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Case study: the crude MCHM chemical spill
investigation and recovery in West Virginia USA
Cite this: Environ. Sci.: Water Res.
Technol., 2017, 3, 312

A. J. Whelton,*a L. McMillan,b C. L.-R. Novy,b K. D. Whitec and X. Huanga
Several recent chemical spills have caused large-scale drinking water contamination incidents in Canada
and the USA. The study goal was to identify key decisions and actions critical to incident investigations
using the 2014 crude MCHM chemical spill in West Virginia USA as a case study. Environmental testing records, scientific reports, government documents, and communication records were reviewed. Results
showed that thorough characterization of the spilled liquid and impacted source water is critical toassessing potential public health risks, estimating chemical fate, and designing infrastructure decontamination procedures that can restore infrastructure use. Premise plumbing water testing was not carried-out by
responders but testing conducted by other organizations identified the decontamination procedures issued

Received 13th December 2015,
Accepted 21st March 2016
DOI: 10.1039/c5ew00294j

by responders and drinking water screening levels were not adequate to protect public health. Rapid
bench-scale tests should be considered to (1) examine water treatment breakdown products, (2) evaluate
chemical sorption and leaching by infrastructure materials (i.e., activated carbon, plastics), (3) predict water
heater decontamination, and (4) estimate chemical volatilization during fixture use. Key actions to support

rsc.li/es-water

an effective response and research needs were identified.

Water impact
Large-scale drinking water contamination incidents can render water utility and premise plumbing infrastructure unusable or marginally effective.
Contaminated water exposure can also cause adverse health impacts prompting the need for immediate medical attention. Loss of safe water access canresult in economic losses and decrease public confidence for a community. Rapid investigations and responses are needed to protect the population fromharm and quickly recover affected infrastructure. The 2014 Elk River chemical spill in West Virginia USA was reviewed as a case study and key actions anddecisions essential to better protecting drinking water, the population, and infrastructure were identified.

Introduction
Between 2014 and mid-2015 a series of large-scale drinking
water contamination incidents prompted the issuance of do
not drink and do not use orders to the entire service population for several U.S. and Canadian water suppliers.1 Source
water contaminants included algal toxins, diesel fuel, crudeoil, and coal processing liquids (Table 1). In most cases, thespecific chemical makeup and toxicity of chemicals in thecontaminated source water were either poorly understood or
unknown, and contaminated water was distributed to thecommunities.
Three incidents in early 2015 resulted in source water contamination and led to large-scale drinking water contaminaa

Division of Environmental and Ecological Engineering and Lyles School of Civil
Engineering, Purdue University, West Lafayette, IN, USA.
E-mail: awhelton@purdue.edubEnvironmental Toxicology Program, University of South Alabama, Mobile, AL,USAc
Department of Civil Engineering, University of South Alabama, Mobile, AL, USA

312 | Environ. Sci.: Water Res. Technol., 2017, 3, 312–332

tion in Nibley City, Utah (diesel fuel), Glendive, Montana(crude oil), and Longueuil, Quebec (diesel fuel). These reference cases revealed a wide array of investigative approaches
applied by government agencies and utilities. In all cases, thecontaminated source water was chlorinated prior to distribution, and contamination was first detected by customer complaints of petroleum odours at the tap. Upon the discovery
that customers were receiving contaminated water, a waterban was established followed by flushing of water utility infrastructure. Customers were then directed to flush their premise plumbing.
Limited information regarding water testing activities during the Glendive and Longueuil incidents was available while
no water testing information for the Nibley incident2 wasfound. In Glendive, a variety of semi-volatile (SVOC) and volatile organic chemicals (VOC) were found in the source water
and water distribution system (Table 2).4 Before premiseplumbing flushing was authorized, airborne VOC testing was
conducted indoors while faucets were running.9,10 Unfortunately, this premise water was not chemically analysed. At

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Table 1 Recent water contamination incidents that caused drinking water outages in the United States and Canada

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Incident characteristics
City, state

Date

Nibley City,
UTa
Glendive, MTb

Apr.
Diesel fuel2015
Jan. 2015 Crude oil

Source watertype

ContaminantsLongueuil, CNc Jan. 2015 Diesel fuelToledo, OHd
Charleston,
WVe

Aug.
Microcystins
2014
Jan. 2014 Coal processing
liquidPopulation affected(people)First detection

Water use
order

Outage duration(days)

Spring

5000

Odour complaint

Do not use

1

YellowstoneRiver
St. LawrenceRiver
Lake Erie

5500

Odour complaint

Do not use

5

230 000

Odour complaint2

500 000

Elk River

300 000

Chemicalmonitoring
Odour complaint

Do notdrink
Do notdrink
Do not use

29aCity of Nibley2,3 and contaminated spring water was disinfected with free chlorine. b EPA.4 City of Glendive5 water treatment plant processes
included sedimentation, filtration, softening, and free chlorine disinfection. c Atkin (2015).6 City of Longueuil7 utilized a conventional
treatment process with coagulation, filtration, disinfection enhanced with ultraviolet, and free chlorination. d City of Toledo8 utilized freechlorination, filtration, and softening. e Ref. 13.

Table 2 Glendive's Yellowstone River and water distribution system sampling results, ppb

Source waterContaminant reported (January 19,
by responders
2014)

Water distribution
system (January 21, 2014)

Benzenen-Butylbenzene
sec-Butylbenzene
Ethylbenzene
Isopropylbenzene
p-Isopropyltoluene
Naphthalenen-Propylbenzene
Toluene
1,2,4-Trimethylbenzene
1,3,5-Trimethylbenzene
o-Xylenem+p-Xylenes

4.09 (max)nrnr
0.37 (max)
nr
nr
nr
nr
6.64 (max)nrnrnr
7.39 (max)

14
0.83
0.58
4.9
1.1
0.71
1.0
1.8
21
15
3.9
8.6
32

Water was analysed in accordance with EPA Method 524; nr =records not found. Water distribution system samples contained 1.37
ppm free chlorine residual at pH 7.6.

Furthermore, it is unclear if the sorption and desorption
capabilities of water treatment media, plastic water distribution and premise plumbing components were considered in
the response. No justifications for premise plumbing flushing protocol design, and estimates of indoor chemical volatilization during flushing were found. After an exhaustive literature review, no study that reviewed other drinking watercontamination incidents to this detail was found. This lackof available data inhibits the identification of post-incident
lessons learned for reference during acute, time-sensitive
contamination events.
The study goal was to identify key decisions during alarge-scale chemical drinking water contamination incident.
Results were intended to assist the water, public health, andgovernment sectors improve their decision-making judgments during incident response and recovery. This case study
was also conducted to identify research needs.
Table 3 Maximum contaminant concentration in the St. Lawrence Riverand treated drinking water exiting the City of Longueuil water treatment
plant, ppb drinking water outages in the United States and Canada

least one resident reported becoming ill while following theflushing guidance issued by government agencies and the water utility.11 In Longueil Canada, water quality and chemical
analysis data for the water treatment plant and distribution
system were available (Table 3), but it is unclear if premiseplumbing water testing was conducted.7,12 In all incidents,
no post-flushing premise water analysis seems to have been
carried-out.
The observed inconsistency in reference case response actions indicates a deficiency in current investigation approaches. For example, it is unclear whether a thoroughchemical analysis of the spilled liquid was completed, as data
were not readily available. No data describing how water
quality information was used to design subsequent water andindoor air sampling actions or actions to examine water treatment process generated by-products were found.

This journal is © The Royal Society of Chemistry 2017

Contaminant category reported by Source
responders
water

Exiting water
treatment plant

BenzeneTolueneEthyl benzene
Xylenes
1,2,4-Trimethylbenzene
Dichloro-2,2-propane
Other VOCs
Total PAHs
Other organic compounds
C10–C50

0.2
2.6
nd
2.7
5.0
nd
nd
nd
nd
nd

0.3
3.8
nd
3.0
10.0
nd
nd
nd
nd
nd

Water samples were collected between January 15 and January 18,
2015 and were analysed in accordance with EPA Methods 524 and624. PAH = Polynuclear aromatic hydrocarbons the mobile laboratory
reported total xylenes (o-, m-, p-) and laboratory testing reported
o-xylene only; nd = not detected above the method detection limit.
Data was reported by City of Longueuil.7

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The 2014 Elk River chemical spill in Charleston, West Virginia was used as a case study because a large number of organizations conducted independent water sampling and limited information was available to the responders:
1. The liquid that contaminated the source water was achemical mixture,
2. More than 2 million people downstream relied on theaffected source water as a water supply,
3. The population that received contaminated drinking
water exceeded 300 000 people (Charleston area 300 000 andCity of Huntington, 86 000), and
4. A water ban remained in effect for up to 10 days insome parts of the Charleston area.
Specific objectives of this study were to (1) review all available records pertaining to incident response and recovery actions created by private, public, and university organizations
that participated, (2) use these results to outline key decisions, and (3) identify research needs for improving watercontamination incident response and recovery.

Elk River incident overview and casestudy approach
Incident overview
On January 9, 2014 more than 10 000 gallons of a coalcleaning liquid spilled from two above-ground storage tanks
into the Elk River. This river was the sole water supply for theCharleston, West Virginia area.13 The spilled liquid was usedin coal preparation plants.14,15 An investigation by the Stateof West Virginia revealed that carbon steel tanks 396 and 397
had corroded and were leaking.16 As of March 2016, the exact
spill volume was still under investigation by the U.S. Chemical Safety and Hazard Investigation Board,17 but the spilledliquid is known to have contained a mixture of “crude
4-methylcyclohexanemethanol (MCHM)” and “stripped polyglycol phenyl ethers (PPH).”
Like the aforementioned reference cases, contaminated
Elk River water passed through the Kanawha Valley Water
Treatment Plant (KVWTP) in Charleston. This facility and the
distribution system was owned and operated by West Virginia
American Water (WVAW).18 Potable water with a distinct
black-liquorice smell was distributed to 300 000 people on
January 9 through 2200 miles of water distribution pipe, 107
storage tanks, and 120 booster stations across 124 pressurezones to upwards of 90 000 buildings.18,21,22 Contaminatedriver water also travelled downstream, entered and passed
through the City of Huntington's water treatment plant. Contaminated river water continued 390 miles further downstream which prompted water municipalities in Ohio, Kentucky, and Indiana to shut down their river water intakes.
The do not use order in Charleston was in effect for up to 10
days in parts of the KVWTP distribution system. The do notuse order warned the population “do not use tap water for
drinking, cooking, cleaning, washing, or bathing”.23,24 The
do not use order also warned customers not to use water except for toilet flushing and firefighting activities.25–27

314 | Environ. Sci.: Water Res. Technol., 2017, 3, 312–332

Environmental Science: Water Research & Technology

Federal health officials established short-term screening
levels (i.e., concentrations considered safe for 14 days of ingestion)
for
three
drinking
water
contaminants:
4-methycyclohexanemethanol (MCHM), polypropylene glycol
phenyl ether (PPH), and dipropylene glycol phenyl ether(DiPPH). After the KVWTP and distribution system had undergone flushing, the order was lifted and the population
was directed to flush the contaminated water out of their premise plumbing. Two and a half months after the spill, GAC
filter media in the KVWTP that had been desorbing 4-MCHM
from treated water was replaced. Several public, private, andnon-profit organizations conducted bench- and field-scaletesting. A detailed timeline of events for one year following
the incident can be found in a supplemental data file published elsewhere.19
Case study approach
Several organizations that collected information and issued
guidance in the wake of this spill are described in Table 4.
Information collected included material safety data sheets(SDS) provided to emergency responders, along with records
for tank liquid analysis, spill site and waterway environmental sampling, water treatment plant and water distribution
system sampling, and premise plumbing sampling. Publichealth data and premise plumbing flushing protocols issued
by the state, WVAW, Kanawha-Charleston Health Department(KCHD), and American Federation of Teachers (AFT) werealso reviewed. Communications by organizations that contributed to incident response and recovery decisions werealso reviewed. Additionally, available fact sheets and reports
prepared by government agencies, private companies, and academic researchers were evaluated.

Results
Constituents in tank 396 liquid and their chemical properties
Hours after the State of West Virginia and WVAW (referred tocollectively as RESP) discovered the spill, they reviewed thecrude MCHM product SDS, which indicated 4-MCHM was
the main constituent. Using this information, RESP developed analytical methods to detect 4-MCHM in the tank 396
liquid and in water.13 Numerous other chemicals were present in the tank liquid (Table 5), as indicated by the crude
MCHM SDS.28
RESP had difficulty identifying the numerous chemicals
present in the water supply. After initial drinking water testing for 4-MCHM had occurred January 9 and the CDC
established a health based screening level,36 Freedom Industries, Inc. disclosed that an additional product called stripped
PPH had also been present in the tank,29 and thus had not
yet been considered in health risk assessments. This disclosure did not come until 12 days after the spill. In response,
RESP37 investigated and found PPH and DiPPH in contaminated drinking water, and the CDC established screening
levels for these compounds.38 Eleven months after the spill,
the U.S. Geological Survey (USGS) reported that methyl

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Table 4 Organizations involved in the incident response and recovery

Name

Role

Eastman Chemical Company
DOW Chemical Company

Manufacturer of crude MCHM present in the Freedom Industries, Inc. storage tank.
Manufacturer of product that was ultimately processed into stripped PPH present in the Freedom
Industries, Inc. storage tank.
Owner of the corroded storage tank and tank farm site on the Elk River. Provided responders a copy ofthe material safety data sheet of crude MCHM and stripped PPH. Hired various consulting firms to
conduct spill site characterization. Originator of stripped PPH.
Regional water supplier that withdrew, treated, and distributed contaminated water to the 300 000
service population from their Charleston water treatment plant and to 86 000 people from their
Huntington plant. Conducted water quality monitoring at their treatment plant and distribution system.
Issued premise plumbing flushing guidance.
Various agencies such as the Departments of Environmental Protection, Homeland Security, Health andHuman Resources conducted water quality monitoring at the water treatment plant and distribution
system, collected and analysed public health data. Issued premise plumbing flushing guidance.
Regional health department that served 250 000 of 300 000 people affected by the water outage in theCharleston area. Compiled and analysed syndromic surveillance records. Issued premise plumbing
flushing guidance.
Established health based 14 day drinking water screening levels for 4-MCHM, PPH, and DiPPH for theingestion exposure pathway.
Deployed a regional on scene coordinator (OSC) to the spill site shortly after the incident. Conductedchemical analysis of water and soil samples collected from the Freedom Industries, Inc. spill site. Issued
a 14 day drinking water screening level for 4-MCHM for the inhalation exposure pathway.
With collaborators, conducted in-home drinking water sampling before and after residents were advised
to flush their premise plumbing, created a water heater decontamination model, conducted plastic pipe
sorption experiments for two crude MCHM ingredients, conducted acute toxicity testing of the spilledliquid on aquatic organisms, developed an indoor air exposure model, estimated physical chemical properties of the liquid's ingredients, and analysed public health data.
Conducted in home drinking water sampling before and after residents were advised to flush theirpremise plumbing. Conducted activated carbon and river sediment sorption, and river water sampling.
Conducted in-home drinking water sampling before and after residents were advised to flush their premise plumbing.
Independent researchers funded by West Virginia that conducted in-home drinking water sampling,odour analysis of the contaminated water, evaluated the health based screening levels established by
CDC and the State of West Virginia, examined breakdown products formed by water treatment
processes.
Experimentally measured physical and chemical properties of trans- and cis-4-MCHM isomers,
conducted odour analysis of pure 4-MCHM and crude MCHM, examined 4-MCHM sorption to activatedcarbon, and potential for aerobic degradation in activated sludge wastewater treatment processes.
Filed a class-action lawsuit against multiple parties involved in the spill. Conducted Elk River water
testing, premise plumbing, and carried-out acute toxicity testing of an aquatic organism with crude
MCHM available in 2014.
Conducted water quality monitoring of the Elk River, Ohio River, and drinking water sampling at theirCharleston, West Virginia office.
Conducted drinking water odour analysis, bench-scale powdered activated carbon (PAC) study for
4-MCHM removal from the water column, and water sampling of the Ohio River.

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Freedom Industries, Inc.

West Virginia American Water(WVAW)

State of West Virginia

Kanawha Charleston Health
Department (KCHD)
Centers for Disease Control andPrevention (CDC)
Environmental Protection Agency(EPA)
The Authors (AUTH)

West Virginia University (WVU)
Downstream Strategies, Inc. (ENVC)
West Virginia Testing Assessment
Project (WVTAP)

Virginia Tech (VT)Group of Attorneys (ATTY)

United States Geological Survey(USGS)Louisville Water Company (LWC)

4-methylcyclohexanecarboxylate (MMCHC), another ingredient in the tank liquid, was present in the water distribution
system.33 Although MMCHC was listed on the crude MCHM
SDS, USGS was the only organization that tested for it. Customers were directed to flush their premise plumbing and it
is unknown the degree airborne exposure occurred due toPPH, DiPPH, and MMCHC volatility.
Another complexity was that as the catalyst used to create
crude MCHM aged, proportions of crude MCHM ingredientschanged,39 however, no compositional analysis data wasavailable for how the levels of major and minor ingredientswere affected. Furthermore, Freedom Industries indicatedthat once the crude MCHM product was obtained from Eastman Chemical Company this product was sometimes
blended with stripped PPH, exposed to HCl to reduce pH,
and water was removed.40 These discoveries emphasize theThis journal is © The Royal Society of Chemistry 2017

risk government agencies and water suppliers face when relying on information generated and provided by parties
connected to the spill. For example, SDSs did not contain anyof this information.28,30 Also evident is the risk encounteredwhen toxicity information is not updated and/or not provided
to users/regulators in their entirety and under context.
While some data regarding the tank liquid are available, its exact composition remains poorly understood. All
testing laboratories reported the total 4-MCHM concentration (i.e., total concentration of trans- and cis-isomers),
which was the most abundant contaminant (Table 5).
4-MCHM isomers were present at a trans- : cis-isomer ratioof 2 : 1.33,41 Two major ingredients and nine additional compounds not reported on product SDSs were detected in thetank liquid and were quantified. Their concentrations sometimes differed between reporting organizations. USGS was

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Table 5 Chemical composition of the spilled liquid, presence of chemicals in the drinking water and environmental media from the spill site, tentatively
identified vs. confirmed compounds

Est. bySpilled liquid
CDC/
F. IND F. IND REICWVTAP USGS
1/14
1/14
3/14
3/14
12/14

Env.
Media

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Product SDS
Product

Contaminant

EAST
1/14

Crude
MCHM

4-Methylcyclohexanemethanol (MCHM)

68–89%

4-(Methoxymethyl)cyclohexanemethanol(MMCHM)
Water
Methyl 4-methylcyclohexanecarboxylate (MMCHC)
Dimethyl 1, 4-cyclohexanedicarboxylate (DMCD)
Methanol
1,4-Cyclohexanedimethanol (CHDM)
Polyglycolethers

4–22%

88.5%a

4–10%
5%
1%
1%
1–2%

Stripped
PPH*
Not on SDS Propylene glycol phenyl ether (PPH)
Dipropylene glycol phenyl ether (DiPPH)
Formaldehyde
Methylene chloride

2-Methoxyethoxybenzene (MEB)
Cyclohexanemethanol (CHM)
Dimethylester 1,4-cyclohexanedicarboxylic acid
4-Methyl, methyl ester cyclohexanecarboxylic acid
(MMCHCA)
4-Methyl cyclohexanecarboxylic acid (MCHCA)
1-Hydroxymethyl-2-methyl-1-cyclohexane (HMC)
n-Hexadecanoic acid
Octadecanoic acid
Other unidentified compounds

79.63%b Yb

ATTY
4/15

Tank
PW site

77–89%b 940b g
kg−1

Y

Yb

Y

Ye

5.60%d Yc
100%

7.3%a
d

11.33%

Yc
1.84%d Yc
Yc
Yc

1.60%
<5%

Y
Y
86b ppm Y
b
15 g
kg−1

Ye

Ye
Ye
Ye
Ye
Ye

Significant figures and units differed because all data was reported “as-is” from sources. EAST is an abbreviation for Eastman Chemical Company; F. IND is an abbreviation for Freedom Industries; PW = potable water; values shown with listed decimal places exactly what were reportedby the testing organization; EAST = Eastman Chemical Company;28 CDC/Freedom Industries;29,30 REIC = Cortruvo;31 WVTAP;32 USGS;33 ATTY =Attorneys.34 a Values were estimated by the CDC and the calculation methodology was not found. b Compound confirmed with an analyticalstandard. c Compound identification was tentative (TIC). d Information provided by reporting organization insufficient to describe analyticalconfirmation. e Compound detected in spill site ground water or storm water one month after the spill by the EPA.35 A variety of aromatic
chemicals were detected in groundwater, but are likely not due to the Freedom Industries chemical spill and are not listed above. The spill site
was formerly the home of a petroleum handling company that was not completely remediated. Units for % detection (w/w, w/v) were notreported.

the only organization to detect MMCHC in the liquid andconfirm its presence with an analytical standard. CHDM wasfound at a much greater concentration (5.6%) when compared to the 1–2% reported on the crude MCHM SDS.
During the spill response, RESP attempted to understandthe fate of the tank liquid's constituents in the Elk River,
KVWTP, and distribution system. Physiochemical properties
such as water solubility, vapour pressure, and log Kow values
for tank liquid ingredients were sought, but most were notfound by RESP because SDSs contained little to no data forthese properties.28,30 Follow-up work by others weeks after the
spill revealed that publicly accessible EPA databases such as
SPARC and EPIWEB either contained or could be used to estimate these properties.19,42 Based on these databases many of
the tank liquid ingredients were moderately to highly soluble
in water (up to 28 000 ppm for some ingredients at 21 °C), volatile (up to 118 mmHg at 21 °C), and their fate was temperature dependent. Others confirmed through experiments
months after the spill that 4-MCHM volatilized from wa-

316 | Environ. Sci.: Water Res. Technol., 2017, 3, 312–332

ter,14,15 and the water solubility and log Kow for each 4-MCHM
isomer was found to be similar (1010 ppm and 2.46 and 1300
ppm and 2.35 at 21 °C for trans- and cis-isomers, respectively).
The trans-isomer however was three times more volatile thanthe cis-isomer.42,43 EPA databases could only estimate theproperties of total 4-MCHM, not properties for each isomer.
Short-term drinking water screening levels. In the hours following the spill's discovery the State of West Virginia asked the
CDC to determine a safe drinking water concentration for
4-MCHM. After reviewing Eastman Chemical Company's
limited36,44,45 toxicological data for crude MCHM, pure
4-MCHM, and the crude MCHM SDS, the CDC established a 14
day health based screening level of 1 ppm for 4-MCHM.36,45
This screening level was based on the ingestion exposure pathway. Hours later, the State of West Virginia added a 100-foldsafety factor, establishing a lower screening level of 0.010 ppm.
During the early days of the response, 0.010 ppm was the minimum detection limit (MDL) of 4-MCHM in water.13 The Stateof West Virginia used their screening level to determine whenThis journal is © The Royal Society of Chemistry 2017

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the water in the KVWTP and distribution system was safe touse.46 WVAW, relied on the CDC recommended 1 ppm
screening level to determine when the water was safe touse.18 The water ban was not lifted until 4-MCHM concentrations exiting the KVWTP were near 0.010 ppm.
Because health officials did not understand which
chemicals were present in the tank liquid and contaminatedwater when the spill occurred, they were unable to fully evaluate drinking water safety before issuing initial drinking watersafety guidance. On January 9, the CDC issued a 28 day
4-MCHM screening level of 1 ppm.36 But, 12 days after this
CDC announcement, Freedom Industries' disclosed stripped
PPH, another chemical mixture, was also in the tank liquid.
This disclosure prompted the CDC to reactively establish 14
day health based screening levels for PPH (1.2 ppm) and DiPPH(1.2 ppm).37 On January 13 WVAW eliminated the do not use
order for some parts of their distribution system. The USGS initiated their own tap water study of their Charleston, West Virginia office building nine days after the spill and detected
MMCHC in the drinking water distribution system.33 While the
CDC and State of West Virginia health risk assessments considered pure MCHM and crude MCHM, for which MMCHC is aconstituent, pure MMCHC was not the subject of independentrisk assessments. The presence and toxicity of breakdown products created as contaminated water travelled through the
KVWTP and the water distribution system were not considered in these assessments. Limited tank liquid and water
sampling data have resulted in an incomplete understanding
about the presence of other chemicals in the water supply.
Two months after the spill, toxicologists working with theWest Virginia Testing Assessment Project (WVTAP) reviewed
available toxicology data for the ingredients listed on SDSs.47
WVTAP toxicologists established lower screening levels thanthe CDC for 4-MCHM (0.120 ppm vs. 1 ppm), PPH (0.850 ppm
vs. 1.2 ppm), and DiPPH (0.250 ppm vs. 1.2 ppm).48 Theselower screening levels were due to differences in risk assessment methodologies and assumptions: exposure pathways(WVTAP considered ingestion, inhalation, and dermal exposure
not just ingestion), a longer exposure period (28 days not 14days), and a more inclusive sensitive population (formula-fed
infant not 10 kg child).20 It is the first-hand experience of author Dr. Whelton that WVTAP did not consider a screening
level for MMCHC because WVTAP was unaware that this chemical was present in the drinking water when their investigation
took place. The 0.010 ppm 4-MCHM screening level establishedby the State of West Virginia was lower than both the CDC 1
ppm and WVTAP 0.120 ppm screening level. The State of West
Virginia accepted the CDC screening levels for PPH and DiPPH.
Exposure to the contaminated water however occurred for
2.5 months, past the 14 day CDC screening levels and 30 day
WVTAP screening levels. GAC filters in the KVWTP were
found to be contaminated with 4-MCHM and were not replaced until 2.5 months after the incident.49 While the CDC
issued screening levels as a short-term urgent evaluation
based on limited information, these levels were not revised
to account for the longer exposure duration that occurred.

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A variety of academic and government organizations are
conducting toxicological research studies and two studies
have been completed as of March 2016. One study foundpure 4-MCHM exhibited toxicity to yeast and human lungcells including DNA damage.50 To date, the authors do notknow of any studies that have been conducted to identify
short- and long-term health impacts of inhalation exposuresexperienced due to this incident. Since the spill, several conference presentations have also been made regarding chemical toxicity. One study reported that a compound similar to
PPH caused “impacted developmental physiology in embryonic zebrafish and negatively affected developing motor, behavioural, and social systems.”51 Another study indicated additive toxicity was detected in vitro when several different celllines were exposed to 4-MCHM and PPH.52 Also reported wasthat crude MCHM exposure induced toxicity for Danio rerio.53
The authors are aware that additional studies are underway
and will be made available by academic institutions in the
coming years. Results from follow-up human health impact
studies on the tank liquid were not found.
While several organizations have acknowledged the inhalation exposure pathway existed,13,45,54,55 no tests have been
conducted to investigate the short- and long-term health effects due to that contaminated water exposure pathway.
Shortly after January 9, the CDC chose not to consider inhalation toxicity in their screening levels “due to the lack of toxicological information on inhalation, lack of an effectivemodel for inhalation, and lack of a method to analyse the actual amount of MCHM in the air”.45 Although months later
the EPA55 established a 4-MCHM inhalation screening level.
The US National Toxicology Program56 initiated testing to examine health effects caused by the ingestion and dermal exposure to contaminated water. However, both organizations
have acknowledged these ongoing studies do not address theinhalation exposure pathway. There is a 20 year precedentthat volatile contaminants can express different toxicity by
the inhalation exposure pathway compared to the ingestionof contaminated water.57 “Inhalation is recognized as being
the easiest and fastest means of exposure because vapours
are readily accessible to the respiratory tract.”58 To date, theauthors are not aware of any studies conducted to identify
the short- or long-term health impacts of inhalation exposures experienced due to this incident. This is surprising because building inhabitants were told to flush their premiseplumbing with hot water and incidents of illness indicativeof inhalation exposures were detected in the population bymultiple local, county, state, and federal agencies.19,59
Source water sampling
Upstream of the water intake. A lack of knowledge remains as to what tank liquid ingredients were present in the
Elk River. Furthermore, the concentration of these chemicals
at the spill site on the day of the spill remains unknown. During the incident response and recovery, RESP sampled waterfrom the raw water intake and took no samples upstream towards or at the spill site. The day after the spill ATTY

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collected one water sample from the Elk River near the spillsite and found 0.47 ppm 4-MCHM. That same day, ATTY
analysed the water for heavy metal concentrations and results
were below state water quality standards. When additional
chemical spills involving crude MCHM and contaminatedstorm water occurred at the spill site January 31, June 12–13,
2014 and July 12, 2015, Elk River testing was only conductedat the raw water intake for 4-MCHM.19,60
Three weeks after the spill was detected contractors working for Freedom Industries, Inc. began chemically analysing
spill site storm water, ground water, and soil samples. The
contractors found significant surface and subsurface chemical
contamination up to 20 feet below ground surface (Table 6).61,62
Subsurface characterizations revealed that contaminatedgroundwater flowing toward the Elk River. EPA35 also tested
spill site water samples and found 4-MCHM, PPH, and variety
of TICs (Table 5). Neither contractors nor the EPA analysed environmental samples for DiPPH despite this compound having
been detected in the contaminated drinking water and having
a CDC established screening level. There was no central datarepository for all environmental monitoring and sampling data
so it was difficult to understand site conditions. Results showthat different government and private organizations characterized environmental media for different chemicals and nojustification for these dissimilar approaches was found.
At the water intake. The day after the spill was discovered,
RESP began analysing 4-MCHM concentrations in Elk River
water at the KVWTP. 4-MCHM concentrations in river water
decreased during the next several days (Fig. 1). On January
10, ATTY also conducted grab sampling near the KVWTP intake and found 0.57 ppm 4-MCHM,34 a concentration much
lower than the 3.3 ppm detected at the KVWTP that sameday. This difference is likely due to the ATTY collecting grab
samples at the surface of the Elk River whereas RESP wateroriginated from lower in the water column where the intake
structure was installed. This difference highlights the importance of consistent water sampling and how methodology
can impact the data reported.
Downstream of the water intake. Several organizations
analysed river water downstream of the KVWTP water intake
for 4-MCHM.33,63–65 The City of Huntington water treatment
plant, owned and operated by WVAW, withdrew and distributed contaminated drinking water to its population with
reported levels of 9 ppb 4-MCHM, while other downstream

Table 6 Maximum 4-MCHM and PPH concentrations detected at thespill site in water and soil, January 2014–October 2014

4-MCHM

PPH

Environmental media<1 mo

1–8 mo<1 mo

1–8 moGround water, ppm
Storm water, ppm
Sump water, ppm
Soils, mg kg−1 (20 ft bgs)

0.014
190
0.180
—

9.5
0.610
440
15 0000.022
950.0095
—

320
18
3.2
9000

Data from consulting firms hired by Freedom Industries;61,62 no
organizations characterized environmental media for DiPPH.

318 | Environ. Sci.: Water Res. Technol., 2017, 3, 312–332

communities shutdown their water intakes and allowed thecontaminated river water to pass. Eight days after the spill,
4-MCHM was detected 390 miles downstream in the Ohio
River near Louisville, Kentucky (Fig. 1). Hydraulic modellingstudies have shown that 4-MCHM concentrations decreased
as contaminated river water flowed downstream.66,67
In the months following the spill, some environmental
fate studies were completed. In downstream rivers the USGS
detected the crude MCHM ingredient MMCHC.33 Benchscale studies indicated that 4-MCHM isomers were susceptible to aerobic and anaerobic degradation.68–70 However,knowledge-gaps remain. From January 13–18 grab samples
were analysed by the Charleston Sanitary Board for
4-MCHM in their wastewater treatment plant influent andeffluent. A total of 13 samples were collected and no
4-MCHM was detected above the 6 ppb 4-MCHM method
detection limit. This was the only wastewater monitoringdata found by the authors during this study. However, otherwastewater facilities and collection systems (i.e., Elk Valley)
received 4-MCHM contaminated wastewater from communities that flushed their premise plumbing (and this WWTP
discharged effluent upstream of the KVWTP intake). The
fate of 4-MCHM and other tank liquid ingredients in thewastewater infrastructure remains poorly understood. Another challenge is that biodegradation studies did not use
the tank liquid (a mixture of stripped PPH and crude
MCHM), but instead examined crude MCHM. It remains unknown if the liquid spilled into the river exhibited the same
degree of biodegradation. No river water or wastewater testing was conducted for PPH, DiPPH, or any other tank liquid
ingredient. Tank liquid dispersion and advection in the water column, chemical partitioning between the water andsediment, and the magnitude of volatilization that took
place remain unreported, and thus unclear. While 4-MCHM
river water monitoring was rapidly conducted by a variety oforganizations, absence of thorough river water characterization has resulted in an incomplete understanding of what
other chemicals were present and their fate. It is also unknown if MMCHC or other tank liquid ingredients were distributed to the City of Huntington population in treateddrinking water due to lack of publicly available data.
Water treatment and distribution system monitoring
Water treatment plant. The day after the spill, RESP beganmonitoring finished drinking water exiting the Charleston
KVWTP for 4-MCHM (Fig. 2), and the highest 4-MCHM concentration detected in the finished water leaving the treatment plant was 3.35 ppm. After Freedom Industries, Inc.
disclosed that stripped PPH was present in the tank liquid,archived water samples were re-analysed and 10 ppb PPH
and 11 ppb DiPPH were detected. No additional testing forthese compounds was conducted and the reasoning for thisdecision was not found.
Drinking water odour. In the days and weeks following thespill, laboratories reported “nondetect” 4-MCHM concentrations in drinking water samples but many residents still

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Fig. 1 Maximum known 4-MCHM concentration (ppm) in river water reported as distance downstream from the spill site starting January 9, 2015as water flowed down the Elk River, into the Kanawha River, and Ohio River.

Fig. 2 4-MCHM concentration at the (a) Kanawha Valley water treatment plant and (b) water distribution system. The dotted lines represent the (i)CDC's 1 ppm health-based 4-MCHM screening level, and (ii) WVTAP's health-based 4-MCHM 0.120 ppm screening level. Reproduced from
Whelton et al.19

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reported a black liquorice odour in their drinking water.19 This
information implied that the drinking water may still be contaminated but the odour threshold concentration of the contaminants present was below the 10 ppb MDL for 4-MCHM.
Shortly after the spill, Louisville Water Company estimated theaqueous odour threshold concentration (OTC) of crude
MCHM to be 1–3 ppb.64 Approximately one month after the
spill, WVTAP conducted a drinking water odour and chemical
oxidation study.71,72 Using the tank liquid, researchers foundthat the aqueous OTC was less than 0.15 ppb, odour recognition concentration was 2.2 ppb, and odour objection concentration was 4.0 ppb. These researchers also suggested that
other chemicals in addition to 4-MCHM contributed to odour,and odour characteristics of drinking water contaminatedwith tank liquid and pure 4-MCHM differed. Pure 4-MCHM
had a different trans-/cis-isomer ratio than trans-/cis-isomers incrude MCHM. Two months after the spill, researchers at Virginia Tech reported that the aqueous OTC of pure 4-MCHM
was 7 ppb.73 Follow-up testing on pure 4-MCHM obtained
from TCI America and crude MCHM obtained from Eastman
Chemical Company revealed air OTCs for each isomer: 0.51
ppb-v (cis-) and 0.12 ppb-v (trans-).74 Additionally, it wasreported that the trans-4-MCHM isomer had a liquorice odour,while the cis-isomer's characteristic odour was not liquorice.74

Impact of unit water treatment operations. KVWTP's main
treatment processes included oxidation with potassium permanganate and free chlorine, powdered activated carbon(PAC) dosing, sedimentation, and multimedia filtration with
GAC filter caps. One month after the spill, 4-MCHM fate in
the water treatment facility was investigated. Neither oxidant
was found to have generated detectable breakdown products68,70,71 or altered the odour of the contaminated drinking
water.71 Because 4-MCHM was detected in the water distribution system but not in the Elk River one month after the spill,
GAC filter media was scrutinized by WVTAP and WVAW. Testing revealed GAC was releasing 4-MCHM into the treateddrinking water. Weeks later powdered activated carbon (PAC)and GAC tests showed these materials were capable of removing 4-MCHM from water.64,70
Water distribution system. Two days after the spill was
detected in Charleston and contaminated water had been
distribution to the population, RESP began quantifying
4-MCHM concentrations in the distribution system. RESP
conducted water sampling at fire hydrants and from selectbuildings after premise plumbing had been flushed (Fig. 2).
More than 2500 water samples were collected by RESP18 andthe highest 4-MCHM concentration found in drinking water
was in the water distribution system (“as reported” 3.773

Table 7 Contaminants specifically targeted during tap water characterization

Water main: 15 min
flush before sampling(days since spilldetected)

Premise plumbing: first-draw sampling (days since spilldetected)Contaminant
Organic contaminants
Acetaldehyde
Formaldehyde
Formic Acid
Methanol
Methylcyclohexane
4-MCHM
PPH
DiPPH
MMCHC
MetalsAl, Sb, As, Ba, Be, B, Cd,
Ca, Cr, Co, Cu, Fe, Pb,
Mg, Mn, Mb, Ni, K, Se,
Ag, Na, St, Tl, Sn, Ti, Zn
Hg, Li, Si, V
General parameters
Odor
Temperature
pH
Turbidity
Chlorine
Total organic carbon
UV254 absorbanceParticulates

ATTY(1–39)a,b

√
√
√
√
√

WVU
(6–20)a,b

√

√

AUTH
(7–12)a,b

ENVC(9–55)a,b

√

√
√
√
√
√

WVTAP
(35–40)a,b

RESP(2–153)cUSGS(13–47)

√
√
√

√

√
√

√
√

√

√

√
√
√

√
√
√
√
√
√
√
√

√
√
√
√
√
√

a

Organization tested both hot and cold water. b Organization tested unflushed plumbing systems; days after spill were calculated using 1/9/
2014 as day 1. Non-residences include undisclosed sampling locations that are not in any of the aforementioned categories. c Locations ofresponder PPH data were not disclosed. PPH testing began 12 days after collection whereas 4-MCHM samples were tested within 24 hours ofcollection. No agents were added to neutralize any chlorine present in the sample.

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Table 8 Number and types of buildings where drinking water was sampled

Water main: 15 min flush
before sampling (days since
spill detected)

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Premise plumbing: first-draw sampling (days since spill detected)
Building type

ATTY (1–39)a,b

ChurchGovernment office
Hotel
Hospital
Residence
Restaurant
Retail business
SchoolNon-residence

1a

WVU (6–20)a,b

AUTH (7–12)a,b

ENVC (9–55)a,b

WVTAP (35–40)a,b

RESP (2–153)c
3

USGS (13–47)
1

1
7
21
1

3

10

1
6

16

11

3
4
274
86

4
b

Organization tested both hot and cold water. Organization tested unflushed plumbing systems; days after spill were calculated using 1/9/
2014 as day 1. Non-residences include undisclosed sampling locations that are not in any of the aforementioned categories. c Locations of responder PPH data were not disclosed. PPH testing began 12 days after collection whereas 4-MCHM samples were tested within 24 hours of collection. No agents were added to neutralize any chlorine present in the sample.

ppm), not exiting the KVWTP. This discovery implies that thetank liquid plume had already passed by the water intake before raw water sampling began and/or water distribution system sampling was not representative of the entire distribution system. No statistical method was applied during
distribution system sampling. As of March 2016, no other water testing data was found.
USGS analysed drinking water collected from their own
Charleston office building after their building was flushed.33
The USGS found 4-MCHM concentrations similar to those observed by RESP. Unlike RESP however, the USGS screened forcontaminants other than 4-MCHM and detected MMCHC,33
but did not quantify its concentration.

Monitoring at premises
Chemicals in Drinking Water – before flushing. RESP did
not conduct sampling to determine the drinking water quality within premise plumbing, only the water distribution system. Beginning the day after the spill organizations not associated with the RESP began conducting premise water
sampling. According to publicly available records,75,76 theseorganizations analysed 121 first-draw water samples for a variety of contaminants (Table 7) from 75 buildings between
January 2014 and February 2014. No organization applied astatistical approach for building selection (Table 8) and the
majority of the premises sampled were residential. No

Fig. 3 4-MCHM concentrations in premise plumbing systems compared to the maximum concentration detected in the water utility
infrastructure, January 9 through March 6, 2014. Non-detectable results not shown; building plumbing system flushing was authorized by WVAW
on January 13 and the last zone was authorized for flushing on January 18; concentrations in USGS offices (January 22 through February 25) werereported as estimates due to matrix interference in analysed water samples; the 14 day and 28 day health based drinking water screening levels for
4-MCHM established by CDC and WVTAP were 1 ppm and 0.120 ppm, respectively.

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hydraulic model for the distribution system was made available
to the groups that conducted premise sampling. In somehomes, 4-MCHM was detected above the CDC screening level
but was non-detectable in others (MDL 10 ppb)19,33,70,77 (Fig. 3).
There remains an incomplete understanding of what
chemicals and concentrations existed in premise plumbing
because: (1) RESP chose to flush premises for 15 minutes before collecting a water sample, (2) water sampling did not begin until contaminated water had been distributed to the
population, (3) water distribution system sampling data imply that the most contaminated water may have passed
through the KVWTP before water distribution system sampling was initiated, (4) while a do not use order was in effect,
the population was permitted to use contaminated water for
toilet flushing activities thereby allowing contaminated water
to pass through premise plumbing without characterization,(5) chemical analyses of premise water was not exhaustive
and thus the presence and concentration of other compounds (i.e., PPH, DiPPH, MMCHC) was not determined. As
a result, while the existing premise water testing data are informative, a poor understanding of the chemical compositionand composition of contaminated premise water remains.
During the incident response, the public became
concerned that chemicals present in their water might sorb
into and out of plastic pipes found in premise plumbing
thereby continually contaminating their drinking water overtime.78 The EPA publicly disputed this claim78 and citedunpublished, restricted access documents.78
Flushing of contaminated water. After 4-MCHM concentrations exiting the KVWTP were near 10 ppb, portions of theservice population were directed to flush their premiseplumbing. To aide in this process WVAW, the State of West
Virginia, KCHD, and the American Federation of Teachers
each issued their own premise plumbing flushingprocedures.79–83 None of the flushing protocols underwent
field validation before use and their similarities and differences have been compared elsewhere.1 A major difference
was that some protocols warned residents to avoid exposure
to contaminated water during flushing, while others did not.
Premise water testing conducted before and after flushingrevealed that premise flushing procedures did not reduce
4-MCHM concentrations in some homes while 4-MCHM concentrations were greater after flushing in others.19,70 A water
heater modelling study completed after the spill indicatedsome of the flushing procedures were not capable of reducing 4-MCHM below the CDC's 1 ppm screening level whenhomes contained large water heaters, low-flow fixtures, andwhen 4-MCHM was present in water used to flush water
heaters.1 An analysis of premise plumbing decontamination
procedures issued in response to past water contamination
incidents in the U.S. revealed similar deficiencies.1
Review of syndromic surveillance and emergency room
medical data indicated that some residents experienced adverse health effects due to contaminated drinking water contact for the weeks following the incident (Fig. 4). A review ofpublic health studies and data19 revealed some of these ill-

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nesses could be attributed to chemical volatilization from thecontaminated water during flushing. Findings from a CDC84
emergency response study conducted four months after the
spill supported these findings. Although, some researchers
have since reported no hospitalizations occurred85 but conclusions by the CDC and the State of West Virginia indicate otherwise.86 Also, not mentioned in the literature is that the West
Virginia Poison Control Center previously admitted some persons receiving calls were untrained,87 so their reported data
may not be reliable. Also, only 36% of the total number ofcalls to the Poison Control Center could be answered due tocall volume challenges.85 The Poison Control Center data,
while informative, may not be representative of the 300 000
population affected. Also confounding available data is thatduring the response to the water contamination incident theState of West Virginia Health Officer publicly stated that thechemical-related hospital admittances could be due to the flu.
During the incident persons who presented to emergency
departments seeking medical care reported being exposed todrinking water by “breathing a mist of vapour.”86 Ninemonths after the incident EPA established a 0.01 ppm-v inhalation 4-MCHM screening level based on the CDC's 1 ppm ingestion based screening level. EPA's methodology has been
explained elsewhere.55 Ambient air testing was conducted by
EPA 10 months after the spill 2014 at the Freedom Industries
spill site during site remediation activities. Air testing revealed
4-MCHM was present in air up to 0.142 ppb-v concentration.88
More than a year after the spill, results from two indoor air
modelling studies were released and predicted that (1) whenresidents flushed their premise plumbing to include showers,
dishwashers, and faucets, the EPA 4-MCHM air screening level
was exceeded89 and (2) 4-MCHM could volatilize into the air
during showering.43 No studies were found that reproduced
volatilization conditions in premises to confirm these predictions. In 2015 the spill site remediation contractor required
respiratory protection for its workers citing that potential airborne 4-MCHM levels could exceed 0.01 ppm-v.90 Despite inhalation exposure evidence and lacking inhalation toxicity
data some state and federal organizations have not made clearthat their toxicological evaluations conducted since the spill
do not apply to the inhalation exposure pathway.91,92
Chemicals in drinking water – after flushing. After premise plumbing flushing, 4-MCHM was sometimes detected in
the premise water. Water distribution system sampling
showed that 4-MCHM was as high as 0.269 ppm eight days after the “do not use” order was lifted (Fig. 3). On February 10,2014 the West Virginia Poison Control Center82 declared
4-MCHM was present at or less than 10 ppb, but premise water sampling data showed concentrations as high as 24 ppb
4-MCHM after flushing (Fig. 3). While this concentration wasless than both CDC (14 day) and WVTAP (28 day) screening
levels, the exposure duration exceeded both screening levels.
Unbeknownst to the Poison Control Center at the time,
KVWTP GAC filters were leaching 4-MCHM into the treateddrinking water93 and plastic pipes may have been desorbing
4-MCHM in premise plumbing.19 Because there was no

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Fig. 4 (a) Visits to emergency departments reported by the U.S. Centers for Disease Control and West Virginia Bureau of Public Health (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 (source: open-access19).

coordinated premise water sampling effort, the highest 4-MCHM
concentration that occurred in buildings remains unknown.
Premise 4-MCHM concentrations decreased in the weeks
following the do not use order (Fig. 1). One month after the
spill, WVTAP conducted the last known in-home water testing effort in 11 residences and detected a maximum concentration of 6.1 ppb 4-MCHM. PPH concentrations in 11 homes
were also measured by WVTAP one month after the spill andwere not detected (0.5 ppb MDL).20 Based on records
reviewed, no other organization characterized premise waterfor PPH during the response. No record was found for any organization that characterized premise water for DiPPH.
Two aldehydes were detected during premise water sampling and their source remains unclear. Formaldehyde waspresent in the spilled liquid and was detected in premisedrinking water four days and one month after the spill.32,94,95
ATTY found formaldehyde in an affected restaurant's toilet
during the water ban at 32 to 33 ppb. This result waspresented by a scientist working for ATTY to a West Virginia
legislative committee and received global press.94–96 The scientist speculated that formaldehyde was a breakdown product of the spilled liquid and residents were being exposed tothis carcinogen.84 The National Toxicology Program previously named formaldehyde as a carcinogen.97 No studies
were found that addressed the claim that 4-MCHM “broke
down in showers or the water system.” WVTAP found formaldehyde and acetaldehyde in premise drinking water one
month after the spill (5.6 to 11 ppb, 2.7 to 2.8 ppb, respectively).32 The literature indicates that both aldehydes could

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have formed as a consequence of water treatment processes98
present at the KVWTP and have been found in drinking waterin other cities up to 20 ppb and 12 ppb, respectively.98–101
Formaldehyde and acetaldehyde were present well below
World Health Organization health standards (50 ppb formaldehyde, 8 ppb acetaldehyde) and standards for drinking water odour (800 ppb formaldehyde; 4 ppb acetaldehyde).102,103
Some TICs were detected in premise water by several organizations (Table 5). Work by WVTAP revealed that some TICs
detected by chemical analysis of laboratory processed premise water samples were the result of interactions between
chlorine disinfectant residual and stabilizers used in thelaboratory's liquid–liquid extraction solvent.20,104 This result
underscored the importance of understanding how TICs areformed and exposed a deficiency in that no standardized water sampling and processing method was applied during theincident response. 3-Chlorocylcohexene, was the only TIC
found with an estimated concentration, 193 to 928 ppb. This
contaminant was reported in drinking water obtained fromflushed residences 18 days after the spill.77
Very few researchers analysed drinking water for metal
contaminants. Many metals were detected in premise drinking water and some exceeded health (Cu, Pb) and aesthetic
based drinking water standards (Al, Fe, Mn) before premise
flushing.19 After flushing, no metals were found to exceed
drinking water standards in the very small number of residences sampled. Blue coloured solids were also collected inhomes during flushing and were analysed by X-ray photoelectron spectroscopy.19 While the State of West Virginia reported

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that the solids exiting the faucet during flushing were sediment,105 chemical analysis revealed some material was notsediment. Blue coloured solids that were collected contained
less than 1% silica, as well as oxygen (58%), aluminium(18%), carbon (17%), zinc (1.4%), phosphorus (1.4%), fluorine (1.0%), chromium (as Cr+6) (0.8%), calcium (0.2%), andcopper (0.1%).
Odour analysis of premise water, combined with analyticalresults for 4-MCHM, enabled the discovery that (1) the tankliquid had a different characteristic odour than pure
4-MCHM, a standard some researchers studied for sensory
analysis, and (2) black liquorice odour was present when
4-MCHM was not detected at or above 10 ppb, the MDL at
the time of the early response. Premise drinking water was
also analysed for other characteristics such as total organiccarbon and ultraviolet absorbance, but these water quality
characteristics were not found to indicate contaminated water.19 This is because drinking water contaminant concentrations were too low and did not have aromatic characteristics
detectable by UV absorbance measurement or organic carbon
concentrations greater than typical drinking water values.

Discussion
This case study underscores the difficulty in responding to asource water contamination incident when limited information regarding the chemicals present, water sampling approaches, techniques, analytical methods, and toxicity arelacking; and when all data, response, and recovery activities
are not centralized. According to discussions with organizations involved in the response and the author's records requests, many of the key incident response and recovery decisions were made informally and no detailed watercontamination response approach existed. Much of the decision rationale and supporting information was not found.
For example, no customer complaint monitoring data has
been disclosed by WVAW and the company declined providing it to the authors citing pending litigation. In the 1993
Cryptosporidium outbreak in Milwaukee customer drinking
water complaints coincided with the detection of contaminated drinking water in the service area.106 In numerous
other water contamination incidents customer complaint
data has been used to estimate when chemical exposures began and to identify when certain parts of the water distribution system received contaminated water.107 Additional datathat would help provide clarity includes any and all chemical
characterization and physical and chemical property datafrom Eastman Chemical Company for the product provided
to Freedom Industries, Inc. Also needed are internal communications by the companies and organizations about thechemicals, spill, decisions, and actions. This type of information could lend greater insight into the reasoning behind theincident response and recovery decisions and help othercommunities prepare for a response in the future. It is hopeful that additional information involved in the ongoing lawsuits is disclosed so that additional understanding of the in-

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cident and its consequences can be obtained. Communities
cannot prepare and respond effectively if they are denied access to critical information needed to protect public health.
It is also evident water supplies and government officials cannot best protect public health if they do not understand what
information is needed for key decisions during an incident
response. This case study has identified several opportunities
for government agencies and water suppliers to improve theirability to respond to and recover from time-critical, acutedrinking water contamination incidents.

Chemical identification and properties
Rapid determination of the chemicals present in the raw water and distribution system was a focus once the spill was
discovered. Unfortunately, little data was available about theconstituents in the tank liquid and no detailed knowledge of
which chemicals (and their properties) were in the water supply. Further, depositions have revealed the crude MCHM's
composition varied and Freedom Industries sometimes altered its composition at their tank farm.
Many of the problems associated with this incident are aconsequence of RESP not fully understanding what chemicals
were present in the contaminated drinking water. RESP108,109
trusted Freedom Industries, Inc. to fully disclose the chemical products that were in the tank liquid which they did not.
No SDS28,30 explained that the tank liquid that spilled into
the Elk River had been previously treated with hydrochloric
acid or dewatered after stripped PPH had been mixed into
crude MCHM.40 RESP did not know where to findphysiochemical property data for many of the suspected tankliquid ingredients, and the RESP and CDC solely focused on
the potential health impacts of 4-MCHM exposure despite avariety of other chemicals being present in the affected waters. As a result of these actions, health officials were unable
to establish acceptable drinking water exposure limits for allof the chemicals present in the contaminated water. It is theauthor's conclusion that RESP and CDC underestimated thehealth risk posed to customers as well as the fate of thechemicals in the utility's water infrastructure and customer's
premise plumbing. For example, the tank liquid chemicals
that were present in the drinking water were not all identified33 before their initial risk assessments were created36 andflushing was recommended, nor was their fate in plumbing
or indoor air understood.19,20,43,70,74,89
Results of this case study show that once a spill occurs,
the spilled liquid should be chemically characterized to ascertain its composition. The findings underscore the need for
responders to also acknowledge toxicity information available
on SDSs may not be accurate. For this reason, it is important
responders obtain samples of the spilled product and rapidly
investigate its composition and toxicity.
In future incidents, government agencies and water utilities should not only rely on the parties who either caused orwere involved in the spill to fully disclose the liquid composition, but initiate their own rapid characterizations. Multiple

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laboratories should analyse the liquid, as this increases theprobability of detecting compounds some laboratories missand ensures quality assurance and quality control methods.
As WVTAP discovered in the response, at least one laboratory
conducting 4-MCHM analysis for the State could not detect
low levels of 4-MCHM in water that they claimed to be able
detect.91 Failure to understand the chemicals present in thewater amplified the consequences of RESP decisions. For example, premise plumbing flushing occurred without fullknowledge of what chemicals customers would be exposed toin their homes or if flushing hot water would result in greater
exposures. Disclosure that the USGS detected MMCHC in thewater distribution system two to four weeks after the spill underscores the need to thoroughly characterize the contaminated drinking water. Officials cannot make scientificallysound judgments if they are unaware of which chemicals arein contaminated drinking water.
Once chemicals have been identified their physiochemical
properties should be obtained so their fate in the affected infrastructure can be assessed. EPA's SPARC and EPISUITE databases can be used in this process. Water solubility, vapour
pressure, log Kow, and Henry's Law Constants can be usefulin making rapid decisions about chemical fate and transport
in water infrastructure systems as well as potential exposure
pathways. For incidents that are expected to take weeks tomonths to recover, experimentally measuring physiochemicalparameters may be useful.

Tentative identified compound (TIC) reporting
The liquid that spilled into the Elk River contained a varietyof organic chemicals without established analytical methods
or drinking water standards. This undoubtedly contributed tothe difficulty of the incident response. While responders rapidly established methods to detect 4-MCHM, the unconventional nature of the spilled liquid warranted a more extensive
chemical characterization including TIC detection andreporting. TIC results from the spilled liquid, ground water,and storm water samples from the Freedom Industries site
provided insight about the chemicals spilled into the watersupply (Table 4). It is unknown if any of these TICs were present in the drinking water because testing was not conducted
and sampling, handling, and analytical approaches differedacross organizations. Also, the majority of laboratories involved in water testing did not report TICs, which is a limitation for an incident of this magnitude. Although, it is wellknown that commercial laboratories sometimes charge morewhen TIC data is requested and can be more comfortable
reporting analytical standard confirmed contaminants.
TIC identification is a standard practice when “there isreasonable probability of contamination with unconventional
pollutants,” and helps to gauge other compounds that mightotherwise be missed in the water.110,111 The value of TIC
reporting was evidenced by the USGS's TIC discovery that
MMCHC was present in drinking and Elk River water samples. Because of MMCHC's tentative identification, USGSThis journal is © The Royal Society of Chemistry 2017

Paper

followed-up and confirmed its presence with an analyticalstandard.33 TIC reporting should be considered in future water contamination incident responses as a screening method.
A challenge that occurred in West Virginia was that analyticalstandards did not readily exist for all TICs. In such scenarios,
science grounded strategies must be developed to make certain the public is best protected from the contaminated watercontaining these possible contaminants.
Rapid bench-scale experiments
A variety of simple bench-scale experiments were conductedin the weeks to months following the spill and should beconsidered for rapid implementation at the onset of future
spill events. These experiments examined the breakdown ofchemicals present in the tank liquid that passed through thewater treatment plant20,70,71 the ability of PAC and GAC to remove 4-MCHM from the water column,42,65,70 sorption anddesorption of 4-MCHM and CHM ingredients into plastic
plumbing pipe,19 and sorption of 4-MCHM into plastic coatings.42 The bench-scale experiments utilized resources at thedisposal of many drinking water testing laboratories: beakers,
oxidants, activated carbon, and plastic pipe samples. Water
characterization was likely the most labour intensive aspectof these experiments. Many of these experiments could be
conducted within hours to a few days after a spill and could
offer much needed data to RESP. However, these experiments
should be undertaken by learned personnel with laboratory
experience to ensure that these bench-scale experiments areaccurately performed to certify valid results.
Infrastructure, water quality, and flushing
Two and a half months after the spill, WVAW had replaced
GAC media in all 16 filters within the KVWTP.49 This was animportant step in removing the continuing source of chemical spill contaminants from the entering water supply. Thisleaching duration exceeded the CDC and WVTAP's estimatedsafe exposure period of 14 and 28 days, respectively. It remains unknown what concentrations of 4-MCHM at premises
can be attributed to GAC filter leaching. No reports were
found that described the chemical sorption/desorption capacity of the GAC present in the KVWTP. The purpose of theplanned testing was to determine how much 4-MCHM andother spilled chemicals had sorbed onto the GAC and estimate the degree GAC filters contributed to 4-MCHM levels at
customer taps during the 2.5 month exposure period. Thus,
the amount of 4-MCHM and possibly other chemicals
leached into the water supply before the filters were replaced
remains poorly understood partly because the recommended
testing was not conducted.
Considerations for premise water sampling and flushing
Premise water sampling applied by numerous non-profit, private, and academic organizations provided an understandingof building tap water chemical and odour quality that was
not obtained from RESP distribution system sampling. No

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statistical methods were used by any organization to determine a representative batch of buildings to sample. A wide
variation in premise water sampling and characterization
methods was observed.
On certain days, higher 4-MCHM concentrations were
found in premises than in the water distribution system. Thisdifference may have been caused by the lag in residents
flushing water from their premise plumbing and/or because
water distribution system sampling data were not representative of 4-MCHM concentrations the entire population encountered. The variety of water characterization techniques (organics, inorganics, and odour) had varying usefulness.

Premise plumbing decontamination and exposure
Premise plumbing flushing protocols released by WVAW, theState of West Virginia, KCHD, and the AFT differed from one
another and were all found to be unclear and/or deficient insome capacity.1 Specifically, the following was not adequately
considered: large water heaters, low-flow fixtures, chemical
sorption and desorption into plastic plumbing components,
water being used to flush premise plumbing contained thecontaminant that was targeted for removal, and the vulnerability of septic tanks to flooding with the recommended large
volumes of flush water. As results show premise plumbing

Environmental Science: Water Research & Technology

was not decontaminated in some homes and the water distribution system also was not decontaminated before premise
flushing was authorized.
Building inhabitant exposure to airborne contaminants
that volatilized from the water during flushing and routine
water use was not considered in the WVAW flushing guidance, the most widely circulated guidance.79 The blackliquorice odour of the contaminated drinking water (at room
temperature) indicated chemicals could volatilize and inhalation was a viable chemical exposure pathway. Spikes in patient admittances at physician offices and hospital emergency
rooms seem to support this exposure pathway. The CDC
dropped plans to consider inhalation as a viable exposure
pathway during their initial 4-MCHM screening level development and cited: “lack of toxicological information and thelack of an effective model to estimate inhalation”.45 Ninemonths later, the EPA established an inhalation screening
level for 4-MCHM. To accurately protect the population it iscritical to understand all exposure pathways including dermal and inhalation rather than assuming ingestion alone
and establish premise flushing procedures that minimize therisk to human health.
A review of past drinking water chemical contamination
incidents revealed that premise flushing procedures issued in
the U.S. have not been based on plumbing system design,

Fig. 5 Stepwise approach for investigating large-scale drinking water chemical contamination incidents.

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operations, or materials. A recent study1 and another underway define several premise plumbing decontamination considerations.112 At present, water heater cleaning scenarios
can be evaluated using a water heater flushing model1 available as an MS Excel spreadsheet. A model for predicting
chemical emission into indoor air during flushing from dishwashers, washing machines, faucets, showers has been developed89 and will be refined. Government agencies and utilities
should consider these easy to use models when determining
how to flush premise plumbing. Additional work should be
conducted to improve these models and better predict chemical levels in indoor air. Organizations should also consider
recommendations for personal protective equipment andpractices building occupants should implement to protect
themselves from exposure.

Key incident response and recovery actions
Key incident response and recovery activities were identified
through this case study (Fig. 5). The stepwise approachpresented can be used to guide drinking water contamination
incident response and recovery decisions. Some of the identified actions could be initiated in parallel (i.e., environmental
media characterization), while others should be conductedsequentially (i.e., obtain physical chemical property data thenestimate exposure risks during water heater flushing).
It is also important to recognize that results of the present
study differ significantly from EPA efforts and their Response
Protocol Toolbox (RPTB).113 The RPTB effort was initiatedshortly after September 11, 2001 in an effort to better understand how to respond to drinking water contamination incidents. First, the RPTB contains a stepwise process for incident investigation, which primarily involves “assessing thethreat, determining if it is credible, and confirming that anincident has occurred”. When chemical spills occur and thewater supply is known to be contaminated, the EPA's RPTB
approach does not seem applicable. Furthermore, cleaningout affected water infrastructure and premise plumbing andprotecting the population during the process is critical forthe community to recover from the incident. The RTPB guidance does not address these actions.
Eight years ago the U.S. water sector outlined several
needed water contamination research activities, some in partnership with the EPA, but very few have been addressed.114
To obtain the necessary data and in light of the fact thatlarge-scale drinking water contamination incidents continue
to occur, the authors propose the U.S. water sector instead
seek alternative research mechanisms and partners. In retrospect, many of the discoveries from the Elk River chemical
spill could have been addressed many years ago.
A variety of activities should be considered to improve thewater and public health sector's ability to investigate and respond to water contamination incidents.
• Develop an approach for rapid analytical characterization of complex liquids (i.e., coal washing liquid, oils, etc.)
and matrices (i.e., river water, drinking water, wastewater).

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• Develop methods to rapidly predict chemical fate in water treatment, water distribution systems, and premiseplumbing.
• Further develop premise plumbing hydraulic and indoor
air exposure assessment models, and develop a better understanding of chemical–material interactions.
• Establish mechanisms whereby persons/organizations
not formally involved in the response can access samples
available to responders and provide data to responders.
• Make data collected by responders centrally and publicly
available during the incident response and recovery.
• Train and conduct disaster response water contamination exercises115 using realistic scenarios including conditions described in this case study.
Using this case study, the water and public health sectors
can improve their ability to rapidly respond to and recoverfrom incidents. The long-term health effects caused by drinking water contamination may continue until pertinent research is conducted. Despite this clear problem, if the waterand public health sectors implement some of the recommendations identified in this study the chances that a population
will be exposed to contaminated water could be diminished or
avoided altogether. Results of this study can help expedite government agency and water utility decision making processes.

Conclusions
The goal of this study was to identify key decisions during
the Elk River chemical spill. This incident was challenging togovernment agencies and WVAW for a number of reasons
within and outside their control. Data from a variety of private, public, and university organizations was collected,
analysed, and included in this case study.
As demonstrated by organizations that responded to thechemical spill, no widely accepted approach to rapidly identify and quantify chemicals present in contaminated drinking
water was applied. As a result, health officials did not fully
understand which chemicals residents were being exposed toin their drinking water for months following the January 9
spill's discovery. Future work is needed to determine adequate methods for rapidly collecting and characterizing
spilled liquids, raw, and treated waters. This will not be trivial and could include a national expert workgroup.
The Elk River chemical spill response and recovery also
underscored the need for rapid and standard tests that canidentify breakdown and transformation products as contaminated water passes through water treatment plants. Also
needed are methods to predict if contaminants are preferentially sequestered as water passes through water treatment
processes (i.e., oxidation, activated carbon) and infrastructure(i.e., pipe/coatings).
The incident revealed that the actions needed to safely decontaminate premise plumbing are poorly understood. A
stepwise decontamination process has been described elsewhere1 but additional work is needed to address knowledgegaps. It is recommended that flushing and otherEnviron. Sci.: Water Res. Technol., 2017, 3, 312–332 | 327

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infrastructure decontamination protocols be thoroughly
tested and air monitoring should be conducted in conjunction with water sampling before the public is told to flush
their premise plumbing. If responders do not fully understand the contaminants present in the contaminated water,
health officials cannot issue guidance to best protect the population from harm. If chemical testing is not thoroughly
conducted during the early stages of the incident, this lack ofdata will affect all downstream public health decisions possibly extending the recovery period, resulting in lost publicconfidence, spread of contamination, and causing the population to experience adverse health impacts.

Acknowledgements
The authors are grateful to the multitude of scientists and engineers that contributed data to this study from the State ofWest Virginia, WVAW, CDC, EPA, WVTAP, Downstream Strategies, Inc., USGS, ALS and Eurofins Laboratories, Thompson
and Barney, PLLC, and Eastman Chemical Company. Thanks
are also extended to Rob Goodwin (West Virginia Clean Water
Hub) and Maya Nye (People Concerned About Chemical
Safety), as well as University of South Alabama and Purdue
University faculty and students for their assistance. Special
thanks are extended to Dr. Randi Brazeau (Metro State Univ.)
for her feedback on the study. Dr. Ronald Gehr (McGill Univ.)is also thanked for assistance understanding the Longueuil
incident. Funding for this work was provided by the U.S. National Science Foundation award CBET # 1424627. Data provided by third-parties was presented as-is. It is assumed that
additional information may exist in ongoing legal proceedings that may or may not ever be made public. This could include chemical formulations, chemical properties, toxicity
and medical data, in-home testing air and water quality results, and medical reports. Dr. Whelton was a member of
WVTAP. The authors do not represent any legal position in litigation related to this spill. In 2015 co-author Andrew
Whelton was deposed as a fact witness by lawyers involved in
the class action lawsuit Crystal Good et al. v. American Water
Works Co. Inc. et al. case number 2:14-CV-01374 in the U.S.
District Court for the Southern District of West Virginia. At
the time this study was completed, the US Chemical Safety
and Hazard Investigation Board and West Virginia Public Service Commission investigations, and US National Toxicology
Program studies were ongoing.

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