Donald A. Whitaker

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.

The design and field implementation of the Detroit Exposure and Aerosol Research Study

The US Environmental Protection Agency recently conducted the Detroit Exposure and Aerosol Research Study (DEARS). The study began in 2004 and involved community, residential, and personal-based measurements of air pollutants targeting 120 participants and their residences. The primary goal of the study was to evaluate and describe the relationship between air toxics, particulate matter (PM), PM constituents, and PM from specific sources measured at a central site monitor with those from the residential and personal locations. The impact of regional, local (point and mobile), and personal sources on pollutant concentrations and the role of physical and human factors that might influence these concentrations were investigated. A combination of active and passive sampling methodologies were employed in the collection of PM mass, criteria gases, semivolatile organics, and volatile organic compound air pollutants among others. Monitoring was conducted in six selected neighborhoods along with one community site using a repeated measure design. Households from each of the selected communities were monitored for 5 consecutive days in the winter and again in the summer. Household, participant and a variety of other surveys were utilized to better understand human and household factors that might affect the impact of ambient-based pollution sources upon personal and residential locations. A randomized recruitment strategy was successful in enrolling nearly 140 participants over the course of the study. Over 36,000 daily-based environmental data points or records were ultimately collected. This paper fully describes the design of the DEARS and the approach used to implement this field monitoring study and reports select preliminary findings.

Measurement of indoor air emissions from dry-process photocopy machines

Presently, no standard test method exists to evaluate the various emissions from office equipment (e.g., ozone, volatile organic compounds, inorganic gases, and particulates) so it is difficult to compare data from different studies.1 As a result, the authors are developing a standardized guidance document for measuring indoor air emissions from office equipment. The ultimate goal is to apply the test method to better understand emissions from office equipment and to develop lower emitting machines. This paper provides background information on indoor air emissions from office equipment with an emphasis on dry-process photocopy machines. The test method is described in detail, along with the results of a study to evaluate the test method using four dry-process photocopy machines. The results from this study indicate that the test method provides acceptable performance for characterizing emissions; that it can adequately identify differences in emissions between machines both in compounds emitted and their emission rates; and that it is capable of measuring both intra- and inter-machine variability in emissions. Challenges and complications were encountered in developing and implementing the test method. These included heat generation, which can cause large increases in chamber temperature; finite paper supplies for photocopy machines, which limit test duration; varying power requirements that may require changes in chamber electrical supply; and remote starting of the machines, which is necessary to maintain chamber integrity. Results show that dry-process photocopy machines can produce emissions of ozone and volatile organic compounds that can potentially have a significant impact on indoor air quality. For the four machines tested in this study, the compounds with the highest emission rates overall were ethylbenzene (28,000 µg/hour), m,p-xylenes (29,000 µg/hour), o-xylene (17,000 µg/hour), 2-ethyl-lhexanol (14,000 µg/hour), and styrene (12,000 fig/hour). Although many of the same compounds tended to be detected in emissions from each of the four photocopiers, the relative contribution of individual compounds varied considerably between machines, with differences greater than an order of magnitude for some compounds.

Multimedia measurements and activity patterns in an observational pilot study of nine young children

A pilot observational exposure study was performed to evaluate methods for collecting multimedia measurements (air, dust, food, urine) and activity patterns to assess potential exposures of young children to pesticides in their homes. Nine children (mean age=5 years) and their caregivers participated in this study, performed in the Duval County, Florida, in collaboration with the Centers for Disease Control and Prevention and the Duval County Health Department. For all nine children, the total time reported for sleeping and napping ranged from 9.5 to 14 h per day, indoor quiet time from 0 to 5.5 h per day, indoor active time from 0.75 to 5.5 h per day, outdoor quiet time from 0 to 1.5 h per day, and outdoor active time from 0.5 to 6.5 h per day. Each home had one to three pesticide products present, with aerosols being most common. Pesticide inventories, however, were not useful for predicting pesticide levels in the home. Synthetic pyrethroids were the most frequently identified active ingredients in the products present in each home. Fifteen pesticide active ingredients were measured in the application area wipes (not detected (ND) to 580 ng/cm2), 13 in the play area wipes (ND-117 ng/cm2), and 14 in the indoor air samples (ND-378 ng/m3) and the socks (ND-1000 ng/cm2). Cis-permethrin, trans-permethrin, and cypermethrin were measured in all nine homes. Chlorpyrifos was measured in all nine homes even though it was not reported used by the participants. All urine samples contained measurable concentrations of 3-phenoxybenzoic acid (3-PBA). The median 3-PBA urinary concentration for the nine children was 2.2 μg/l. A wide variety of pesticide active ingredients were measured in these nine homes at median concentrations that were often higher than reported previously in similar studies. These data highlight the need for additional observational studies in regions where pesticides are used in order to understand the factors that affect young childrens exposures and the education/mitigation strategies that can be used to reduce childrens exposures.

24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies.

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).

Comparison of 24 h averaged VOC monitoring results for residential indoor and outdoor air using Carbopack X-filled diffusive samplers and active sampling—a pilot study

Analytical results obtained by thermal desorption GC/MS for 24 h diffusive sampling of 11 volatile organic compounds (VOCs) are compared with results of time-averaged active sampling at a known constant flow rate. Air samples were collected with co-located duplicate diffusive sampling tubes and one passivated canister. A total of eight multiple-component sampling events took place at fixed positions inside and outside three private homes. Subsequently, a known amount of sample air was transferred from the canister to an adsorbent tube for analysis by thermal desorption GC/MS. Results for the 11 most prevalent compounds--Freon 11, 1,3-butadiene, benzene, toluene, tetrachloroethene, ethylbenzene, m,p-xylene, o-xylene, 4-ethyltoluene, 1,3,5-trimethylbenzene, and p-dichlorobenzene--show that the ratio of average study values (diffusive sampling to active sampling) is 0.92 with 0.70 and 1.14 extreme ratios. Absolute percent difference for duplicate samples using diffusive sampling was <10% for the four most prevalent compounds. Agreement between the two sampling approaches indicates that the prediction of approximately constant diffusive sampling rates based on previous laboratory studies is valid under the field conditions.

Methodologies for estimating cumulative human exposures to current-use pyrethroid pesticides

We estimated cumulative residential pesticide exposures for a group of nine young children (4–6 years) using three different methodologies developed by the US Environmental Protection Agency and compared the results with estimates derived from measured urinary metabolite concentrations. The Standard Operating Procedures (SOPs) for Residential Exposure Assessment are intended to provide a screening-level assessment to estimate exposure for regulatory purposes. Nonetheless, dermal exposure estimates were typically lower from the SOP (1–1300 nmol/day) than from SHEDS (5–19,000 nmol/day) or any of the four different approaches for estimating dermal exposure using the Draft Protocol for Measuring Childrens Non-Occupational Exposure to Pesticides by all Relevant Pathways (Draft Protocol) (5–11,000 nmol/day). Indirect ingestion exposure estimates ranged from 0.02 to 21.5 nmol/day for the SOP, 0.5 to 188 nmol/day for SHEDS, and 0 to 3.38 nmol/day for the Draft Protocol. Estimates of total absorbed dose ranged from 3 to 37 nmol/day for the SOPs, 0.5 to 100 nmol/day for SHEDS, and 1 to 216 nmol/day for the Draft Protocol. The concentrations estimated using the Draft Protocol and SHEDS showed strong, positive relationships with the 3-phenoxybenzoic acid metabolite measured in the childrens urine samples (R2=0.90 for the Draft Protocol; R2=0.92 for SHEDS). Analysis of different approaches for estimating dermal exposure suggested that the approach assuming an even distribution of pesticide residue on the childs body was most reasonable. With all three methodologies providing reasonable estimates of exposure and dose, selection should depend on the available data and the objectives of the analysis. Further research would be useful to better understand how best to estimate dermal exposure for children and what exposure factors (e.g., activities, transfer coefficients, measurement techniques) are most relevant in making dermal exposure estimates.

Optimizing a dansylhydrazine (DNSH) based method for measuring airborne acrolein and other unsaturated carbonyls

The Passive Aldehydes and Ketones Sampler (PAKS) method has been developed to measure airborne carbonyls (aldehydes and ketones) by derivatizing the carbonyls with dansylhydrazine (DNSH) on a solid sorbent. The method collection efficiencies are approximately 100% for most saturated carbonyls, but are significantly lower for unsaturated carbonyls. In this study, we examined the mechanisms of DNSH reactions with unsaturated carbonyls, focusing on acrolein. With a better understanding of these mechanisms, we modified the sampling substrate conditions and HPLC analysis conditions of the original PAKS method, resulting in substantially improved collection efficiencies for acrolein and crotonaldehyde. Evaluated under a variety of conditions (temperature, humidity, presence of ozone), the modified PAKS method had a collection efficiency of 99%+/- 5% for acrolein (N= 36) and 96%+/- 20% for crotonaldehyde (N= 6). The acrolein-DNSH derivative was stable within 9.6% of the initial amount, after 14 days of storage at 4 degrees C, on the collection medium; and stable within 2.8% of the initial amount, after 16 days of storage at room temperature, in extract.

Relationship between PM2.5 collected at residential outdoor locations and a central site.

Abstract Regression models are developed to describe the relationship between ambient PM2.5 (particulate matter [PM] ≤2.5 μm in aerodynamic diameter) mass concentrations measured at a central-site monitor with those at residential outdoor monitors. Understanding the determinants and magnitude of variability and uncertainty in this relationship is critical for understanding personal exposures in the evaluation of epidemiological data. The repeated measures regression models presented here address temporal and spatial characteristics of data measured in the 2004–2007 Detroit Exposure and Aerosol Research Study, and they take into account missing data and other data features. The models incorporate turbulence kinetic energy and planetary boundary layer height, meteorological data that are not routinely considered in models that relate central-site concentrations to exposure to health effects. It was found that turbulence kinetic energy was highly statistically significant in explaining the relationship of PM2.5 measured at a particular stationary outdoor air monitoring site with PM2.5 measured outside nearby residences for the temporal coverage of the data.

Sample integrity evaluation and EPA method 325B interlaboratory comparison for select volatile organic compounds collected diffusively on Carbopack X sorbent tubes

A sample integrity evaluation and an interlaboratory comparison were conducted in application of U.S. Environmental Protection Agency (EPA) Methods 325A and 325B for diffusively monitoring benzene and other selected volatile organic compounds (VOCs) using Carbopack X sorbent tubes. To evaluate sample integrity, VOC samples were refrigerated for up to 240 days and analyzed using thermal desorption/gas chromatography-mass spectrometry at the EPA Office of Research and Development laboratory in Research Triangle Park, NC, USA. For the interlaboratory comparison, three commercial analytical laboratories were asked to follow Method 325B when analyzing samples of VOCs that were collected in field and laboratory settings for EPA studies. Overall results indicate that the selected VOCs collected diffusively on sorbent tubes generally were stable for 6 months or longer when samples were refrigerated. This suggests the specified maximum 30-day storage time of VOCs collected diffusively on Carbopack X passive samplers and analyzed using Method 325B might be able to be relaxed. Interlaboratory comparison results were in agreement for the challenge samples collected diffusively in an exposure chamber in the laboratory, with most measurements within ±25% of the theoretical concentration. Statistically significant differences among laboratories for ambient challenge samples were small, less than 1 part per billion by volume (ppbv). Results from all laboratories exhibited good precision and generally agreed well with each other.