dimethylsiloxane) (PDMS)-coated fiber. Its high extraction efficiency enabled the positive identification of unknown compounds at sub-part-per-billion level in full-scan mode with a benchtop quadruple GC/MS. The desorption temperature indicated that the analyte interactions with the C18-bonded silica were stronger than those with the PDMS polymer. The dependence of the equilibration time on the molecular weight was not observed for the porous multifiber SPME. The boundary layer between the fiber coating and the sample matrix could be the absorption control step in SPME under mild agitation. The special experimental conditions in the porous multifiber SPME, such as air interference and polar organic solvent wetting, were investigated.

Recovery of atrazine, bromacil, chlorpyrifos, and metolachlor from water samples after concentration on solid-phase extraction disks: interlaboratory study.

An interlaboratory comparison was conducted in 1997 and 1998 to examine the feasibility of using C18 solid-phase extraction disks (Empore) to simultaneously determine the herbicides atrazine, bromacil, and metolachlor and the insecticide chlorpyrifos in water samples. A common fortification source and sample processing procedure were used to minimize variation in initial concentrations and operator inconsistencies. The protocol consisted of paired laboratories in different locations coordinating their activities and shipping fortified water samples (deionized or local surface water) or Empore disks on which the pesticides had been retained and then quantitating the analytes by a variety of gas chromatographic methods. Average recoveries from all laboratories were >80% for atrazine, bromacil, and metolachlor, and >70% for chlorpyrifos. Detection of bromacil was unachievable at some locations because of chromatographic problems. Shipping samples between cooperating laboratories did not affect the recovery of atrazine, chlorpyrifos, or metolachlor in either matrix. Recoveries tended to be higher from disks shipped to cooperating laboratories compared with those from fortified water. Shipping disks eliminated many problems associated with the shipment of water samples, such as bottle breakage, higher shipping cost, and possible pesticide degradation. Recoveries of bromacil and metolachlor were lower from fortified surface water samples than from fortified deionized water samples. This collaborative research demonstrated that pesticides in water samples can be concentrated on solid-phase extraction disks at one location and quantitated under diverse analytical conditions at another location. The extraction efficiencies of the disks were comparable with or better than the recoveries obtained from the shipped water samples, and the problems associated with shipping water samples were eliminated by using the disks.

A preliminary examination of the translocation of microencapsulated cyfluthrin following applications to the perimeter of residential dwellings.

Methods have been developed to monitor the translocation of microencapsulated cyfluthrin following perimeter applications to residential dwellings. A pilot study was implemented to determine both the potential for application spray to drift away from dwellings and the intrusion of residues into homes following perimeter treatments. Residential monitoring included measuring spray drift using cellulose filter paper and the collection of soil samples from within the spray zone. In addition, interior air was monitored using fiberglass filter paper as a sorbent medium and cotton ball swabs were used to collect surface wipes. Fortification of matrixes resulted in recoveries of > 90%. Spray drift was highest at the point of application and declined to low but measurable levels 9.1 m from the foundations of dwellings. Soil residues declined to low, but measurable levels by 45 days post-application. No cyfluthrin was measured from indoor air; however, some interior surfaces had detectable levels of cyfluthrin until three days post-application. Findings indicate that spray drift resulting from perimeter applications might contaminate non-target surfaces outside the spray zone. Soil borne residues may serve as persistent sources for human exposure and potentially intrude into dwellings through the activities of occupants and pets. Residues do not appreciably translocate through air and consequently inhalation is not a likely route for human exposure. Surface residues detected indoors suggest that the physical movement of residues from the exterior to the interior might be a viable route of movement of residues following this type of application.

Separation of fungicides by micellar electrokinetic capillary chromatography.

Capillary electrophoresis with ultraviolet detection (CE/UV) of selected fungicides (carbendazim, metalaxyl, propiconazole, and vinclozolin) using different buffer compositions was investigated. Capillary zone electrophoresis (CZE) with 10 mM sodium phosphate (pH 7.0) was not useful in separating the four fungicides used in this study. However, the four fungicides were well resolved by employing micellar electrokinetic capillary chromatography (MEKC). Among the two surfactants tested in MEKC, bile salts provided better separation compared to sodium dodecyl sulfate (SDS). A buffer consisting of 10 mM sodium phosphate with 100 mM sodium cholate and 10% methanol (pH 7.0) gave best results; excellent separation of the four compounds was achieved in less than 15 min. The CE/UV method was validated by analyzing deionized and lake-water samples fortified with known concentrations for the four fungicides. Average recoveries of the fungicides in lake water of 4 micrograms/L level ranged from 42 to 87%.

Distribution of chlorpyrifos in air and on surfaces following crack and crevice application to rooms.

Measureable levels of chlorpyrifos were seen in air and on horizontal and vertical surfaces over an 84-day sampling period following application by two different methods. Pressurized aerosol applications had the highest airborne levels over the 84-day sampling period, and movement into adjacent, nontreated rooms was seen 7 days after application. Highest surface residues found were located at floor/wall interfaces and were due probably as a result of splash or overspray around treated areas. Residue levels from desk sides were very low and all surface residues were highly variable. One could not predict what surface levels would be based upon airborne concentrations.

Trapping efficiency of selected adsorbents for various airborne pesticides.

A study was conducted to compare the efficiency of five adsorbents used by government and private laboratories to collect airborne pesticides. Six pesticides, acephate, chlordane, chlorpyrifos, diazinon, heptachlor, and propoxur, were vaporized in a closed system and collected on each of the adsorbents, Chromosorb 102, ORBO 42, ORBO 44 (chlordane and heptachlor only), polyurethane foam (PUF) or Tenax GC, by drawing 250 L of air through the adsorbent. There were no differences in collection efficiency of the five pesticides on Chromosorb 102, ORBO's 42/44, and PUF. The efficiency with Tenax was somewhat less with several of the pesticides.

A sampling method to determine insecticide residues on surfaces and its application to food-handling establishments.

Known amounts of acephate, chlorpyrifos, and diazinon were applied to Formica, unfinished plywood, stainless steel, and vinyl tile. Cotton-ball and dental wick materials were dipped in 2-propanol and "swiped" over the treated surface area two time. More acephate was found on the second swipe compared to the first from vinyl tile, similar amounts on both swipes from plywood, and less on the second swipe from formica and stainless steel. The ratio of chlorpyrifos on Swipe 1 compared to Swipe 2 found with cotton-ball on both formica and stainless steel surfaces was equivalent (6:1), but a considerable difference was seen when two dental wick swipes were used. Residues of diazinon removed from formica and stainless steel were equivalent, regardless of the swiping material used. Residues of chlorpyrifos were detected by taking swipes of surfaces in two restaurants and a supermarket up to 6 mo after a prescribed application by a commercial pest control firm. The data show that measurable amounts of chloropyrifos can be detected on surfaces not treated with the insecticide for at least 6 mo.

DDVP residues in air following application to a tobacco-storage warehouse.

A 10% solution of DDVP was sprayed until a total volume of 20.9 liters of the solution had been released into the air in a tobacco-storage warehouse. Air samples were taken at various times after application in three different experiments to measure DDVP levels with time and to determine if DDVP concentrations exceeded the threshold limit (TVL). In the three experiments, residue levels were highest initially in the center of the warehouse compared to a corner, but residue levels tended to equalize over the sampling period. The data indicated that workers entering storage warehouses after application of DDVP would not encounter hazardous levels of this material.

Concentration and movement of diazinon in air.

Airborne concentrations of diazinon were measured in rooms for 21 days after crack and crevice application. Residue levels were largest in treated rooms (38 micrograms/m3) after application, followed by adjacent (1 microgram/m3) and upper and lower rooms (ca. 0.4 microgram/m3). Low levels of diazinon were detected in all rooms 21 days after application. Small amounts of diazinon (corrected to an 8 min application period) were detected on respirator pads (2.6 microgram) and waist pads (2.3 microgram) worn by the applicator.