Jeffrey N. Morgan

Pesticides and their Metabolites in the Homes and Urine of Farmworker Children Living in the Salinas Valley, CA

In support of planning efforts for the National Childrens Study, we conducted a study to test field methods for characterizing pesticide exposures to 20 farmworker children aged 5–27 months old living in the Salinas Valley of Monterey County, California. We tested methods for collecting house dust, indoor and outdoor air, dislodgeable residues from surfaces and toys, residues on clothing (sock and union suits), food, as well as spot and overnight diaper urine samples. We measured 29 common agricultural and home use pesticides in multiple exposure media samples. A subset of organophosphorus (OP), organochlorine (OC) and pyrethroid pesticides were measured in food. We also analyzed urine samples for OP pesticide metabolites. Finally, we administered four field-based exposure assessment instruments: a questionnaire; food diary; home inspection; and a self-administered child activity timeline. Pesticides were detected more frequently in house dust, surface wipes, and clothing than other media, with chlorpyrifos, diazinon, chlorthal-dimethyl, and cis- and trans-permethrin detected in 90% to 100% of samples. Levels of four of these five pesticides were positively correlated among the house dust, sock, and union suit samples (Spearmans ρ=0.18–0.76). Pesticide loading on socks and union suits was higher for the group of 10 toddlers compared to the 10 younger crawling children. Several OP pesticides, as well as 4,4′-DDE, atrazine, and dieldrin were detected in the food samples. The child activity timeline, a novel, low-literacy instrument based on pictures, was successfully used by our participants. Future uses of these data include the development of pesticide exposure models and risk assessment.

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 individuals 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 individuals 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.

An overview of measurement method tools available to communities for conducting exposure and cumulative risk assessments

Community-based programs for assessing and mitigating environmental risks represent a challenge to participants because each brings a different level of understanding of the issues affecting the community. These programs often require the collaboration of several community sectors, such as community leaders, local governments and researchers. Once the primary concerns, community vulnerabilities and assets are identified, participants plan on how to address immediate actions, rank known risks, collect information to support decision making, set priorities and determine an evaluation process to assess the success of the actions taken. The evaluation process allows the community to develop new action plans based on the results obtained from earlier actions. Tracking the success of the community actions may be as simple as a visual/tangible result (e.g., cleaning a park) or as complex as the collection of specific measurements to track the reduction of toxic pollutants or to determine the presence of a specific contaminant. Recognizing that communities may need to perform measurements to meet their goals, this paper provides an overview of the available measurement methods for several chemicals and biologicals in relevant environmental samples to a community setting. The measurement methods are organized into several categories according to their level of complexity, estimated cost and sources. Community project technical advisors are encouraged to examine the objective(s) of the community to be addressed by a measurement collection effort and the level of confidence that needed for the data to make appropriate decisions. The tables provide a starting point for determining which measurement method may be appropriate for specific community needs.

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

Childrens 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 Childrens 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 childrens 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.