Influences on transfer of selected synthetic pyrethroids from treated Formica to foods.

Children's unstructured eating habits and activities may lead to excess dietary exposures not traditionally measured by the US Environmental Protection Agency. Influence of these activities on transfer of pesticides from treated Formica to foods was studied. The objective was to perform simulation experiments using four foods (bread, apple slices, bologna, and sugar cookies) exposed to treated Formica after varied time intervals between surface contamination and contact (1, 6, and 24 h) and frequency of contact with and without recontamination. Pesticides investigated included permethrin, bifenthrin, cyfluthrin, cypermethrin, and deltamethrin. Data will be used as input parameters for transfer efficiencies (TEs) within the Children's Dietary Intake Model (CDIM), which predicts total dietary exposure of a child. Pesticide transfer from surfaces to bologna and apples was more efficient than to bread and cookies. For the bread and cookies, all pyrethroids had a TE that ranged from below detectible levels to ≤ 4%. A combined average of 32-64% and 19-43% was transferred to bologna and apples, respectively, for the three contact times for all pyrethroids. The TEs of the varied time intervals indicated that increased time between contamination and contact showed little difference for bologna, bread, and cookies, but a significant difference for apples. As long as pesticide levels are measureable on surfaces in children's eating environment, it can be concluded that transfer of pesticides to foods will take place. Foods' characteristics had an important function in the transfer of pesticides when multiple contacts occurred. Regardless of recontamination, pesticides were efficiently transferred from the treated surface to bologna. The bologna did not reach a saturation point during the contacts. Pesticides were also efficiently transferred to apples, but reached a maximum TE during the second contact. The distribution of activity factors within CDIM needs to reflect the differences in the characteristics of the foods.

Analysis of permethrin isomers in composite diet samples by molecularly imprinted solid-phase extraction and isotope dilution gas chromatography-ion trap mass spectrometry.

Determination of an individual's aggregate dietary ingestion of pesticides entails analysis of a difficult sample matrix. Permethrin-specific molecularly imprinted polymer (MIP) solid-phase extraction cartridges were developed for use as a sample preparation technique for a composite food matrix. Vortexing with acetonitrile and centrifugation were found to provide optimal extraction of the permethrin isomers from the composite foods. The acetonitrile (with 1% acetic acid) was mostly evaporated and the analytes reconstituted in 90:10 water/acetonitrile in preparation for molecularly imprinted solid-phase extraction. Permethrin elution was accomplished with acetonitrile and sample extracts were analyzed by isotope dilution gas chromatography-ion trap mass spectrometry. Quantitation of product ions provided definitive identification of the pesticide isomers. The final method parameters were tested with fortified composite food samples of varying fat content (1%, 5%, and 10%) and recoveries ranged from 99.3% to 126%. Vegetable samples with incurred pesticide levels were also analyzed with the given method and recoveries were acceptable (81.0-95.7%). Method detection limits were demonstrated in the low ppb range. Finally, the applicability of the MIP stationary phase to extract other pyrethroids, specifically cyfluthrin and cypermethrin, was also investigated.

Development of an analytical scheme for the determination of pyrethroid pesticides in composite diet samples.

Analysis of an individual's total daily food intake may be used to determine aggregate dietary ingestion of given compounds. However, the resulting composite sample represents a complex mixture, and measurement of such can often prove to be difficult. In this work, an analytical scheme was developed for the determination of 12 select pyrethroid pesticides in dietary samples. In the first phase of the study, several cleanup steps were investigated for their effectiveness in removing interferences in samples with a range of fat content (1-10%). Food samples were homogenized in the laboratory, and preparatory techniques were evaluated through recoveries from fortified samples. The selected final procedure consisted of a lyophilization step prior to sample extraction. A sequential 2-fold cleanup procedure of the extract included diatomaceous earth for removal of lipid components followed with a combination of deactivated alumina and C(18) for the simultaneous removal of polar and nonpolar interferences. Recoveries from fortified composite diet samples (10 microg kg(-1)) ranged from 50.2 to 147%. In the second phase of this work, three instrumental techniques [gas chromatography-microelectron capture detection (GC-microECD), GC-quadrupole mass spectrometry (GC-quadrupole-MS), and GC-ion trap-MS/MS] were compared for greatest sensitivity. GC-quadrupole-MS operated in selective ion monitoring (SIM) mode proved to be most sensitive, yielding method detection limits of approximately 1 microg kg(-1). The developed extraction/instrumental scheme was applied to samples collected in an exposure measurement field study. The samples were fortified and analyte recoveries were acceptable (75.9-125%); however, compounds coextracted from the food matrix prevented quantitation of four of the pyrethroid analytes in two of the samples considered.

Surface-to-food pesticide transfer as a function of moisture and fat content.

Transfer of pesticides from household surfaces to foods may result in excess dietary exposure in children (i.e., beyond that inherent in foods due to agricultural application). In this study, transfer was evaluated as a function of the moisture and fat content of various foods. Surfaces chosen for investigation were those commonly found in homes and included Formica, ceramic tile, plastic, carpet, and upholstery fabric. Each surface type was sprayed with an aqueous emulsion of organophosphates, fipronil, and synthetic pyrethroids. In the first phase of the study, multiple foods (apples, watermelon, wheat crackers, graham crackers, white bread, flour tortillas, bologna, fat-free bologna, sugar cookies, ham, Fruit Roll-ups, pancakes, and processed American cheese) were categorized with respect to moisture and fat content. All were evaluated for potential removal of applied pesticides from a Formica surface. In the second phase of the study, representative foods from each classification were investigated for their potential for pesticide transfer with an additional four surfaces: ceramic tile, plastic, upholstery, and carpet. Moisture content, not fat, was found to be a determining factor in most transfers. For nearly all surfaces, more efficient transfer occurred with increased hardness (Formica and ceramic tile). Comparatively, the polymer composition of the plastic delivered overall lower transfer efficiencies, presumably due to an attraction between it and the organic pesticides of interest.

Transfer efficiencies of pesticides from household flooring surfaces to foods.

The transfer of pesticides from household surfaces to foods was measured to determine the degree of excess dietary exposure that occurs when children's foods contact contaminated surfaces prior to being eaten. Three household flooring surfaces (ceramic tile, hardwood, and carpet) were contaminated with an aqueous emulsion of commercially available pesticides (diazinon, heptachlor, malathion, chlorpyrifos, isofenphos, and cis- and trans-permethrin) frequently found in residential environments. A surface wipe method, as typically used in residential exposure studies, was used to measure the pesticides available on the surfaces as a basis for calculating transfer efficiency to the foods. Three foods (apple, bologna, and cheese) routinely handled by children before eating were placed on the contaminated surfaces and transfers of pesticides were measured after 10 min contact. Other contact durations (1 and 60 min) and applying additional contact force (1500 g) to the foods were evaluated for their impact on transferred pesticides. More pesticides transferred to the foods from the hard surfaces, that is, ceramic tile and hardwood flooring, than from carpet. Mean transfer efficiencies for all pesticides to the three foods ranged from 24% to 40% from ceramic tile and 15% to 29% from hardwood, as compared to mostly non-detectable transfers from carpet. Contact duration and applied force notably increased pesticide transfer. The mean transfer efficiency for the seven pesticides increased from around 1% at 1 min to 55- 83% when contact duration was increased to 60 min for the three foods contacting hardwood flooring. Mean transfer efficiency for 10-min contact increased from 15% to 70% when a 1500 g force was applied to bologna placed on hardwood flooring. Contamination of food occurs from contact with pesticide-laden surfaces, thus increasing the potential for excess dietary exposure of children.