Intake Fraction Variability Between Air Pollution Emission Sources Inside an Urban Area

The cost‐effective mitigation of adverse health effects caused by air pollution requires information on the contribution of different emission sources to exposure. In urban areas the exposure potential of different sources may vary significantly depending on emission height, population density, and other factors. In this study, we quantified this intraurban variability by predicting intake fraction (iF) for 3,066 emission sources in Warsaw, Poland. iF describes the fraction of the pollutant that is inhaled by people in the study area. We considered the following seven pollutants: particulate matter (PM), nitrogen oxides (NO_x), sulfur dioxide (SO₂), benzo[a] pyrene (BaP), nickel (Ni), cadmium (Cd), and lead (Pb). Emissions for these pollutants were grouped into four emission source categories (Mobile, Area, High Point, and Other Point sources). The dispersion of the pollutants was predicted with the CALPUFF dispersion model using the year 2005 emission rate data and meteorological records. The resulting annual average concentrations were combined with population data to predict the contribution of each individual source to population exposure. The iFs for different pollutant‐source category combinations varied between 51 per million (PM from Mobile sources) and 0.013 per million (sulfate PM from High Point sources). The intraurban iF variability for Mobile sources primary PM emission was from 4 per million to 100 per million with the emission‐weighted iF of 44 per million. These results propose that exposure due to intraurban air pollution emissions could be decreased more effectively by specifically targeting sources with high exposure potency rather than all sources.     

Estimating Dermal Uptake of Nonionic Organic Chemicals from Water and Soil: I. Unified Fugacity-Based Models for Risk Assessments

Contamination of water and soil that might eventually contact human skin makes it imperative to include the dermal uptake route in efforts to assess potential environmental health risks. Direct measurements of dermal uptake from either water or soil are only available for a small number of the thousands of chemicals likely to be found in the environment. We propose here a mass-transfer model for estimating skin permeability and dermal uptake for organic chemicals that contaminate soil and water. Statistical relationships between measured permeabilities and chemical properties reveal that permeability varies primarily with the octanol-water partition coefficient (Kow) and secondarily with the molecular weight. From these results, we derive a fugacity-based model for skin permeability that addresses the inherent permeability of the skin, the interaction of the skin with the environmental medium on skin (water or soil), and retains a relatively simple algebraic form. Model predictions are compared to measured human skin permeabilities for some 50 compounds in water and four compounds in soil. The model is adjusted to account for dermal uptake during both short-term (10-20 min) and long-term (several hour) exposures. This model is recommended for compounds with molecular weight less than or equal to 280 g.     

Dermal Uptake of Organic Chemicals from a Soil Matrix

Uptake of chemicals from soil on human skin is considered. Based on a review of literature on the structure of human skin, the processes by which chemicals pass through this boundary, and experiments that reveal the rate and magnitude of this transport process; a two-layer model is presented for estimating how chemical uptake through the stratum corneum depends on chemical properties, skin properties, soil properties and exposure conditions. The model is applied to two limiting scenarios--(1) continuous deposition and removal of soil on the skin surface and (2) a one-time deposition of soil onto the skin surface. The fraction of soil-bound chemical that passes through the stratum corneum is dependent on the skin-soil layer thickness; the dimensionless Henry's law constant, Kh and the octanol-water partition coefficient, Kow of the soil-bound chemical. The nature of this dependence is discussed.     

Parameter Uncertainty and Variability In Evaluative Fate and Exposure Models

The human toxicity potential, a weighting scheme used to evaluate toxic emissions for life cycle assessment and toxics release inventories, is based on potential dose calculations and toxicity factors. This paper evaluates the variance in potential dose calculations that can be attributed to the uncertainty in chemical-specific input parameters as well as the variability in exposure factors and landscape parameters. A knowledge of the uncertainty allows us to assess the robustness of a decision based on the toxicity potential; a knowledge of the sources of uncertainty allows us to focus our resources if we want to reduce the uncertainty. The potential dose of 236 chemicals was assessed. The chemicals were grouped by dominant exposure route, and a Monte Carlo analysis was conducted for one representative chemical in each group. The variance is typically one to two orders of magnitude. For comparison, the point estimates in potential dose for 236 chemicals span ten orders of magnitude. Most of the variance in the potential dose is due to chemical-specific input parameters, especially half-lives, although exposure factors such as fish intake and the source of drinking water can be important for chemicals whose dominant exposure is through indirect routes. Landscape characteristics are generally of minor importance.     

A Systematic Uncertainty Analysis of an Evaluative Fate and Exposure Model

Multimedia fate and exposure models are widely used to regulate the release of toxic chemicals, to set cleanup standards for contaminated sites, and to evaluate emissions in life-cycle assessment. CalTOX, one of these models, is used to calculate the potential dose, an outcome that is combined with the toxicity of the chemical to determine the Human Toxicity Potential (HTP), used to aggregate and compare emissions. The comprehensive assessment of the uncertainty in the potential dose calculation in this article serves to provide the information necessary to evaluate the reliability of decisions based on the HTP A framework for uncertainty analysis in multimedia risk assessment is proposed and evaluated with four types of uncertainty. Parameter uncertainty is assessed through Monte Carlo analysis. The variability in landscape parameters is assessed through a comparison of potential dose calculations for different regions in the United States. Decision rule uncertainty is explored through a comparison of the HTP values under open and closed system boundaries. Model uncertainty is evaluated through two case studies, one using alternative formulations for calculating the plant concentration and the other testing the steady state assumption for wet deposition. This investigation shows that steady state conditions for the removal of chemicals from the atmosphere are not appropriate and result in an underestimate of the potential dose for 25% of the 336 chemicals evaluated.     

Health Risk Assessment for Planned Waste Incinerators: Getting the Right Science and the Science Right

Health risk assessment is widely advocated in the United Kingdom as the most comprehensive means of assessing the health risks posed by the emissions of a planned waste incinerator. Its main advantage over other methods of assessment, such as air quality impact assessment, is its ability to address explicitly the direct (inhalation) and indirect (ingestion and dermal contact) health risks posed by different chemicals, including those that are not thought to have a threshold below which no adverse effect will take place. This article examines the level and quality of the emissions assessments included in 61 waste incinerator environmental statements (ESs); in particular, it focuses on the quality of the exposure assessment and risk characterization stages of the health risk assessment process. The article concludes that the ES has not always provided interested stakeholders with the best available information upon which to determine the tolerability of the health risks posed by waste incinerator emissions Some recommendations are made as to how this problem might be addressed in future environmental impact assessment (EIA) processes.     

Can oral toxicity data for PFAS inform on toxicity via inhalation?

Per- and poly-fluoroalkyl substances (PFAS) are ubiquitous in the environment and are detected in wildlife and humans. With respect to human exposure, studies have shown that ingestion is the primary route of exposure; however, in certain settings, exposure via inhalation could also be a significant source of exposure. While many studies examined toxicity of PFAS via ingestion, limited information is available for PFAS toxicity via the inhalation route, translating into a lack of exposure guidelines. Consequently, this article examined whether route-to-route extrapolation to derive guidelines for inhalation exposure is appropriate for PFAS. Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) were used as exemplary PFAS given the abundance of toxicity data for these two compounds. Our evaluation determined that available toxicity and toxicokinetic data support route-to-route extrapolation for PFAS in order to derive inhalation-based standards. Results from this analysis suggest that an air concentration of 7.0 × 10⁻⁵ mg/m³ (or 0.07 μg/m³) would be an appropriate RfC for PFOA and PFOS assuming the 2016 EPA RfD of 0.00002 mg/kg-day, whereas use of the interim RfDs proposed in 2022 of 1.5 × 10⁻⁹ and 7.9 × 10⁻⁹ mg/kg would yield much lower RfCs of 5.25 × 10⁻⁹ and 2.77 × 10⁻⁸ mg/m³ (or 5.25 × 10⁻⁶ and 2.77 × 10⁻⁵ μg/m³) for PFOA and PFOS, respectively.     

Validation of a Novel Air Toxic Risk Model with Air Monitoring

Three modeling systems were used to estimate human health risks from air pollution: two versions of MNRiskS (for Minnesota Risk Screening), and the USEPA National Air Toxics Assessment (NATA). MNRiskS is a unique cumulative risk modeling system used to assess risks from multiple air toxics, sources, and pathways on a local to a state‐wide scale. In addition, ambient outdoor air monitoring data were available for estimation of risks and comparison with the modeled estimates of air concentrations. Highest air concentrations and estimated risks were generally found in the Minneapolis‐St. Paul metropolitan area and lowest risks in undeveloped rural areas. Emissions from mobile and area (nonpoint) sources created greater estimated risks than emissions from point sources. Highest cancer risks were via ingestion pathway exposures to dioxins and related compounds. Diesel particles, acrolein, and formaldehyde created the highest estimated inhalation health impacts. Model‐estimated air concentrations were generally highest for NATA and lowest for the AERMOD version of MNRiskS. This validation study showed reasonable agreement between available measurements and model predictions, although results varied among pollutants, and predictions were often lower than measurements. The results increased confidence in identifying pollutants, pathways, geographic areas, sources, and receptors of potential concern, and thus provide a basis for informing pollution reduction strategies and focusing efforts on specific pollutants (diesel particles, acrolein, and formaldehyde), geographic areas (urban centers), and source categories (nonpoint sources). The results heighten concerns about risks from food chain exposures to dioxins and PAHs. Risk estimates were sensitive to variations in methodologies for treating emissions, dispersion, deposition, exposure, and toxicity.     

Peak Exposures in Epidemiologic Studies and Cancer Risks: Considerations for Regulatory Risk Assessment

We review approaches for characterizing “peak” exposures in epidemiologic studies and methods for incorporating peak exposure metrics in dose–response assessments that contribute to risk assessment. The focus was on potential etiologic relations between environmental chemical exposures and cancer risks. We searched the epidemiologic literature on environmental chemicals classified as carcinogens in which cancer risks were described in relation to “peak” exposures. These articles were evaluated to identify some of the challenges associated with defining and describing cancer risks in relation to peak exposures. We found that definitions of peak exposure varied considerably across studies. Of nine chemical agents included in our review of peak exposure, six had epidemiologic data used by the U.S. Environmental Protection Agency (US EPA) in dose–response assessments to derive inhalation unit risk values. These were benzene, formaldehyde, styrene, trichloroethylene, acrylonitrile, and ethylene oxide. All derived unit risks relied on cumulative exposure for dose–response estimation and none, to our knowledge, considered peak exposure metrics. This is not surprising, given the historical linear no‐threshold default model (generally based on cumulative exposure) used in regulatory risk assessments. With newly proposed US EPA rule language, fuller consideration of alternative exposure and dose–response metrics will be supported. “Peak” exposure has not been consistently defined and rarely has been evaluated in epidemiologic studies of cancer risks. We recommend developing uniform definitions of “peak” exposure to facilitate fuller evaluation of dose response for environmental chemicals and cancer risks, especially where mechanistic understanding indicates that the dose response is unlikely linear and that short‐term high‐intensity exposures increase risk.     

Environmental Exposure of the Adult French Population to Permethrin

This work aims to assess the exposure to permethrin of the adult French population from available contamination measurements of outdoor air, indoor air, and settled dust. Priority is given to the assessment of chronic exposure, given the potential of permethrin to induce cancers and/or endocrine disorders. A statistical method was devised to calculate exposure to permethrin by different pathways (inhalation, indirect dust ingestion, and dermal contact). This method considers anthropometric parameters, the population's space–time budget, and recent methods for calculating dermal exposure. Considering the media of interest, our results pointed to house dust as the main environmental source of permethrin exposure, followed by indoor and outdoor air. Dermal contact and indirect dust ingestion may be more important exposure pathways than inhalation. A sensitivity analysis indicated that exposure estimates were mainly affected by variability within contamination data. This study is the first step in aggregated exposure and risk assessment due to pyrethroid exposure. Outdoor air, indoor air, and settled dust may constitute significant exposure sources, in addition to diet, which could be important. The next step entails assessing internal doses and estimating the proportion of each exposure source and pathway relative to internal exposure.     

Cardiac Sensitization Thresholds of Halon Replacement Chemicals Predicted in Humans by Physiologically-Based Pharmacokinetic Modeling

Human exposure to halons and halon replacement chemicals is often regulated on the basis of cardiac sensitization potential. The dose-response data obtained from animal testing are used to determine the no observable adverse effect level (NOAEL) and lowest observable adverse effect level (LOAEL) values. This approach alone does not provide the information necessary to evaluate the cardiac sensitization potential for the chemical of interest under a variety of exposure concentrations and durations. In order to provide a tool for decision-makers and regulators tasked with setting exposure guidelines for halon replacement chemicals, a quantitative approach was established which allowed exposures to be assessed in terms of the chemical concentrations in blood during the exposure. A physiologically-based pharmacokinetic (PBPK) model was used to simulate blood concentrations of Halon 1301 (bromotrifluoromethane, CF₃Br), HFC-125 (pentafluoroethane, CHF₂CF₃), HFC-227ea (heptafluoropropane, CF₃CHFCF₃), HCFC-123 (dichlorotrifluoroethane, CHCl₂CF₃), and CF₃I (trifluoroiodomethane) during inhalation exposures. This work demonstrates a quantitative approach for use in linking chemical inhalation exposures to the levels of chemical in blood achieved during the exposure.     

The Cancer Risk Associated with Residential Exposure to Soil Containing Radioactive Coal Combustion Residuals

Coal combustion residuals (CCRs) are composed of various constituents, including radioactive materials. The objective of this study was to utilize methodology on radionuclide risk assessment from the Environmental Protection Agency (EPA) to estimate the potential cancer risks associated with residential exposure to CCR‐containing soil. We evaluated potential radionuclide exposure via soil ingestion, inhalation of soil particulates, and external exposure to ionizing radiation using published CCR radioactivity values for ²³²Th, ²²⁸Ra, ²³⁸U, and ²²⁶Ra from the Appalachia, Illinois, and Powder River coal basins. Mean and upper‐bound cancer risks were estimated individually for each radionuclide, exposure pathway, and coal basin. For each radionuclide at each coal basin, external exposure to ionizing radiation contributed the greatest to the overall risk estimate, followed by incidental ingestion of soil and inhalation of soil particulates. The mean cancer risks by route of exposure were 2.01 × 10⁻⁶ (ingestion), 6.80 × 10⁻⁹ (inhalation), and 3.66 × 10⁻⁵ (external), while the upper bound cancer risks were 3.70 × 10⁻⁶ (ingestion), 1.18 × 10⁻⁸ (inhalation), and 6.15 × 10⁻⁵ (external), using summed radionuclide‐specific data from all locations. The upper bound cancer risk from all routes of exposure was 6.52 × 10⁻⁵. These estimated cancer risks were within the EPA's acceptable cancer risk range of 1 × 10⁻⁶ to 1 × 10⁻⁴. If the CCR radioactivity values used in this analysis are generally representative of CCR waste streams, then our findings suggest that CCRs would not be expected to pose a significant radiological risk to residents living in areas where contact with CCR‐containing soils might occur.     

Pathway Analysis for Population-Total Health Impacts of Toxic Metal Emissions

This article describes a simple model for quantifying the health impacts of toxic metal emissions. In contrast to most traditional models it calculates the expectation value of the total damage (summed over the total population and over all time) for typical emission sites, rather than "worst-case" estimates for specific sites or episodes. Such a model is needed for the evaluation of many environmental policy measures, e.g., the optimal level of pollution taxes or emission limits. Based on the methodology that has been developed by USEPA for the assessment of multimedia pathways, the equations and parameters are assembled for the assessment of As, Cd, Cr, Hg, Ni, and Pb, and some typical results are presented (the dose from seafood is not included and for Hg the results are extremely uncertain); the model is freely available on the web. The structure of the model is very simple because, as we show, if the parameters can be approximated by time-independent constants (the case for the USEPA methodology), the total impacts can be calculated with steady-state models even though the environment is never in steady state. The collective ingestion dose is found to be roughly 2 orders of magnitude larger than the collective dose via inhalation. The uncertainties are large, easily an order of magnitude, the main uncertainties arising from the parameter values of the model, in particular the transfer factors. Using linearized dose-response functions, estimates are provided for cancers due to As, Cd, Cr, and Ni as well as IQ loss due to Pb emissions in Europe.     

Daily Inhalation Rate and Time‐Activity/Location Pattern in Japanese Preschool Children

Lack of data on daily inhalation rate and activity of children has been an issue in health risk assessment of air pollutants. This study aimed to obtain the daily inhalation rate and intensity and frequency of physical activity in relation to the environment in Japanese preschool children. Children aged four–six years (n= 138) in the suburbs of Tokyo participated in this study, which involved three days' continuous monitoring of physical activity using a tri‐axial accelerometer and parent's completion of a time/location diary during daily life. The estimated three‐day mean daily inhalation rate (body temperature, pressure, saturated with water vapor) was 9.9 ± 1.6 m³/day (0.52 ± 0.09 m³/kg/day). The current daily inhalation rate value of 0.580 m³/kg/day proposed for use in health risk assessment in Japan is confirmed to be valid to calculate central value of inhaled dose of air pollutants in five‐ to six‐year‐old children. However, the 95th percentile daily inhalation rate of 0.83 m³/kg/day based on measurement for five‐year‐old children is recommended to be used to provide an upper bound estimate of exposure that ensure the protection of all five‐ to six‐year‐old children from the health risk of air pollutants. Children spent the majority of their time in sedentary and light level of physical activity (LPA) when indoors, while 85% of their time when outdoors was spent in LPA and moderate‐to‐vigorous physical activity. The results suggest the need to consider variability of minute respiratory ventilation rate according to the environment for more refined short‐term health risk assessment.     

Validation of Multimedia Models Assessing Exposure to PAHs—The SOLEX Study

Polluted soils have become a public health problem. While population exposure to soil pollutants is generally quantified using multimedia models, their estimations have not been validated, and studies that attempted to do so are scarce. The objective of the SOLEX study was to compare the predictions of pyrene exposure levels (converted into 1 hydroxypyrene) computed by several models with the results of urinary 1-hydropyrene (1-HOP) assays among 110 employees working at three sites polluted during their past use as manufactured gas plants. Four models were used: AERIS (Canada), CalTOX (California, USA), CLEA (UK), and HESP (The Netherlands). Three occupational exposure scenarios--with office, mixed, and outdoor workers--were constructed, based upon job activities during two measurement campaigns, one in winter and one in summer. The exposure levels estimated by the four models could differ markedly (from 7 up to 80 times) according to the exposure scenario. Also, the predominant exposure routes differed according to the model (direct soil ingestion for HESP and CalTOX, inhalation for AERIS, and dermal absorption for CLEA). The predictions of CalTOX are consistent with the 1-HOP measurements for all the scenarios. For HESP, the consistency is observed for the scenarios, office and mixed, for which the pyrene level in the soil is low. AERIS and CLEA yield results that are systematically above the 1-HOP measurements. This study confirms that validation of the models is crucial and points out to the need to proceed to assess components of the models that are the most influential using appropriate statistical analysis in combination with true field data.     

Route-to-Route Extrapolation of the Toxic Potency of MTBE

MTBE is a volatile organic compound used as an oxygenating agent in gasoline. Inhalation from fumes while refueling automobiles is the principle route of exposure for humans, and toxicity by this route has been well studied. Oral exposures to MTBE exist as well, primarily due to ground-water contamination from leaking stationary sources, such as underground storage tanks. Assessing the potential public health impacts of oral exposures to MTBE is problematic because drinking water studies do not exist for MTBE, and the few oil-gavage studies from which a risk assessment could be derived are limited. This paper evaluates the suitability of the MTBE database for conducting an inhalation route-to-oral route extrapolation of toxicity. This includes evaluating the similarity of critical effect between these two routes, quantifiable differences in absorption, distribution, metabolism, and excretion, and sufficiency of toxicity data by the inhalation route. We conclude that such an extrapolation is appropriate and have validated the extrapolation by finding comparable toxicity between a subchronic gavage oral bioassay and oral doses we extrapolate from a subchronic inhalation bioassay. Our results are extended to the 2-year inhalation toxicity study by Chun et al. (1992) in which rats were exposed to 0, 400, 3000, or 8000 ppm MTBE for 6 hr/d, 5 d/wk. We have estimated the equivalent oral doses to be 0, 130, 940, or 2700 mg/kg/d. These equivalent doses may be useful in conducting noncancer and cancer risk assessments.     

Comparison of Standard Radiological Risk Models and Using RESRAD to Derive Generic Risk-Based Area Factors for Final Status Surveys

The RESidual RADioactivity (RESRAD) computer code has been used for years to calculate carcinogenic risk and radiological dose from exposure to radionuclides. The basic ingestion, inhalation, and direct gamma intake equations used by RESRAD, Risk Assessment Guidance for Superfund (RAGS), and the Soil Screening Guidance for Radionuclides (SSG) are similar and can produce similar results, but there are some notable differences. Of particular interest is the fact that RESRAD incorporates sophisticated environmental transport models. Associated environmental parameters allow risk assessors to consider, among other variables, the size (i.e., surface area) of the contaminated zone, a variable not typically addressed quantitatively under the RAGS/SSG paradigm. Considering the similarities between basic RESRAD, RAGS, and SSG intake equations and given the broad acceptance of RESRAD, it stands to reason that RESRAD-derived area factors may be used to supplement RAGS/SSG human health risk calculations. This would allow risk assessors to retrofit existing results or otherwise modify standard RAGS/SSG equations for use in site closeout planning under the Multi-Agency Radiation Survey and Site Investigation Manual (MARSSIM), given a key component of the MARSSIM method is the consideration of small areas of elevated activity or "hot spots" through the use of area factors.     

Exposure Assessment Approaches for Engineered Nanomaterials

Products based on nanotechnology are rapidly emerging in the marketplace, sometimes with little notice to consumers of their nanotechnology pedigree. This wide variety of nanotechnology products will result (in some cases) in unintentional human exposure to purposely engineered nanoscale materials via the dermal, inhalation, ingestion, and ocular pathways. Occupational, consumer, and environmental exposure to the nanomaterials should be characterized during the entire product lifecycle—manufacture, use, and disposal. Monitoring the fate and transport of engineered nanomaterials is complicated by the lack of detection techniques and the lack of a defined set of standardized metrics to be consistently measured. New exposure metrics may be required for engineered nanomaterials, but progress is possible by building on existing tools. An exposure metric matrix could organize existing data by relating likely exposure pathways (dermal, inhalation, ocular, ingestion) with existing measurements of important characteristics of nanoscale materials (particle number, mass, size distribution, charge). Nanomaterial characteristics not commonly measured, but shown to initiate a biological response during toxicity testing, signal a need for further research, such as the pressing need to develop monitoring devices capable of measuring those aspects of engineered nanomaterials that result in biological responses in humans. Modeling the behavior of nanoparticles may require new types of exposure models that individually track particles through the environment while keeping track of the particle shape, surface area, and other surface characteristics as the nanoparticles are transformed or become reactive. Lifecycle analysis could also be used to develop conceptual models of exposure from engineered nanomaterials.     

A regression-based approach for estimating primary and secondary particulate matter intake fractions.

One of the common challenges for life cycle impact assessment and risk assessment is the need to estimate the population exposures associated with emissions. The concept of intake fraction (a unitless term representing the fraction of material or its precursor released from a source that is eventually inhaled or ingested) can be used when limited site data are available or the number of sources to model is large. Although studies have estimated intake fractions for some pollutant-source combinations, there is a need to quickly and accurately estimate intake fractions for sources and settings not previously evaluated. It would be expected that limited source or site information could be used to yield intake fraction estimates with reasonable accuracy. To test this theory, we developed regression models to predict intake fractions previously estimated for primary fine particles (PM2.5) and secondary sulfate and nitrate particles from power plants and mobile sources in the United States. Our regression models were able to predict pollutant-specific intake fractions with R2 between 0.53 and 0.86 and equations that reflected expected relationships (e.g., intake fraction increased with population density, stack height influenced the intake fraction of primary but not secondary particles). Further analysis would be needed to generalize beyond this case study and construct models applicable across source categories and settings, but our analysis demonstrates that inclusion of a limited number of parameters can significantly reduce the uncertainty in population-average exposure estimates.     

Biogeographical Analysis of Chemical Co‐Occurrence Data to Identify Priorities for Mixtures Research

A challenge with multiple chemical risk assessment is the need to consider the joint behavior of chemicals in mixtures. To address this need, pharmacologists and toxicologists have developed methods over the years to evaluate and test chemical interaction. In practice, however, testing of chemical interaction more often comprises ad hoc binary combinations and rarely examines higher order combinations. One explanation for this practice is the belief that there are simply too many possible combinations of chemicals to consider. Indeed, under stochastic conditions the possible number of chemical combinations scales geometrically as the pool of chemicals increases. However, the occurrence of chemicals in the environment is determined by factors, economic in part, which favor some chemicals over others. We investigate methods from the field of biogeography, originally developed to study avian species co‐occurrence patterns, and adapt these approaches to examine chemical co‐occurrence. These methods were applied to a national survey of pesticide residues in 168 child care centers from across the country. Our findings show that pesticide co‐occurrence in the child care center was not random but highly structured, leading to the co‐occurrence of specific pesticide combinations. Thus, ecological studies of species co‐occurrence parallel the issue of chemical co‐occurrence at specific locations. Both are driven by processes that introduce structure in the pattern of co‐occurrence. We conclude that the biogeographical tools used to determine when this structure occurs in ecological studies are relevant to evaluations of pesticide mixtures for exposure and risk assessment.