Exposure to selected preservatives in personal care products: case study comparison of exposure models and observational biomonitoring data.

Exposure models provide critical information for risk assessment of personal care product ingredients, but there have been limited opportunities to compare exposure model predictions to observational exposure data. Urinary excretion data from a biomonitoring study in eight individuals were used to estimate minimum absorbed doses for triclosan and methyl-, ethyl-, and n-propyl- parabens (TCS, MP, EP, PP). Three screening exposure models (European Commission Scientific Commission on Consumer Safety [SCCS] algorithms, ConsExpo in deterministic mode, and RAIDAR-ICE) and two higher-tier probabilistic models (SHEDS-HT, and Creme Care & Cosmetics) were used to model participant exposures. Average urinary excretion rates of TCS, MP, EP, and PP for participants using products with those ingredients were 16.9, 3.32, 1.9, and 0.91 µg/kg-d, respectively. The SCCS default aggregate and RAIDAR-ICE screening models generally resulted in the highest predictions compared to other models. Approximately 60-90% of the model predictions for most of the models were within a factor of 10 of the observed exposures; ~30-40% of the predictions were within a factor of 3. Estimated exposures from urinary data tended to fall in the upper range of predictions from the probabilistic models. This analysis indicates that currently available exposure models provide estimates that are generally realistic. Uncertainties in preservative product concentrations and dermal absorption parameters as well as degree of metabolism following dermal absorption influence interpretation of the modeled vs. measured exposures. Use of multiple models may help characterize potential exposures more fully than reliance on a single model.

Consensus Modeling of Median Chemical Intake for the U.S. Population Based on Predictions of Exposure Pathways.

Prioritizing the potential risk posed to human health by chemicals requires tools that can estimate exposure from limited information. In this study, chemical structure and physicochemical properties were used to predict the probability that a chemical might be associated with any of four exposure pathways leading from sources-consumer (near-field), dietary, far-field industrial, and far-field pesticide-to the general population. The balanced accuracies of these source-based exposure pathway models range from 73 to 81%, with the error rate for identifying positive chemicals ranging from 17 to 36%. We then used exposure pathways to organize predictions from 13 different exposure models as well as other predictors of human intake rates. We created a consensus, meta-model using the Systematic Empirical Evaluation of Models framework in which the predictors of exposure were combined by pathway and weighted according to predictive ability for chemical intake rates inferred from human biomonitoring data for 114 chemicals. The consensus model yields an R2 of ∼0.8. We extrapolate to predict relevant pathway(s), median intake rate, and credible interval for 479 926 chemicals, mostly with minimal exposure information. This approach identifies 1880 chemicals for which the median population intake rates may exceed 0.1 mg/kg bodyweight/day, while there is 95% confidence that the median intake rate is below 1 µg/kg BW/day for 474572 compounds.

A Model for Risk-Based Screening and Prioritization of Human Exposure to Chemicals from Near-Field Sources.

Exposure- and risk-based assessments for chemicals used indoors or applied to humans (i.e., in near-field environments) necessitate an aggregate exposure pathway framework that aligns chemical exposure information from use sources to internal dose and eventually to their potential for health effects. Such a source-to-effect continuum is advocated to balance the complexity of human exposure and the insufficiency of relevant data for thousands of existing and emerging chemicals. Here, we introduce the Risk Assessment, IDentification And Ranking-Indoor and Consumer Exposure (RAIDAR-ICE) model, which establishes an integrated framework to evaluate human exposure due to indoor use and direct application of chemicals to humans. As a model evaluation, RAIDAR-ICE faithfully reproduces exposure estimates inferred from biomonitoring data for 37 chemicals with direct and indirect near-field sources. RAIDAR-ICE generates different rankings for 131 chemicals based on different exposure- and risk-based assessment metrics, demonstrating its versatility for diverse chemical screening goals. When coupled with a far-field RAIDAR model, the near-field RAIDAR-ICE model enables assessment of aggregate human exposure. Overall, RAIDAR-ICE is a powerful tool for high-throughput screening and prioritization of human exposure to neutral organic chemicals used indoors.

Model-based exploration of the drivers of mountain cold-trapping in soil.

A pollutant is said to undergo mountain cold-trapping if it is found at higher concentrations in a surface medium (soil, snow, foliage) high on a mountain, where it is colder, than in the same medium lower on the mountain. The processes that lead to mountain cold-trapping in soil were explored for a set of hypothetical Perfectly Persistent Pollutants (PPPs) by varying several environmental parameters in a fugacity based fate and transport box model. These parameters were: the spatial scale of the mountain; the rate and location of rain; the amount of particles in the atmosphere; the presence and magnitude of the upslope temperature gradient. The relative potential of each hypothetical PPP to exhibit mountain cold-trapping was expressed in terms of its Mountaintop Contamination Potential (MCP). The PPPs with the highest MCPs were those that neither were deposited from the atmosphere to the surface in the lower zones in the model nor left the model domain without being deposited at all. The simulations revealed that under most conditions wet-gaseous deposition is the biggest driver of mountain cold-trapping in soils, and its effects are greatly enhanced by large negative temperature gradients and increased precipitation upslope. Dry-gaseous and wet-and-dry-particle deposition processes cause similar PPPs to exhibit mountain cold-trapping, and the contributions to MCP by the dry processes are of the same magnitude as wet-particle deposition. Dry gaseous deposition alone is insufficient to cause mountain cold-trapping in soils under any conditions modelled here. Those measuring organic contaminants in mountains should expect to find that mountains with different climates cold-trap different pollutants, and that some mountains may not exhibit upslope enrichment of any species.

Application of XAD-resin based passive air samplers to assess local (roadside) and regional patterns of persistent organic pollutants.

We used XAD-resin based passive air samplers (PAS) to measure atmospheric levels of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) at five ombrotrophic bogs in Eastern Canada. The aims of our study were to investigate the influence of local roads on contaminant levels in the bogs, to derive the regional pattern of atmospheric concentrations, and to assess the uncertainties of the method. Expanded uncertainties based on the duplicate PAS deployed at 24 sites were good for the PAHs, while the deployment period of approx. 100 days was too short to yield acceptable uncertainties for PCBs. The regional PAH distribution was in good agreement with the calculated source proximity of the sampled bogs. We conclude that XAD-resin based PAS deployed for comparatively short periods are well suited for measuring atmospheric concentrations of volatile PAHs, while in remote regions longer deployment is necessary for less volatile PAHs and for PCBs.

On the construction, comparison, and variability of airsheds for interpreting semivolatile organic compounds in passively sampled air.

Air mass origin as determined by back trajectories often aids in explaining some of the short-term variability in the atmospheric concentrations of semivolatile organic contaminants. Airsheds, constructed by amalgamating large numbers of back trajectories, capture average air mass origins over longer time periods and thus have found use in interpreting air concentrations obtained by passive air samplers. To explore some of their key characteristics, airsheds for 54 locations on Earth were constructed and compared for roundness, seasonality, and interannual variability. To avoid the so-called "pole problem" and to simplify the calculation of roundness, a "geodesic grid" was used to bin the back-trajectory end points. Departures from roundness were seen to occur at all latitudes and to correlate significantly with local slope but no strong relationship between latitude and roundness was revealed. Seasonality and interannual variability vary widely enough to imply that static models of transport are not sufficient to describe the proximity of an area to potential sources of contaminants. For interpreting an air measurement an airshed should be generated specifically for the deployment time of the sampler, especially when investigating long-term trends. Samples taken in a single season may not represent the average annual atmosphere, and samples taken in linear, as opposed to round, airsheds may not represent the average atmosphere in the area. Simple methods are proposed to ascertain the significance of an airshed or individual cell. It is recommended that when establishing potential contaminant source regions only end points with departure heights of less than ∼700 m be considered.

Transport of semivolatile organic compounds to the Tibetan plateau: spatial and temporal variation in air concentrations in mountainous Western Sichuan, China.

The distribution of organochlorine pesticides and polychlorinated biphenyls in air along an altitudinal transect on Balang Mountain in western China was measured by deploying XAD-2 resin based passive air samplers in duplicate at seven sites with elevations ranging from 1242 to 4485 m above sea level for five consecutive six-month periods between 2005 and 2008. Analyzed by gas chromatography-high resolution mass spectrometry, concentrations of hexachlorobenzene were highest, followed by hexachlorocyclohexanes, DDT-related compounds and PCB congeners 28 and 52. Except for hexachlorobenzene, which had largely uniform concentrations in space and time, there were clear seasonal variations with concentrations in summer being higher than in winter. With a few exceptions, concentrations that vary little with altitude suggest that the presence of these chemicals in the area is almost entirely due to atmospheric transport, most likely from the Chengdu plain. This is supported by similarities in the relative abundance of different compounds and in the differences between summer and winter concentrations measured in the city of Chengdu and in the mountains. Furthermore, air mass trajectories during the sampling period often originate to the East, passing over the Western part of the Sichuan basin, including the Chengdu plain, prior to arriving at the sampling sites. Higher summer time values in the mountains are due to more contaminated air being blown into the region, presumably due either to higher pesticide usage in summer or due to higher temperatures leading to higher evaporation in source regions. Air and soil from the region are in equilibrium with respect to alpha-HCH, gamma-HCH, and HCB, whereas a situation of net deposition prevails for p,p'-DDE and p,p'-DDT.

On the mechanism of mountain cold-trapping of organic chemicals.

The preferential accumulation of selected organic pollutants at higher altitude has been observed in a number of mountain regions. It is proposed that this phenomenon is due to differences in the efficiency of precipitation scavenging at various elevations, which, in turn, is due to the temperature dependence of organic vapor partitioning into rain, snow, and aerosols. The occurrence and extent of enrichment with elevation depends on whether the scavenging efficiency of a chemical is sensitive to temperature within the range encountered along a mountain slope. A multicompartment fate and transport model parameterized for mountain systems suggeststhat substances with equilibrium partitioning coefficients at 25 degrees C between water and air from 10(3.5) to 10(5.5) and between atmospheric particles and air from 10(9) to 10(11) are most likely to be subject to mountain cold-trapping. Such substances remain in the atmospheric vapor phase at higher valley temperatures, but are scavenged efficiently at the lower temperatures prevailing at higher altitudes. This implies that substances subject to mountain cold-trapping are approximately 2 orders of magnitude less volatile than substances that experience global cold-trapping. For example, while lighter PCBs get preferentially trapped at higher latitudes, the heavier PCBs are predicted to experience the strongest mountain cold-trapping. These model results agree with the results of field studies, with the exception of those studies that rely on sample media such as plant foliage for which precipitation is not the dominant deposition pathway. It appears that very fast deposition processes are required to trap contaminants along mountain slopes, whereas such processes reduce contaminant transport to remote polar regions.

Cold-trapping of persistent organic pollutants in the mountain soils of western Sichuan, China.

In the Chinese province of Sichuan steep mountains rise from the very densely populated and intensely cultivated Chengdu basin more than 4000 elevational meters to the Tibetan Plateau. This steep physical gradient is exceptionally well suited to investigate the transport of persistent pesticides and other organic contaminants from low to high elevations. In spring and autumn 2006, 25 soil samples were taken at five elevations ranging from 2636 to 4479 m along the East-facing slope of Balang Mountain in Wolong Nature Reserve. Analysis of soil extracts was done by gas chromatography-high resolution mass spectrometry. Whereas hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), and dichlorodibenzotrichloroethane and its degradation products (DDTs) were present at levels of a few ng/g, only two light PCB congeners were detected at levels below 1 ng/g in soil. Soil concentration for all analytes increased significantly and exponentially with altitude. The rate of concentration increase, expressed quantitatively through the slope of the linear regression between the logarithm of the concentrations and altitude, increases along the sequence HCB < PCB < HCH < or = DDT. This trend is consistent with, and therefore lends additional observational support to, a mountain cold-trapping mechanism based on the temperature dependence of precipitation scavenging.