Residential Tap Water Contamination Following the Freedom Industries Chemical Spill: Perceptions, Water Quality, and Health Impacts
- Andrew J. Whelton ,
- LaKia McMillan ,
- Matt Connell ,
- Keven M. Kelley ,
- Jeff P. Gill ,
- Kevin D. White ,
- Rahul Gupta ,
- Rajarshi Dey , and
- Caroline Novy
Abstract

During January 2014, an industrial solvent contaminated West Virginia’s Elk River and 15% of the state population’s tap water. A rapid in-home survey and water testing was conducted 2 weeks following the spill to understand resident perceptions, tap water chemical levels, and premise plumbing flushing effectiveness. Water odors were detected in all 10 homes sampled before and after premise plumbing flushing. Survey and medical data indicated flushing caused adverse health impacts. Bench-scale experiments and physiochemical property predictions showed flushing promoted chemical volatilization, and contaminants did not appreciably sorb into cross-linked polyethylene (PEX) pipe. Flushing reduced tap water 4-methylcyclohexanemethanol (4-MCHM) concentrations within some but not all homes. 4-MCHM was detected at unflushed (<10 to 420 μg/L) and flushed plumbing systems (<10 to 96 μg/L) and sometimes concentrations differed among faucets within each home. All waters contained less 4-MCHM than the 1000 μg/L Centers for Disease Control drinking water limit, but one home exceeded the 120 μg/L drinking water limit established by independent toxicologists. Nearly all households refused to resume water use activities after flushing because of water safety concerns. Science based flushing protocols should be developed to expedite recovery, minimize health impacts, and reduce concentrations in homes when future events occur.
Introduction
| product | reported ingredient | estimated composition of the spilled liquid |
|---|---|---|
| crude MCHM | 4-methylcyclohexanemethanol (MCHM) | 68% to 89% |
| 4-(methoxymethyl)cyclohexanemethanol | 4% to 22% | |
| water | 4% to 10% | |
| methyl 4-methylcyclohexanecarboxylate | 5% | |
| dimethyl 1,4-cyclohexanedicarboxylate | 1% | |
| methanol | 1% | |
| 1,4-cyclohexanedimethanol | 1% to 2% | |
| stripped PPHa | propylene glycol phenyl ether (PPH) | amount unclear |
| dipropylene glycol phenyl ether (DiPPH) | amount unclear |
Thirteen days after the spill, the Centers for Disease Control and Prevention (CDC) reported that the spilled product contained “88.5% Crude MCHM, 7.3% Stripped PPH, and 4.2% water”, although the CDC’s calculation methodology was not disclosed. Stripped PPH was blended into Eastman Chemical Company’s Crude MCHM by Poca Blending Company in Nitro, WV. The Stripped PPH product contained both PPH and DiPPH compounds.
Figure 1

Figure 1. 4-MCHM Monitoring Results for the (a) Kanawha Valley Water Treatment Facility from January 10 to January 15, 2014 and (b) Water Distribution System from January 10 to March 6, 2014. 4-MCHM has both trans- and cis-isomers (9) and 4-MCHM concentrations reported by WVAW, the State, and in the present study were reported as the combined trans- and cis- isomer concentration. Distribution system samples were collected at various locations to include hydrants, storage tanks, booster stations, public buildings including schools, hospitals, and private businesses. The dotted horizontal lines represent the (i) CDC’s 4-MCHM screening level (1000 μg/L), (ii) WVTAP’s 4-MCHM screening level (120 μg/L). Only results where the value was greater than the MDL are shown (i.e., more than 1100 “non-detect” results are not shown). Also not shown are March 2014 testing results where water leaving the water treatment plant contained 0.42 to 0.60 μg/L 4-MCHM. Testing was also conducted in June 2014 after the water treatment plant’s activated carbon filters were replaced. 4-MCHM was not found above a MDL of 0.38 μg/L exiting the water treatment plant or in the distribution system.
| contaminant name and assumption by health officials | CDC (January 2014) | WVTAP (March 2014) |
|---|---|---|
| 4-MCHM, μg/L | 1000 | 120 |
| PPH, μg/L | 1200 | 850 |
| DiPPH, μg/L | 1200 | 250 |
| exposure duration | 14 days | 28 days |
| most sensitive population | 1 year old child | formula fed infant |
| exposure routes | ingestion only | ingestion, inhalation, dermal |
WVTAP included toxicologists from academic and public health organizations located in Israel, the United Kingdom, and United States. In January 2014, the State of West Virginia applied a 100-fold safety factor to the CDC’s 4-MCHM screening level because of concern that limited toxicology data existed. The State of West Virginia’s screening level for 4-MCHM was 10 μg/L.
Materials and Methods
Survey Instrument and Participating Households
Sampling Activity and Analysis
Premise Plumbing Flushing Procedure
Contaminant Interaction with PEX Pipe
Syndromic Surveillance
Physiochemical Properties and Statistical Analysis
Results and Discussion
In-Home Survey Results and Comparison to Public Health Studies
Household Demographics and Premise Plumbing Characteristics
Resident Behaviors and Perceptions
Resident Health Impacts
| symptom | organization conducting study and date information was publicly released | ||||||
|---|---|---|---|---|---|---|---|
| household interview survey | syndromic surveillance record review | WVTAP household interview survey (16) | CDC/BPH emergency department record review (19) | BPH physician record review (20) | KCHD household telephone survey (17) | CDC household interview survey (18) | |
| (this study) Jan. 2014 | (this study) Jan. 2014 | Feb. 2014 | Mar. 2014 | Mar. 2014 | Apr. 2014 | Jul. 2014 | |
| dermatologic | |||||||
| skin irritation | 40.3 | 63.2§ | 53.9 | ||||
| rash | 12.5 | 47.6 | 40 | 28.5 | 21.6 | § | 43.6 |
| itching | 10 | 19.8 | 60.0 | ||||
| eye irritation | 12.5 | 25.3 | 10 | 14.6 (pain) | 13.3 | 26.4 | 5.1 |
| gastrointestinal | |||||||
| nausea | 31.3 | 21.0 | 30 | 37.9 | 26.42Δ | 12.8 | |
| vomiting | 0.0 | 13.7 | 10 | 28.2 | 8.3 | Δ | 5.1 |
| abdominal pain | 6.3 | 24.4 | 8.3 | 27.0Φ | 5.1 | ||
| diarrhea | 6.3 | 16.3 | 0 | 24.4 | 5.0 | Φ | 12.8 |
| respiratory | |||||||
| unspecified | 17.0 | ||||||
| sore throat | 9.4 | 14.9 | 8.3 | 10.3 | |||
| cough | 6.9 | 12.7 | 15.0 | 15.4 | |||
| orientation | |||||||
| dizziness | 18.8 | 40 | 25.2ε | 7.7 | |||
| headache | 12.5 | 13.7 | 30 | 21.9 | 11.7 | ε | 10.3 |
| other | 12.5 | 80 | 14.1 | 23.1 | |||
Numbers in columns total to greater than 100% because multiple symptoms were reported by each surveyed person/household. Blank entries indicate that the data set did not classify symptoms in that specific category; Kanawha-Charleston Health Department (KCHD) syndromic surveillance data represent 224 patients from 10 physicians; The household survey as part of WVTAP (15) represents 10 households in eight of the nine counties affected; The Centers for Disease Control and Prevention (CDC) and West Virginia Department of Health and Human Resources (DHHR) Bureau of Public Health (BPH) emergency department data represent 356 patients from 10 emergency departments; The West Virginia BPH physician record review represents 60 persons; The KCHD randomized telephone survey represents 499 persons and the title of the effort was Community Assessment Population Survey; The KCHD telephone survey included categories where multiple symptoms were listed. Symptoms that were used in combined categories are denoted with symbols; The CDC’s Community Assessment for Public Health Emergency Response (CASPER) household survey data represent 171 households; The present study household survey data represents 16 households. For some of the reports there are significant differences between when the report was dated complete and when it was released to the public. Studies are presented chronologically as the data became publicly available.
Water Use Activity
Figure 2

Figure 2. (a) Visits to emergency departments reported by the CDC and BPH (b) syndromic surveillance cases of clinically defined chemical exposure from January 9 through February 9, 2014. Records represent 10 emergency medical departments with 356 patients and 10 physician offices with 224 patients, respectively.
Organic Contaminant Levels in the Unflushed and Flushed Homes
Odor and 4-MCHM Levels
Figure 3

Figure 3. Tap water 4-MCHM concentration for unflushed homes at different in-home locations. The dashed line represents the method detection limit (MDL) of 10 μg/L; Homes 5 and 6 did not contain 4-MCHM in concentrations above the MDL; Home 1’s bathroom faucet concentration was below the MDL; Distances shown in parentheses reflect the straight-line distance from each household to the WVAW treatment plant. Single water samples were analyzed from each tap.
Figure 4

Figure 4. Tap water 4-MCHM concentration before and after the premise plumbing system flush. Results from a single kitchen or bathroom tap at each home is shown; Dark blue bars represent preflush concentration, light gray bars represent postflush; The text in parentheses describes the straight-line distance to the WVAW treatment plant and number of days after the Do Not Use Order was issued before the plumbing system was flushed; The dashed line represents the MDL of 10 μg/L. Postflush sample for Home 1 was below the MDL; No 4-MCHM was found above the MDL in Home 5 before or after flushing; Single water samples were analyzed from each tap; Water pre- and postflush was not analyzed from all 10 homes visited.
Surrogate Tap Water Contamination Indicators in Flushed and Unflushed Homes
| parameter (1) | EPA limit | unflushed homes | flushed homes | ||||
|---|---|---|---|---|---|---|---|
| min | max | above limit? | min | max | above limit? | ||
| health standards, maximum contaminant level (MCL) | |||||||
| As | 0.010 | <0.000 58 | 0.000 66 | no | <0.000 58 | <0.000 58 | no |
| Ba | <2 | 0.02 | 0.05 | no | 0.02 | 0.03 | no |
| Be | 0.004 | <0.000 082 | <0.000 082 | no | <0.000 082 | 0.000 094 | no |
| Cd | <0.005 | 0.000 08 | 0.000 20 | no | 0.000 073 | 0.000 703 | no |
| Cr | <0.1 | 0.0003 | 0.0009 | no | 0.0003 | 0.0011 | no |
| Cu | < 1.3 | 0.006 | 1.700 | yes | 0.006 | 0.030 | no |
| Pb | 0–0.015 | 0.0001 | 0.0200 | yes | 0.0002 | 0.0050 | no |
| aesthetic standards, secondary maximum contaminant level (SMCL) | |||||||
| Al | 0.05–0.2 | 0.01 | 1.00 | yes | 0.001 | 0.15 | no |
| Fe | < 0.3 | 0.006 | 1.900 | yes | 0.010 | 0.280 | no |
| Mn | < 0.05 | 0.0005 | 0.06 | yes | 0.0002 | 0.0200 | no |
| Zn | <5 | 0.19 | 0.86 | no | 0.20 | 0.32 | no |
All values shown are reported in mg/L; MCL = Maximum contaminant level; Health standards are primary MCLs while aesthetic standards are secondary MCLs.
Limitations and Implications
Supporting Information
Additional figure and tables related to the materials and methods, results and discussion, and event timeline. This material is available free of charge via the Internet at http://pubs.acs.org.
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Acknowledgment
Thanks are extended to the 16 households who participated in this study, along with Rob Goodwin and Maya Nye whom helped us identify households visited. We also acknowledge Drs. Kateryna Artyushkova and Jose M. Cerrato at the Univ. New Mexico for their XPS analysis. Dr. Kevin West (Univ. South Alabama) is thanked for providing COSMOS-RS water solubility estimation data. The authors appreciate Coleman Miller, Fredrick Avera, and Mahmoud Alkahout (University South Alabama), who conducted the sorption studies. Drs. David Ladner (Clemson University), Simoni Triantafyllidou (Virginia Tech), Kevin Morley (AWWA), Maryam Salehi, and Chad Javert (Purdue University) also provided feedback on manuscripts contents. WVAW staff, State of West Virginia officials, and WVTAP researchers are also thanked for their insights. The authors greatly appreciate feedback provided by the anonymous reviewers.
| CDC | Centers for Disease Control and Prevention |
| cPVC | chlorinated polyvinyl chloride |
| DiPPH | dipropylene glycol phenyl ether |
| EPA | Environmental Protection Agency |
| KCHD | Kanawha-Charleston Health Department |
| 4-MCHM | 4-methylcyclohexanemethanol |
| GC/MS | gas chromatography–mass spectrometry |
| LLE | liquid liquid extraction |
| MCL | primary maximum contaminant level |
| MDL | method detection limit |
| PB | poly(1-butene) |
| PEX | cross-linked polyethylene |
| PPH | propylene glycol phenyl ether |
| SMCL | secondary maximum contaminant level |
| SPME | solid phase microextraction |
| SUVA | specific ultraviolet absorbance |
| TERA | toxicological excellence in risk assessment |
| TOC | total organic carbon |
| WVAW | West Virginia American Water |
| WV BPH | West Virginia Bureau of Public Health |
| WV DHHR | West Virginia Department of Health and Human Resources |
| WVTAP | West Virginia Testing Assessment Project |
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Abstract

Figure 1

Figure 1. 4-MCHM Monitoring Results for the (a) Kanawha Valley Water Treatment Facility from January 10 to January 15, 2014 and (b) Water Distribution System from January 10 to March 6, 2014. 4-MCHM has both trans- and cis-isomers (9) and 4-MCHM concentrations reported by WVAW, the State, and in the present study were reported as the combined trans- and cis- isomer concentration. Distribution system samples were collected at various locations to include hydrants, storage tanks, booster stations, public buildings including schools, hospitals, and private businesses. The dotted horizontal lines represent the (i) CDC’s 4-MCHM screening level (1000 μg/L), (ii) WVTAP’s 4-MCHM screening level (120 μg/L). Only results where the value was greater than the MDL are shown (i.e., more than 1100 “non-detect” results are not shown). Also not shown are March 2014 testing results where water leaving the water treatment plant contained 0.42 to 0.60 μg/L 4-MCHM. Testing was also conducted in June 2014 after the water treatment plant’s activated carbon filters were replaced. 4-MCHM was not found above a MDL of 0.38 μg/L exiting the water treatment plant or in the distribution system.
Figure 2

Figure 2. (a) Visits to emergency departments reported by the CDC and BPH (b) syndromic surveillance cases of clinically defined chemical exposure from January 9 through February 9, 2014. Records represent 10 emergency medical departments with 356 patients and 10 physician offices with 224 patients, respectively.
Figure 3

Figure 3. Tap water 4-MCHM concentration for unflushed homes at different in-home locations. The dashed line represents the method detection limit (MDL) of 10 μg/L; Homes 5 and 6 did not contain 4-MCHM in concentrations above the MDL; Home 1’s bathroom faucet concentration was below the MDL; Distances shown in parentheses reflect the straight-line distance from each household to the WVAW treatment plant. Single water samples were analyzed from each tap.
Figure 4

Figure 4. Tap water 4-MCHM concentration before and after the premise plumbing system flush. Results from a single kitchen or bathroom tap at each home is shown; Dark blue bars represent preflush concentration, light gray bars represent postflush; The text in parentheses describes the straight-line distance to the WVAW treatment plant and number of days after the Do Not Use Order was issued before the plumbing system was flushed; The dashed line represents the MDL of 10 μg/L. Postflush sample for Home 1 was below the MDL; No 4-MCHM was found above the MDL in Home 5 before or after flushing; Single water samples were analyzed from each tap; Water pre- and postflush was not analyzed from all 10 homes visited.
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