Clay Nelson

Relative Bioavailability and Bioaccessibility and Speciation of Arsenic in Contaminated Soils

Background: Assessment of soil arsenic (As) bioavailability may profoundly affect the extent of remediation required at contaminated sites by improving human exposure estimates. Because small adjustments in soil As bioavailability estimates can significantly alter risk assessments and remediation goals, convenient, rapid, reliable, and inexpensive tools are needed to determine soil As bioavailability. Objectives: We evaluated inexpensive methods for assessing As bioavailability in soil as a means to improve human exposure estimates and potentially reduce remediation costs. Methods: Nine soils from residential sites affected by mining or smelting activity and two National Institute of Standards and Technology standard reference materials were evaluated for As bioavailability, bioaccessibility, and speciation. Arsenic bioavailability was determined using an in vivo mouse model, and As bioaccessibility was determined using the Solubility/Bioavailability Research Consortium in vitro assay. Arsenic speciation in soil and selected soil physicochemical properties were also evaluated to determine whether these parameters could be used as predictors of As bioavailability and bioaccessibility. Results: In the mouse assay, we compared bioavailabilities of As in soils with that for sodium arsenate. Relative bioavailabilities (RBAs) of soil As ranged from 11% to 53% (mean, 33%). In vitro soil As bioaccessibility values were strongly correlated with soil As RBAs (R2 = 0.92). Among physicochemical properties, combined concentrations of iron and aluminum accounted for 80% and 62% of the variability in estimates of RBA and bioaccessibility, respectively. Conclusion: The multifaceted approach described here yielded congruent estimates of As bioavailability and evidence of interrelations among physicochemical properties and bioavailability estimates.

Changes in silver nanoparticles exposed to human synthetic stomach fluid: Effects of particle size and surface chemistry

The significant rise in consumer products and applications utilizing the antibacterial properties of silver nanoparticles (AgNPs) has increased the possibility of human exposure. The mobility and bioavailability of AgNPs through the ingestion pathway will depend, in part, on properties such as particle size and the surface chemistries that will influence their physical and chemical reactivities during transit through the gastrointestinal tract. This study investigates the interactions between synthetic stomach fluid and AgNPs of different sizes and with different capping agents. Changes in morphology, size and chemical composition were determined during a 30 min exposure to synthetic human stomach fluid (SSF) using Absorbance Spectroscopy, High Resolution Transmission Electron and Scanning Electron Microscopy (TEM/SEM), Dynamic Light Scattering (DLS), and Nanoparticle Tracking Analysis (NTA). AgNPs exposed to SSF were found to aggregate significantly and also released ionic silver which physically associated with the particle aggregates as silver chloride. Generally, the smaller sized AgNPs (<10nm) showed higher rates of aggregation and physical transformation than larger particles (75 nm). Polyvinylpyrrolidone (pvp)-stabilized AgNPs prepared in house behaved differently in SSF than particles obtained from a commercial source despite having similar surface coating and size distribution characteristics.

Variability Associated with As in Vivo–in Vitro Correlations When Using Different Bioaccessibility Methodologies

To evaluate the capabilities of in vitro assays to predict arsenic (As) relative bioavailability (RBA), we examined the relationship between As bioaccessibility, determined using a number of in vitro bioaccessibility (IVBA) methodologies (SBRC, IVG, PBET, DIN and UBM) and As RBA determined in a mouse assay for nine As-contaminated soils and 1 NIST reference material (2710a). Significant differences (P < 0.05) in As IVBA were observed within and between assays indicating that different IVBA methodologies may not produce congruent data, as a result of variability in the extracting medium constituents and/or differences in the pH of gastric and intestinal phases. When results of in vivo determinations of As RBA were compared with As IVBA results, there was no significant difference in slopes of the relationships (P = 0.49-0.88) when SBRC, IVG, PBET, DIN, and UBM gastric and intestinal phase data were used. A significantly (P < 0.05) smaller y-intercept was, however, determined for the in vivo-SBRC gastric phase correlation compared to SBRC, IVG, PBET, and DIN intestinal phase, a factor that may influence prediction of As RBA, especially for soils with low As RBA. When in vivo-in vitro relationships were compared to previously derived correlations from the literature, some differences were observed. These differences may be attributed to factors affecting both in vivo and in vitro data including physiological differences in animal models (e.g., mouse versus swine), which may influence As absorption, differences in the approach used to estimate As RBA, and variability arising from subtle interoperator differences in performance of in vitro assays.

Independent Data Validation of an in Vitro Method for the Prediction of the Relative Bioavailability of Arsenic in Contaminated Soils

In vitro bioaccessibility (IVBA) assays estimate arsenic (As) relative bioavailability (RBA) in contaminated soils to improve accuracy in human exposure assessments. Previous studies correlating soil As IVBA with RBA have been limited by the use of few soil types and sources of As, and the predictive value of As IVBA has not been validated using an independent set of As-contaminated soils. In this study, a robust linear model was developed to predict As RBA in mice using IVBA, and the predictive capability of the model was independently validated using a unique set of As-contaminated soils. Forty As-contaminated soils varying in soil type and contaminant source were included in this study, with 31 soils used for initial model development and nine soils used for independent model validation. The initial model reliably predicted As RBA values in the independent data set, with a mean As RBA prediction error of 5.4%. Following validation, 40 soils were used for final model development, resulting in a linear model with the equation RBA = 0.65 × IVBA + 7.8 and an R(2) of 0.81. The in vivo-in vitro correlation and independent data validation presented provide critical verification necessary for regulatory acceptance in human health risk assessment.

Predicting oral relative bioavailability of arsenic in soil from in vitro bioaccessibility

ABSTRACT Several investigations have been conducted to develop in vitro bioaccessibility (IVBA) assays that reliably predict in vivo oral relative bioavailability (RBA) of arsenic (As). This study describes a meta-regression model relating soil As RBA and IVBA that is based upon data combined from previous investigations that examined the relationship between As IVBA and RBA when IVBA was determined using an extraction of soil in 0.4 M glycine at pH 1.5. Data used to develop the model included paired IVBA and RBA estimates for 83 soils from various types of sites such as mining, smelting, and pesticide or herbicide application. The following linear regression model accounted for 87% of the observed variance in RBA (R2 = .87): RBA(%) = 0.79 × IVBA(%) + 3.0. This regression model is more robust than previously reported models because it includes a larger number of soil samples, and also accounts for variability in RBA and IVBA measurements made on samples collected from sites contaminated with different As sources and conducted in different labs that have utilized different experimental models for estimating RBA.

Relationship Between Total and Bioaccessible Lead on Children’s Blood Lead Levels in Urban Residential Philadelphia Soils

Relationships between total soil or bioaccessible lead (Pb), measured using an in vitro bioaccessibility assay, and childrens blood lead levels (BLL) were investigated in an urban neighborhood in Philadelphia, PA, with a history of soil Pb contamination. Soil samples from 38 homes were analyzed to determine whether accounting for the bioaccessible Pb fraction improves statistical relationships with childrens BLLs. Total soil Pb concentration ranged from 58 to 2821 mg/kg; the bioaccessible Pb concentration ranged from 47 to 2567 mg/kg. Childrens BLLs ranged from 0.3 to 9.8 μg/dL. Hierarchical models were used to compare relationships between total or bioaccessible Pb in soil and childrens BLLs. Total soil Pb concentration as the predictor accounted for 23% of the variability in child BLL; bioaccessible soil Pb concentration as the predictor accounted for 26% of BLL variability. A bootstrapping analysis confirmed a significant increase in R2 for the model using bioaccessible soil Pb concentration as the predictor with 99.0% of bootstraps showing a positive increase. Estimated increases of 1.3 μg/dL and 1.5 μg/dL in BLL per 1000 mg/kg Pb in soil were observed for this study area using total and bioaccessible Pb concentrations, respectively. Childrens age did not contribute significantly to the prediction of BLLs.

In vivo and in vitro methods for evaluating soil arsenic bioavailability: relevant to human health risk assessment

ABSTRACT Arsenic (As) is the most frequently occurring contaminant on the priority list of hazardous substances, which lists substances of greatest public health concern to people living at or near U.S. National Priorities List site. Accurate assessment of human health risks from exposure to As-contaminated soils depends on estimating its bioavailability, defined as the fraction of ingested As absorbed across the gastrointestinal barrier and available for systemic distribution and metabolism. Arsenic bioavailability varies among soils and is influenced by site-specific soil physical and chemical characteristics and internal biological factors. This review describes the state-of-the science that supports our understanding of oral bioavailability of soil As, the methods that are currently being explored for estimating soil As relative bioavailability (RBA), and future research areas that could improve our prediction of the oral RBA of soil As in humans. The following topics are addressed: (1) As soil geochemistry; (2) As toxicology; (3) in vivo models for estimating As RBA; (4) in vitro bioaccessibility methods; and (5) conclusions and research needs.

Estimating relative bioavailability of soil lead in the mouse

ABSTRACT Lead (Pb) in soil is an important exposure source for children. Thus, determining bioavailability of Pb in soil is critical in evaluating risk and selecting appropriate strategies to minimize exposure. A mouse model was developed to estimate relative bioavailability of Pb in NIST SRM 2710a (Montana 1 Soil). Based on Pb levels in tissues, the mean relative bioavailability of this metal in this soil was 0.5. Estimates of relative bioavailabilities derived from mouse compared favorably with those obtained in juvenile swine. The mouse model is thus an efficient and inexpensive method to obtain estimates of relative bioavailability of soil Pb.

Relating soil geochemical properties to arsenic bioaccessibility through hierarchical modeling

ABSTRACT Interest in improved understanding of relationships among soil properties and arsenic (As) bioaccessibility has motivated the use of regression models for As bioaccessibility prediction. However, limits in the numbers and types of soils included in previous studies restrict the usefulness of these models beyond the range of soil conditions evaluated, as evidenced by reduced predictive performance when applied to new data. In response, hierarchical models that consider variability in relationships among soil properties and As bioaccessibility across geographic locations and contaminant sources were developed to predict As bioaccessibility in 139 soils on both a mass fraction (mg/kg) and % basis. The hierarchical approach improved the estimation of As bioaccessibility in studied soils. In addition, the number of soil elements identified as statistically significant explanatory variables increased when compared to previous investigations. Specifically, total soil Fe, P, Ca, Co, and V were significant explanatory variables in both models, while total As, Cd, Cu, Ni, and Zn were also significant in the mass fraction model and Mg was significant in the % model. This developed hierarchical approach provides a novel tool to (1) explore relationships between soil properties and As bioaccessibility across a broad range of soil types and As contaminant sources encountered in the environment and (2) identify areas of future mechanistic research to better understand the complexity of interactions between soil properties and As bioaccessibility.

Evaluation of a low-cost commercially available extraction device for assessing lead bioaccessibility in contaminated soils

The U.S. EPAs in vitro bioaccessibility (IVBA) method 9200.1-86 defines a validated analytical procedure for the determination of lead bioaccessibility in contaminated soils. The method requires the use of a custom-fabricated extraction device that uses a heated water bath for sample incubation. In an effort to improve ease of use, increase sample throughput, and reduce equipment acquisition and maintenance costs, an alternative low-cost, commercially available extraction device capable of sample incubation via heated air and end-over-end rotation was evaluated. An intra-laboratory study was conducted to compare lead bioaccessibility values derived using the two extraction devices. IVBA values were not statistically different (α = 0.05) between the two extraction devices for any of the soils (n = 6) evaluated in this study, with an average difference in mean lead IVBA of 0.8% (s.d. = 0.5%). The commercially available extraction device was able to generate accurate lead IVBA data as compared to the U.S. EPAs expected value for a National Institute of Standards and Technology standard reference material soil. The relative percent differences between high and low IVBA values for each soil, a measure of instrument precision, were also not statistically different (α = 0.05) between the two extraction devices. The statistical agreement of lead IVBA values observed using the two extraction devices supports the use of a low-cost, commercially available extraction device as a reliable alternative to a custom-fabricated device as required by EPA method 9200.1-86.