PROJECT SUMMARY: ANALYSIS OF EXPOSURE, DOSE AND RISK ASSOCIATED WITH TAP WATER CONTAMINATED WITH CHLOROFORM FOR: Mahnomen Public Water System Fond du Lac Band of Lake Superior Chippewa BY: U.S. EPA Office of Research and Development Center for Environmental Solutions and Emergency Response Revision 8 Dated July 2020 EPA/600/S-20/254 ------- ANALYSIS OF EXPOSURE, DOSE AND RISK ASSOCIATED WITH TAP WATER CONTAMINATED WITH CHLOROFORM INTRODUCTION: Many municipal water supply systems use chlorine for primary disinfection or residual protection for drinking water. Because it is difficult to completely remove organics from the drinking water, organic carbon reacts with residual chlorine to create disinfection by-products. As organic matter and chlorine react, trihalomethanes (THMs) are formed, one of which being chloroform. This is of concern due to the high volatility of chloroform and the carcinogenic risk that it potentially presents to individuals from inhaling chloroform. The most significant exposure pathway is believed to be showering (Davis et al. 2016). Here, we analyze water concentrations and estimate air concentrations. We also analyze potential exposures, doses, and risk from the inhalation of chloroform during showering. We perform these analyses for a range of chloroform tap water concentrations that were observed in the Belich Addition (Mahnomen) Public Water System in November 2019. The Mahnomen Public Water System is part of the Fond du Lac Band of Lake Superior Chippewa in Minnesota. This analysis was conducted at the request of EPA Region 5's Water Enforcement and Compliance Assurance Branch. APPROACH: The goal of these analyses is to evaluate the range of observed chloroform tap water concentrations in the Mahnomen Public Water System with respect to several criteria. First, we compare the range of observed chloroform tap water concentrations to a Minnesota water criterion level for chloroform in drinking water (Minnesota Department of Health, 2016) to provide a reference point of comparison. We use California Environmental Protection Agency's acute reference exposure level (mg/m3) for chloroform exposure to evaluate estimated shower enclosure air concentrations that were determined using the range in observed chloroform water concentrations for the Mahnomen community. Also, we use the United States Environmental Protection Agency's (EPA) previously published carcinogenic slope factor for inhalation dose of chloroform to estimate a lifetime cancer risk from the inhalation of chloroform during showering reported by Nazaroff and Alvarez-Cohen in 2001. Finally, we use EPA's unit risk factor (URF) for exposure to chloroform, (ug/m3)"1, to estimate an individual's lifetime cancer risk (U.S. Environmental Protection Agency 1976). The analyses provided here are based on a range of chloroform concentrations observed in the tap water of the Mahnomen Public Water System obtained on November 6, 2019. These chloroform concentrations ranged from 100 (micrograms (10~6 grams) per liter) ug/L to 250 ug/L. The approach described here is also described in the associated Microsoft Excel workbook (Chloroform_exposure_calculations_REV6_7-14-20.xlsx), "OVERVIEW_ASSESSMENT," tab. All the calculations outlined here are performed in the Excel workbook. The approach utilizes Henry's Law Constant to estimate the concentration of chloroform in the shower enclosure air during a showering event using two models: "SIMPLE MODEL" (Sanders, 2002) and "COMPLEX MODEL" (Davis, et al. 2016). The parameter values used in each model were obtained from the Davis et al. (2016) paper because they represent a typical shower as well as behavior of individuals taking showers. A typical shower occurs in an enclosure of 2 m3, has a water flow rate of 9 L/min, and has a duration of 7.7 minutes. We assume individuals take one shower per day. Each model is based on equilibrium conditions. Sanders (2002) developed a simple screening model to determine the concentration of contaminant in air. Assumptions in this model consist of water temperature, the total amount of water used during the showering event (Vwater), and the volume of the shower stall (Vair). This model is derived from the dimensionless expression of Henry's Law Constant and can be found in the Microsoft Excel spreadsheet, tab "SIMPLE MODEL." 2 I ------- Davis etal. (2016) designed a slightly more detailed (complex) model to estimate the concentration of contaminant in the air. More assumptions were taken into account in this model, including air exchange rate (/.„«). generation rate (G2), and transfer efficiency shower duration (7). This model is described in the tab "COMPLEX MODEL." For the estimation of an individual's dose, Chowdhury (2013) developed a dose model to estimate the daily intake of the contaminant through inhalation. This model took into account the assumptions of adsorption efficiency of the contaminant (Er) into a person's lungs, breathing rate (R), shower duration (t), shower frequency (/¦)• exposure frequency (EF), exposure duration (ED), averaging time (AT), and body weight (BW). This model can be found in the tab "DOSEMODEL." EPA previously published a carcinogenic slope factor for chronic exposure to chloroform through inhalation (http://www.dartmouth.edu/~cush.man/courses/engs37/RiskAssessment.pdf) Nazaroff and Alvarez-Cohen (2001). EPA currently does not seem to provide an inhalation slope factor for chloroform ("https://www.epa.gov/iris'). This previously published slope factor, (8.2 x 10"2 mg/kg-day)"1, for chloroform intake via inhalation was used to help assess an individual's risk. To be conservative, we used the Sanders (2002) "SIMPLEMODEL," results for chloroform air concentrations to estimate individual doses and then multiplied each dose by this slope factor to estimate risk. Additionally, male and female doses, due to their different average body masses, were assessed for risk. We also evaluated risk using EPA's Unit Risk Factor (URF) of 2.3 x 10~5 for the inhalation exposure of chloroform ("https://cfpub.epa.gov/ncea/iris2/chemicalLanding.cfin7substance n.mbr=25 ) (U.S. Environmental Protection Agency 1976). Here risk is for exposure to the chloroform during showering. For these estimates of risk, using the observed range of chloroform tap water concentrations, we used the chloroform air concentrations estimated from the "SIMPLE MODEL." RESULTS: In the SUMMARY table below (taken from the "OVERVIEW_ASSESSMENT" tab), we first compare the Minnesota water quality value of 20 ug/L (ppb) with the chloroform concentrations observed in the tap water of Mahnomen community. This comparison is a ratio of observed tap water concentration divided by the Minnesota water quality criterion to show how many times the criterion is exceeded. The Minnesota water quality criterion for chloroform does not directly apply to showering but instead is a general criterion for chloroform in tap water. The observed chloroform concentrations exceed the criterion by about 5 to 13 times. We compare the observed range of chloroform concentrations to the Minnesota criterion as a reference point for comparison. Using the "SIMPLE MODEL" and "COMPLEX MODEL" approaches described in the associated Excel spreadsheet, chloroform air concentrations are calculated using the Sanders and Davis et. al. models, respectively. Next, we compare the calculated air concentrations from each model with the California EPA chronic air exposure level for chloroform as a ratio of calculated air concentration (mg/m3) divided by the California criterion. The ratios show how many times the calculated shower air concentration for the low and high observed chloroform water concentrations exceed the criterion (approx. 10 to 50 times). In the "DOSE MODEL" tab of the associated Microsoft Excel spreadsheet, we use a dose equation to calculate a person's (male and female) absorbed dose from inhaling chloroform during showering. For these dose calculations (Chowdhury, 2013) we use the "SIMPLE MODEL" calculated air concentrations. After doses are calculated, risks are estimated using an earlier EPA carcinogenic slope 3 ------- factor, (mg/kg-day)1, for inhalation of chloroform reported by Nazaroff and Alvarez-Cohen (2001). This slope factor ("https://www.epa.gov/iris') no longer seems to be available via U.S. EPA's Integrated Risk Information System (IRIS), but is used here for comparison. The "DOSEMODEL" tab estimates a person's dose (in units' mg/kg-day) from the inhalation of chloroform during showering and uses the approach described by (Chowdhury 2013). Multiplying the slope factor by the dose results in a unitless risk value. The added risk ranges from 2.8E"4 to 8.3E"4 or about 3 in 10,000 to 8 in 10,000 added risk. The lifetime exposure risk is calculated by multiplying the URF by the estimated chronic, lifetime air concentration to which an individual is exposed. This results in an estimated lifetime exposure risk to chloroform during showering. The added risk ranges from 7.0E"5 to 1.8E4 or about 7 in 100,000 to 2 in 10,000 added risk. These results are provided in the SUMMARY table below. SUMMARY TABLE: EXPOSURE, DOSE, AND RISK ASSESSMENT (Results are a measure of how much greater chloroform water and air concentrations are compared to criteria. Also, an assessment of inhalation dose and risk during showering considering various established criteria.) WATER (Chloroform concentrations observed in the Belich Road community tap water ranged from lOOug/L (ppb) to 250 ug/L) Evaluation criteria values Ratio of Obs/Criterion (Low cone) Ratio of Obs/Criterion (High cone) Minnesota water quality guidance value for Chloroform (ug/L) in drinking water. (https://www.health.state.mn.us/communities/enviro nment/risk/docs/guidance/gw/chlo roforminfo.pdf). Ratio values (observed concentration divided by criterion) exceeding 1 are deemed unacceptable. 20 5.0 12.5 | | AIR Evaluation criteria values Simple model ratio (air conc/criterion) Complex model ratio (air conc/criterion) The chloroform concentrations observed in the Mahnomen community tap water ranged from 100 ug/L (ppb) to 250 ug/L. {Based on low coric chloroform observed) {Based on high coric chloroform observed) {Based on low coric chloroform observed) {Based ori high coric chloroform observed) California EPA acute reference exposure level (mg/m3) is deemed an acceptable acute air exposure concentration for chloroform. Ratio values exceeding 1 are deemed unacceptable. 0.15 20 51 10 24 DOSE Evaluation criteria values Risk fro ¦ m Dose (male) ...... Risk from ¦ Dose (female) Risks calculated using air cone based on SIMPLE MODEL (Low cone obs) (High concobs) (Low concobs) (High concobs) EPA IRIS work published an earlier carcinogenic slope factor (mg/kg-day)1 for chloroform via inhalation, which assumes chronic, long-term exposure. Note that the SIMPLE_MODEL estimated chloroform air concentrations were used for dose calculation. Risks greater than 1E-6 are deemed unacceptable. 8.10E-02 2.8E-04 7.1E-04 3.3E-04 8.3E-04 RISK Evaluation criteria values ............. Risk from Air ........................ Exposure (URF*Air Cone) Risk from Air Exposure (URF*Air Cone) Risks calculated using air cone based on SIMPLE MODEL {Low obs cone) {High obs coric) EPA's unit risk factor (URF) for lifetime exposure (per ug/m3). Estimate of lifetime risk from inhalation exposure during showering. Risks greater than 1E-6 are deemed unacceptable. https://cfpub.epa.gov/ncea/iris2/chemicalLanding.cf m?substance_nmbr=25 2.30E-05 7.0E-05 1.8E-04 * http://www.dartmouth.edu/~cushman/courses/engs37/RiskAssessment.pdf ------- DISCUSSION: The observed chloroform concentrations in the Mahnomen Public Water System exceed Minnesota's Department of Health criterion for chloroform in drinking water by a factor of about 5 to 13 times (Minnesota Department of Health, 2016). While the Minnesota water quality criterion for chloroform does not apply to showering, this comparison provides a reference point and illustrates that the observed chloroform concentrations in the tap water of the Mahnomen Public Water System are elevated. Results show that the estimated shower enclosure air exposure concentrations, using both the simple and complex models, exceed the California acute air concentration criterion for chloroform by a factor of approximately 10 to 50 times. The complex model estimates were lower because the model incorporates an air exchange rate, or loss term, to provide less conservative results than the simple model. The Davis et. al., model was modified to represent equilibrium conditions to be consistent with the "SIMPLE MODEL". Comparing the estimated doses to an earlier EPA published carcinogenic risk factor (slope factor), considering both males and females, showed that individual added lifetime risk associated with showering in these potential air concentrations of chloroform exceeds the EPA's acceptable risk of 1 x 10~6 acceptable (one in a million) risk. Estimated risks from an absorbed dose of chloroform acquired during showering ranged from approx. 3E~4 to 8E~4 or about 3 in 10,000 to 8 in 10,000 added risk. Added risks greater than IE 6 (one in a million) are deemed unacceptable. Finally, we also calculated risk from inhalation exposure (using EPA's URF for chloroform) during showering. For exposure risk we calculated chloroform air concentrations in the shower using the "SIMPLE MODEL." These risks, determined for the low and high observed chloroform concentrations, also exceeded the EPA's acceptable lifetime risk, with risks ranging from approximately 7E~5 to 2E~4 or about 7 in 100,000 to 2 in 10,000 added risk. Again, added risks greater than one in a million are deemed unacceptable. Although risks (both dose-based and exposure-based) were not specifically provided using the more detailed, less conservative "COMPLEX_MODEL," these risks also exceed EPA's one in a million acceptable lifetime risk. Given the exceedance of the various criteria, mitigated measures should probably be considered. REFERENCES 1. Sanders, P. F., (2002) A screening model for predicting concentrations of volatile organic chemicals in shower stall air, Division of Science, Research and Technology, New Jersey Department of Environmental Protection, P.O. Box 409, Trenton, NJ 08625. https://www.ni.gov/dep/dsr/research/A%20Screening%20Model%20for%20Predicting%20Concentra tions%20of%20VOCs%20in%20Shower%20Stall%20Air-RPS.pdf. accessed 6/17/2020. 2. Davis M.J., Janke R., Taxon T.N. (2016) Assessing Inhalation Exposures Associated with Contamination Events in Water Distribution Systems. PLoS ONE 11(12): eO 168051. https://doi.oo mrnal .pone .0168051. 3. Chowdhury S. (2016) Exposure assessment for trihalomethanes in municipal drinking water and risk reduction strategy. Sci Total Environ. 2013;463-464:922-930. doi:10.1016/j.scitotenv.2013.06.104. 5 ------- 4. Minnesota Department of Health. (2016). Chloroform and Drinking Water. https://www.health.state.mn.us/communities/environment/risk/docs/guidance/gw/chlorofomiinfo.pdf accessed on 6/18/2020. 5. Nazaroff and Alvarez-Cohen (2001). Risk Assessment (carcinogenic slope factor for inhalation of chloroform). http://www.dartmouth.edu/~cushman/courses/engs37/RiskAssessment.pdf. 6. U.S. Environmental Protection Agency (1976). Unit Risk Factor for Chloroform. https://cfbub.epa.gov/ncea/iris2/chemicalLanding.cfm7substance n.mbr=25. accessed 6/17/2020. DISCLAIMER: This document and the associated Excel spreadsheet include contributions from EPA and individuals outside the United States Government. It has been subjected to review by the U.S. EPA's Office of Research and Development (ORD) and approved for sharing to individuals and parties that have an interest in these results. The sampling and analysis results for the chloroform observed in the tap water of the Mahnomen Public Water System were not subjected to EPA's quality system requirements. The views expressed in this summary are those of the author(s) and do not necessarily represent the views or the policies of the U.S. Environmental Protection Agency. The results and discussion in this project summary have not been formally disseminated by the Agency and should not be construed to represent any Agency determination or policy. 6 ------- |