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 Impact of Infrastructure Coating Materials on Storm-Water
Quality: Review and Experimental Study
Andrew J. Whelton, Ph.D., M.ASCE 1; Maryam Salehi, Ph.D. 2; Matthew Tabor, S.M.ASCE 3;
Bridget Donaldson 4; and Jesus Estaba 5
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Abstract: A literature review and 30-day leaching regime were conducted to determine the extent storm-water infrastructure coatings affect
water quality. Newly installed polymer-enhanced cement mortar (PECM) and polyurea (PEUU) storm-water pipe coatings were removed
from the field and underwent 10 three-day water immersion periods. For both materials, the greatest water quality alterations occurred during
the first water contact period, followed by significant reductions in water quality alterations. Mineral release from PECM consistently elevated
pH from 7.1 to 10.1–11.8 throughout the entire study. Organic contaminant release [total organic carbon (TOC) and UV254 ] was also detected
for PECM during the first two water contact periods only. Alkalinity increased by 534 mg=L as CaCO3 because of the first contact period and
18–50 mg=L as CaCO3 for each remaining periods. Isocyanate resin from PEUU reacted with water and reduced water pH by 1.0 to 1.2 pH
units during the early contact periods and lesser magnitude for the remaining exposure period. Chemical oxygen demand (COD), TOC, and
UV254 results showed that organic contaminants were released from PEUU. A limited quantity of organic contaminants released by PEUU
was biodegradable. Nitrogen compounds were detected only during the first PEUU water contact period. DOI: 10.1061/(ASCE)EE.1943-
7870.0000662. © 2013 American Society of Civil Engineers.
CE Database subject headings: Coating; Leaching; Pipes; Infrastructure; Epoxy; Cement; Polyurethane; Water quality; Stormwater
management; Experimentation.
Author keywords: Coating; Leaching; Pipe; Culvert; Polyurea; Epoxy; Cement; Polyurethane; CIPP.

Introduction Protection Agency (EPA) Office of Research, and Development

2009; Kanchwala 2010; Oram 2004; Tullis et al. 2010]. Spray–on
Much of the US storm-water infrastructure has or is about to reach coatings are less costly than open–trench asset replacement, can
the end of its useful life and primarily consists of concrete and met- halt material deterioration, sometimes provide structural support,
allic structures [Missouri Department of Transportation (MODOT) and extend infrastructure service life by 25–75 years (Ellison et al.
2008; Transportation Research Board (TRB) 2002]. These materi- 2010). Coatings are generally prepared on site by mixing ingre-
als are highly susceptible to corrosion and many have deteriorated dients followed by spray application. Popular coatings include
past the point of rehabilitation and require replacement. For assets cement mortar (CM), epoxy (EP), polyurethane (PU), polyurea
that have not structurally failed, trenchless pipeline rehabilitation (PEUU), and PU=PEUU blends.
technologies such as spray–on coatings are being applied [Cooney An emerging concern regarding storm-water infrastructure
et al. 2011; Hollingshead and Tullis 2009; Salem and Najafi 2008; rehabilitation is that rinse waters generated during and shortly after
Piehl 2005; Ariaratnam 1998; American Water Works Association material installation can pose downstream water quality and aquatic
(AWWA) 2000, 2007a, b, 2008; Conroy et al. 1995; Environmental toxicity hazards. For example, multiple fish kills, aquatic vertebrate
inhibition, and air contamination incidents have been documented
1
Assistant Professor, Dept. of Civil Engineering, 3120 Shelby Hall, at several different cured-in-place pipe (CIPP) installations in
Univ. of South Alabama, Civil Engineering, Mobile, AL 36688 the United States, Canada, and Europe (Table 1). Cured-in-place-
(corresponding author). E-mail: [email protected] pipe is a popular rehabilitation technology that involves insertion
2
Postdoctoral Research Associate, Dept. of Civil Engineering, 3142
and curing of a polymer-impregnated fabric into an existing pipe
Shelby Hall, Univ. of South Alabama, Civil Engineering, Mobile, AL
36688. E-mail: [email protected]
[Brier 2010; Kampbell 2009; Burkhard 2008; Griffin 2008;
3
Undergraduate Research Assistant, Dept. of Civil Engineering, 3142 National Association of Sewer Service Companies (NASSCO)
Shelby Hall, Univ. of South Alabama, Civil Engineering, Mobile, AL 2008; Hoffstadt 2000; Lee 2008; Snyder 2004]. These field–cured
36688. E-mail: [email protected] CIPP environmental contamination incidents have resulted in
4
Senior Research Scientist, Virginia Center for Transportation Innova- hospital evacuations, emergency response, fish kills, litigation, and
tion and Research, Virginia Dept. of Transportation, 530 Edgemont Road, moratoriums on technology use (Table 1). Commonly, rinse waters
Charlottesville, VA 22903. E-mail: [email protected] are discharged on site in a drainage ditch, stream bed, or to nearby
5
Undergraduate Research Assistant, Dept. of Civil Engineering, 3142 waterways and sanitary sewers. Like CIPP, coating technologies are
Shelby Hall, Univ. of South Alabama, Civil Engineering, Mobile, AL polymer based, cured on site, and are rinsed after installation.
36688. E-mail: [email protected]
However, little to no testing has been carried out to quantify the
Note. This manuscript was submitted on July 2, 2012; approved on
September 27, 2012; published online on September 29, 2012. Discussion environmental impacts of coating rinse waters.
period open until October 1, 2013; separate discussions must be submitted Waste discharge to waterways can cause impairment and harm
for individual papers. This paper is part of the Journal of Environmental aquatic life. Water pH, dissolved oxygen, nutrient, and turbidity
Engineering, Vol. 139, No. 5, May 1, 2013. © ASCE, ISSN 0733-9372/ levels can help describe waterway health. The largest variety of
2013/5-746-756/$25.00. aquatic animals prefer a water pH range of 6.5 to 8.0, whereas

746 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / MAY 2013

J. Environ. Eng. 2013.139:746-756.

 outside this range, most organism physiological systems are also greatly increased alkalinity concentration (>500 mg=L as
stressed and reproduction is reduced. Low pH can also facilitate CaCO3 ), TDS concentration, and metal levels during the first several
heavy metal dissolution and bioavailability. A great quantity of days of water contact. As contact water was replaced, gradual reduc-
organic compounds discharged into a waterway [sometimes moni- tions in alkalinity and TDS alterations were observed. Other inves-
tored as total organic carbon (TOC) or chemical oxygen demand tigators have detected similar CM water quality impacts during
(COD) concentration] can also facilitate oxygen depletion as aero- laboratory CM potable water pipe leaching studies, within newly
bic and facultative microorganisms utilize oxygen to break down CM coated potable water pipelines, and for new concrete used for
organic matter for energy. The amount of oxygen consumed by structural marine purposes (Fitch 2003; Gove et al. 2002; Berend
these organisms is known as the biochemical oxygen demand and Trouwborst 1999; Guo et al. 1998; Germaneau et al. 1993;
(BOD). Excess nutrients (e.g., nitrogen/phosphorous) could also Kanare and West 1993; Colucci et al. 1993; Yuskus 1984; Douglas
promote nuisance levels of algae and other aquatic vegetation and Merrill 1991, 1993; Douglas et al. 1996; Guo 1997). Water pH
(e.g., macrophytes), and indirect dissolved oxygen (DO) consump- and alkalinity levels are affected because major CM components
tion through nitrification. such as silicates (Ca3 SiO5 , Ca2 SiO4 ) and aluminates (Ca3 Al2 O6 )
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In the present study, a literature review and polymer-enhanced are released. Once dissolved in water, CaðOHÞ2 forms, which
cement mortar (PECM) and PEUU coating leaching experiment were dissociates into Caþ2 and OH− ions (Deb et al. 2010). Heavy
conducted to identify the water quality impacts of storm-water pipe and transition metals also have been found to leach from CM pipe
coating materials. Because of unpublished environmental and safety rehabilitation coatings into waters (Table 2) for up to two years
concerns, the California Transportation Agency (CALTRANS) (Berend and Trouwborst 1999). Metal sources include minerals
effectively banned the use of coatings that contain isocyanate (i.e., silicates, aluminates) and residue remaining in kilns used to
materials, including PEUU (G. DeCou, personal communication, create cement (Guo et al. 1998). Because of ion dissolution, total
January 13, 2012). While transportation agencies have begun to dissolved solids and water hardness concentrations typically increase
assess and respond to water quality impacts resulting from CIPP because of CM contact.
installations (McLuckie 2011; J. Sicluna, personal communication,
November 1, 2010; Donaldson 2009; Donaldson and Baker 2008),
no studies were found that documented water quality impacts caused Epoxy
by PECM or PEUU materials. The goal of the present work was to Although water quality impacts from epoxy coatings were not
quantify water quality alterations caused by newly installed PECM experimentally evaluated in this study, a literature review of those
and PEUU storm-water pipe coatings. Specific objectives included materials was conducted to better understand contaminant release
the characterization of inorganic and organic contaminants imparted from coatings. Water quality impacts of epoxy coatings have been
to water over a 30-day exposure period and identification of actions documented by many investigators, and in the field, contaminants
to minimize environmental impacts. have been found to be released after epoxy-lined drinking water
piping had been in service for five months (Crathorne and Warren
1986), six months (Crathorne et al. 1990), and two years (Jackson
Literature Review et al. 2007). Specific contaminants detected in contact waters in-
Most related literature applies to CM (not PECM) and epoxy cluded organic compounds, such as carcinogenic and emerging
coatings, few studies were found for PU coatings, and no reports were contaminants. Sources were identified as resin, hardener, additives,
found for either PEUU or PU=PEUU blend coatings (Table 1). Of ingredient degradation products, and solvents used for coating
these records, almost all pertain to chemical leaching phenomena application. Certain solvents were assumed to have evaporated
for approved potable water infrastructure coatings; none pertain to during coating cure but were still detected in contact waters. Like
storm-water infrastructure. Moreover, most reports describe testing CM coatings, the greatest contaminant release occurred shortly
for which a series of water stagnation contact periods were conducted, after epoxy installation, and impacts decreased over time. Water
not dynamic/flowing water experiments. Although potable water quality monitoring of EP coatings in the field and studied in labo-
literature is informative, many of those coatings analyzed were pre- ratories showed elevated aqueous TOC and COD concentrations
viously approved by the National Sanitation Foundation International (A. Bruchet, personal communication, October 2010; Heim and
(NSFI) Standard 61 (ANSI/NSFI 2007). In the United States, NSFI Dietrich 2007; Jackson et al. 2007; Modayil et al. 2002; Bae et al.
Standard 61 certified products have undergone short-term premarket 2002; Romero et al. 2002; Rigal and Danjou 1999; Crathorne et al.
testing, leading to a determination that they do not cause drinking 1990; Alben et al. 1989; Crathorne and Warren 1986; Satchwill
water to exceed U.S. Environmental Protection Agency maximum 2002). Notably, Bae et al. (2002) found that organic chemical re-
contaminant levels and certain NSFI Standard 61 limits for several lease from three brands of drinking-water-approved epoxy were not
unregulated contaminants. No certification exists for storm-water similar. In another study, toluene was detected in contact water and
coatings. Thus, it is possible that greater quantities of contaminants originated from equipment cleaning before use, not the coating it-
are released from coatings installed for storm-water infrastructure than self (Modayil et al. 2002). Extended curing time has been found to
similar materials installed in potable infrastructure. A summary of reduce contaminant release (Alben et al. 1989), whereas greater
contaminants detected in coating contact waters is provided in Table 2, water temperature facilitated contaminant release (Bae et al. 2002).
and coating synthesis reactions are shown in Fig. 1.
Polyurethane and Polyurea
Cement Mortar
Only two reports were found that quantified the impact of a PU
Cement mortar coatings for potable water contact and bridge repair infrastructure coating on water quality. Both of those studies were
have been found to increase water pH; alkalinity; total dissolved sol- conducted in batch, and no reports were found that examined
ids (TDS); hardness; and concentrations of alkali, transition metals, PEUU coatings. In one study, PU produced a consistent 0.2 to
and heavy metals. For example, one drinking-water-approved CM 0.7 water pH reduction during the 30-day exposure period at room
coating significantly increased water pH over an entire 30–day test temperature (Deb et al. 2010). Total organic carbon concentration
period from 6.5–8.0 to 10.2–12.5 (Deb et al. 2010). This CM coating increased by 0.0010 to 0.0022 mg=cm2 · day for 1-day exposure

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J. Environ. Eng. 2013.139:746-756.

 Table 1. CIPP Related Air, Water, and Soil Contamination Incidents and Reports in the United States, Europe, and Canada
Incident date, Styrene Information lacking that inhibits strategic
location Media level Description of incident or report specification development and inspection
Californi (G. DeCou, — — Following new CIPP specifications by A CALTRANS investigation is underway
personal communication, VDOT, CALTRANS developed similar to determine risks
January 13, 2012; specifications. The California Regional
W. Alwan, personal Water Quality Control Board has since
communication, 2012) placed a moratorium on CIPP
Hamilton, Ottawa, Air and Not Odors detected kilometers from worksite Information was provided in platform
Toronto, Canada water reported and within nearby private residences. presentation file; details of release
(Bauer 2012) Actions implemented: 0.04 ppm sewer conditions, curing water or discharge
discharge limit; GAC curing water water characteristics, and material
treatment; ambient temperature and properties not described; short-term
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testing required before discharge; exhaust release only considered

fans used; nearby building occupants
notified
New York Air Not Odors permeated into nearby residences; Only perspective of reporter; no
(Doran 2012) reported residents complained and evacuated their quantitative data
homes
Ontario, Canada Water Not Treatment processes at two wastewater Details of wastewater treatment facility
(Sullo 2012) reported facilities impacted during low flow impacts not reported; 0.058 ppm and
periods; odors reported near worksites; 35 ppm styrene concentration reported,
subsequent installations involved capture but location not described; short-term
and treatment of excess resin, condensate, release only considered
and process water; 0.072 ppm allowable
discharge concentration to waterways
Massachusetts Air 60 to 70 ppm Fumes caused daycare center evacuation; Styrene level in water not reported; CIPP
(Dayal 2011) headaches reported; emergency characteristics and procedures not
responders called to site examined; short–term release only
considered
Ottawa, Canada — — Ministry of Trans. CIPP moratorium Data not published
(Ontario Ministry of because of a fish kill; investigation
Transportation, personal ongoing and under litigation
communication,
Feb. 5, 2011)
Minnesota Soil and Not 5,678 L (1,500 G) of resin spilled and Detailed test results were not provided,
(Marohn 2011a, b, c) air reported residual left for five months; state- only an event summary
mandated soil testing and cleanup; odor
caused building evacuations;
12.2 m ð40 ftÞ × 30.5 m ð100 ftÞ ×
0.32 m ð1.25 ftÞ contaminated area of soil
Michigan Air Not Hazardous materials response team Only perspective of reporter, interviews
(Banovic 2011) reported (HAZMAT) responded; odors from with emergency responders; no
nearby operation entered school quantitative information provided
ventilation system; building evacuated;
children transported to hospital for
chemical exposure symptoms
Massachusetts Air Not Firefighters ordered evacuation of Only perspective of reporter, interviews
(Tempesta 2011) reported elementary school because of strong odor; with emergency responders; no
dizzy and light-headed symptoms quantitative information provided
reported
Pennsylvania Air Not Elementary and high school students Only perspective of reporter, interviews
(Hayes and tested were evacuated for fear of gas leak; odors with sanitation authority; no quantitative
Biedka 2011) from nearby CIPP operation were the cause information provided
Montana Air Not Fire department evacuated nearby affected Only perspective of reporter, and
(Banks 2010) reported building because of complaints of strong interviews with emergency responders; no
odors, nausea, and headaches quantitative information provided
Washington Water Not Citizens discovered creek had odor, saw Detailed test results were not provided,
[Washington State reported an oil sheen, resin, white milky water, and only an event summary
Department of Ecology dead crayfish. Water flowed through
(WSDOE) 2010] relined pipe during relining the night
before; odor remained for at least 14 days
following event; state fined contractor
Virginia Air Not Nearby installation caused odor; fire Only perspective of reporter and nearby
(ARLnow.com 2010) reported department responded residents; no quantitative information
provided
Virginia Water Up to 77 ppm Seven storm-water sites monitored after Properties of cured CIPP not examined;
(Donaldson 2009) installation over 1 year; contaminants short-term release only considered
detected above fish toxicity levels

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 Table 1. (Continued.)
Incident date, Styrene Information lacking that inhibits strategic
location Media level Description of incident or report specification development and inspection
Nevada Water 60 to 70 ppm Process water treated by GAC; GAC Replicates not provided; properties of
(Loendorf and effluent <2 ppm then discharged into a cured CIPP not examined; short-term
Waters 2009) sanitary sewer release only considered
Florida Water 100 ppm Fish kill because of uncured resin released Data not published
(Donaldson 2009) into a storm-water drain
Pennsylvania Air Not Firefighters evacuated nearby apartment Only perspective of reporter and
(WPXI-TV 2009) reported buildings; initially suspected cyanide gas, interviews with emergency responders; no
but styrene was ultimately detected quantitative information provided
New York Water 41,110, Four CIPP installations tested for styrene Data not published
(M. O’Reilly, New York 120, 130 ppm in curing release water; stricter
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State Department of specifications now required for use at New

Transportation, personal York State DOT
communication,
October 28, 2010)
Massachusetts Air Not Contractor released styrene vapors and Air and aqueous levels not monitored;
(Moore 2008) tested discharged to sanitary sewer; utility details of installation not described
cease–desist order issued
Virginia (Lee 2008) Water Up to 51 ppm Water sampling of process water during Concentration data not reported;
fabric insertion and curing; curing helped properties of cured CIPP not examined
reduce styrene aqueous levels
Bielefeld, Water Up to 100 ppm Water sampling during and after curing Raw data not available; discharged styrene
Holland (Lee 2008) and flushing; curing helped reduce styrene level unknown; concentration variability
aqueous levels not reported; cured CIPP not examined
California Water Not Suspected wastewater treatment facility No water sampling conducted; properties
(Henry 2008) tested sludge settling and UV disinfection of cured CIPP not examined; short-term
harmed by process water that was release only considered
discharged into the sanitary sewer
Unknown location Water 100 ppm An estimated 11.3 L (3 G) to 15.1 L (4 G) Details of release and follow-up were not
(Lockheed Martin 2007) of uncured resin released during a CIPP provided
installation into a storm-water drain;
Residual uncured resins were carried to a
creek, resulting in the death of more than
5,500 fish of various species. Water
sampling at a manhole downstream of the
spill showed styrene present
Somerset, Air Not Foul styrene odor permeated into Only perspective of reporter and building
UK (Wills 2007) tested residence through drain because of nearby residents; no air sampling conducted
installation
New York Air Not Foul styrene odor permeated into Only perspective of reporter and building
(Lysiak 2007) tested buildings through drain because of nearby residents; no air sampling conducted
installations
British Columbia, Water 2 to 85 ppm Fish kill because of process water Only perspective of reporter who
Canada (Gerrits 2007) discharged into nearby tributary investigated the fish kill; little quantitative
information provided
Ottawa, Canada Air Two sites: Venting determined to be necessary to Styrene level in water not reported; CIPP
(Bauer and 20, 115 ppm prevent air backup into nearby residences/ not examined; short-term release only
McCartney 2004) buildings considered
Virginia Air 500 ppm HAZMAT team responded because of Only perspective of reporter and building
(Gowen 2004) styrene vapor backup into nearby residents; little quantitative information
buildings; illness symptoms reported provided
Connecticut Water and 0.596 ppm Estimated 18.1 kg (40 lbs) to 73.0 kg Actual data not provided in letter to state;
[Groundwater and soil (161 lbs) of process water and resin delay between incident and sampling
Environmental Services, released to storm-water pipe and retention inhibits complete understanding of the
Inc. (GESI) 2004] pond; water able to be captured was release; soil sampling recommended by
discharged to sanitary sewer; after consultant but data not reported
12 days, 0.0291 ppm concentration
detected; remediation required by state
Florida (Saewitz 2001) Air Not tested Styrene odor detected; hospital evacuated; Only perspective of reporter and building
HAZMAT team responded residents; little quantitative information
provided

and by 0.0001 to 0.0009 mg=cm2 · day at day 15, when TOC potable water pipe to eliminate tetrachloroethylene (PCE) release
sampling was halted. A chlorinated isocyanate compound was also from the original vinyl lining (Gove et al. 2003). Although PCE
detected, but its concentration was not quantified. The second PU leaching was reduced by the PU coating application, other water
study pertained to the application of a PU coating onto a vinyl-lined quality characteristics were not reported. On the basis of a review

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 Table 2. Literature Summary of Contaminants Detected in Coating Contact Waters Not Including Results of the Present Work
Material
(number of studies) Contaminants detected in contact water and their sourcea Summary
CM (14) Water pH and alkalinity: hydroxide ions from cement pH, alkalinity, TDS, hardness, and various metals imparted
Metals (aluminum, arsenic, barium, beryllium, cadmium, to water
calcium, chromium, iron, lead, manganese, nickel, potassium,
selenium, silica, thallium, zinc): minerals and residue from
kilns used for cement production
Total dissolved solids/hardness: ions from cement
EP (14) Resins and hardeners: BADGE, BFDGE, bisphenol A, THMD, TOC and COD affected by organic compound release; specific
PTSA VOC and EDC contaminants also released
Solvents: MEK, MIBK, toluene, benzene, styrene, xylenes
Antioxidants, stabilizers, and degradates: benzaldehyde, benzyl
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alcohol, phthalate, nonylphenol, 4–tert–butylphenol

PU (1) Water pH: resin reacts with water to form CO2 The single lab study examined only one PU coating; water
2,4–DTBP: antioxidant degradate pH and TOC were affected
Chlorophenol isocyanate: resin modifier
PEUU (0) No lab or field data available
PU/PEUU blend (0) No lab or field data available
a
Bisphenol A diglycydyl ether (BADGE); Bisphenol F diglycidyl ether (BFDGE); trimethylhexamethylenediamine (THMD); p–toluene sulphonic acid
(PTSA), Methyl iso butyl ketone (MIBK); Methyl ethyl ketone (MEK); 2,4–Di–tert–butylphenol (DTBP); Total dissolved solids (TDS); Volatile
organic compound (VOC); Endocrine disrupting compounds (EDC).

Fig. 1. Synthesis reaction schemes for: (a) epoxy; (b) polyurethane; (c) polyurea coatings

of PU formulation literature (Wicks et al. 2007), organic com- and phytoplankton growth for three months and resulted in elevated
pounds detected in PU contact water could include resin, hardener DO levels. The specific reasons for increased microbiological growth
(i.e., polyols), binders, and ingredient degradation products. No were not explained. Hardened PEUU polymer was also found on top
water contact data were found for PEUU coatings. Like PU, PEUU of the sediment and was suspected to be caused by the reaction of
is also synthesized with isocyanate resin, but the formulation isocyanate resin and water (Fig. 2). Because of this hardened PEUU
includes polyamine hardener instead of a polyol. Similar water layer, the investigators suspected that certain macrobenthic organism
quality impact phenomena are expected for PEUU. populations were reduced because of “physical obstruction by the
Although not described by published leaching studies, a water pH PEUU layer, lack of oxygen, and elevated carbon dioxide concen-
reduction can be attributed to reaction between isocyanate resin and trations” (Heimbach et al. 1996).
water (Fig. 2) (Yakabe et al. 1999; Heimbach et al. 1996; Gilbert
1988; Brochhagen and Grieveson 1984; Saunders and Frisch 1962;
Shkapenko et al. 1960). Isocyanate resins quickly hydrolyze and Experimental
form carbamic acid intermediates, which quickly decompose to
diamines and evolve CO2 (Sterner 2010; Hegarty et al. 1975).
Specimens
For example, the half–life of phenyl isocyanate resin in water was
approximately 20 seconds (Castro et al. 1985). Heimbach et al. Polymer enhanced cement mortar and PEUU coating samples were
(1996) found that isocyanate resin dosing to artificial ponds caused removed 24 h after their installation on metallic storm-water pipes
significant water pH reductions (pH 9 to 6.5) as well as macrophyte in Virginia in the spring of 2012. Because PEUU is known to fully

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J. Environ. Eng. 2013.139:746-756.

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Fig. 2. Reaction schemes for: (a) 4,4′–diphenylmethane diisocyanate and water to form a carbamic acid functionalization; (b) carbamic acid
functional group decomposition to form a diamine; (c) diamine reaction with 4,4′–diphenylmethane diisocyanate to form polyurea. The pKa value
was reported by Christensson et al. (1978)

cure within minutes of application, and the PECM manufacturer carbon calibration standards (0, 2, 4, and 5 μg=L) resulted in cal-
stated 24 h were required for product curing, specimens exhumed ibration curve correlation coefficients of 0.997–0.999. Chemical
were presumed to be fully cured. These cured materials were not oxygen demand was quantified according to the U.S. EPA reactor
rinsed before or after removal. The nominal specimen surface area digestion method using 2 mL aliquots (APHA et al. 2000). A 5-day
was 145.6 cm2 (PECM) and 920.2 cm2 (PEUU). Specimens were biochemical oxygen demand (BOD5 ) was conducted according
stored in sealed plastic bags with a damp cloth at 4°C until tested. to SM 5210B for water from the first 3-day exposure period.
Samples were damp at the time of testing. Biochemical oxygen demand dilution water was seeded with
24 h stabilized primary influent from a local activated sludge
Immersion Testing wastewater treatment facility. Biochemical oxygen demand sam-
ples were created using approximately 20 mL (PEUU) and 160 mL
Because there is no standardized water quality impact test for storm- (PECM) of sample water. Total nitrogen and BOD5 measurements
water infrastructure rehabilitation materials, and a dynamic approach were conducted to gain insight into possible oxygen consumption
would introduce many variables (e.g., flow rate, turbulence, surface downstream from rehabilitated pipe attributable to aerobic and
area), a static closed-system testing procedure was applied. Ten days nitrification processes.
after specimen removal from the field, samples were immersed in
precleaned glass jars, covered with a glass plate (headspace free) that
contained synthetic water (pH 7.1) with an alkalinity concentration of Statistical Analyses
47 mg=L as CaCO3 . Immersion testing involved 10 consecutive Mean and standard deviation values were calculated for each water
3-day static exposure periods (22°C). Contact water was prepared quality characteristic. Results were statistically analyzed using two
using Type I Millipore water, sodium bicarbonate, and hydrochloric approaches. A two way analysis of variance was applied to deter-
acid. After each 3-day contact period, water was removed and mine if there was a significant variance between contact waters of
characterized. Triplicate samples were taken and analyzed for each PECM, PEUU, and the control. The Tukey–Kramer multiple
water sampling period. After each 3-day period, newly prepared syn- comparison test was carried out using results of each source.
thetic water replaced the water in each container. A surface area to The Type I error applied for all statistics was 0.10 for rejection
water volume ratio (SA=V) of 1.0 cm2 =mL was desired, but the CM of the null hypothesis. The alternative hypothesis tested for each
sample provided was not in great enough quantity. The SA=V for sampling period was that contact water quality for each material
each test was 0.16 cm2 =mL (PECM), 1.04 cm2 =mL (PEUU), and differed from the control solution after the 3-day exposure.
0 cm2 =mL (control vessel).

Water Quality Characterization Results and Discussion

Analyses were carried out according to approved standard methods

Materials
(SM) [American Public Health Association (APHA) et al. 2000].
Water pH was analyzed using a research-grade accumet AB15 pH According to the PECM material safety data sheet (MSDS), the
meter (Fisher Scientific; Pittsburgh, Pennsylvania) according to material contained highly alkali cement components (pH 12–14),
SM 4500 − Hþ . Alkalinity concentration was measured by end point fly ash, aggregate, and ad components were present. Although the
titration (pH 4.5) using 0.025 N sulfuric acid according to SM 2320B. MSDS indicated that the coating was crosslinked after curing, the
Turbidity was quantified using a DR 2000 direct reading HACH specific “polymer” was not specified. The literature review showed
spectrophotometer (Loveland, Colorado) (Standard Method 2130). that the incorporation of a polymer into a CM coating was not
A HACH DR 5000™ UV–VIS spectrophotometer was used common. The PEUU material safety data sheet indicated that
to characterize ultraviolet (UV) absorption at 254 nm and total PEUU was created using a mixture of 4,4′–diphenylmethane
nitrogen (TN) concentration (after sample digestion). Total nitrogen diisocyanate (MDI) and a modified isocyanate. The formulation
was quantified in 2 mL samples after persulfate digestion at also contained multiple amine-based hardener compounds
105°C. Nitrogen standards [Ammonia–p–Toluenesulfonate (PTSA), (polyoxpropylenediamine, diethyltoluenediamine, and unspecified
Glycine–PTSA, and Nicotinic–PTSA] demonstrated 98–99% polyamines). The literature review revealed that PEUU coatings are
recovery. Standard method 5310A was followed to determine typically created using 50–60% isocyanate resin and 10–40% poly-
aqueous total organic carbon TOC concentration. Total organic amine hardener by weight.

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J. Environ. Eng. 2013.139:746-756.

 Inorganic and Turbidity Contaminants measurements. The PEUU, however, released organic contami-
nants during the entire 30-day exposure period. The PEUU coating
Experimental results showed that newly installed PECM and
significantly altered UV254 absorbance, as well as COD, TOC, TN,
PEUU coatings altered water quality in different ways. As expected,
PECM coatings consistently increased pH during the 30-day study and BOD5 concentration: COD concentration (98.3
7.6 mg=L),
from approximately 7.1 to 10.1–11.8. The greatest pH increase oc- TOC concentration (19.9
0.3 mg=L), and UV254 absorbance
curred during the first exposure period, after which the magnitude of (0.087
0.003) were greatest during the first exposure period
pH change decreased gradually (Fig. 3). Polymer-enhanced cement (Fig. 4). Subsequent water contact periods resulted in gradual re-
mortar also significantly elevated alkalinity (534.2
91.6 mg=L as ductions of COD and TOC concentrations as well as UV254 absorb-
CaCO3 ) for the first 3-day exposure period. Elevations were typically ance. Day 21, 24, and 30 samples of PEUU contact water produced
18–50 mg=L for each remaining contact period. Alkalinity was COD levels that were not statistically different than those of
equivalent to that of the control solution by day 30. the control water. Day 27 results were again statistically different;
The PEUU coating significantly reduced water pH during however, TOC and UV254 absorbance results imply organic
compounds were imparted to water during the entire experiment.
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eight of the 10 contact periods, and alkalinity was not affected.

The greatest water pH reductions occurred during the first two This difference between TOC and COD results can be attributed
periods, during which pH decreased from 7.1 to 5.9 and 7.5 to to inherent variability of the COD quantification method applied
6.5, respectively. For the other periods, pH reductions were 0.02 and the limit of detection for the TOC method. As expected,
to 0.37 pH units. Water pH reductions may have resulted as un- correlations were observed among COD and TOC concentrations
reacted isocyanate resin reacted with water to form CO2 . Because and UV254 absorbance (Fig. 5). Correlation coefficients were 0.947
the primary source of alkalinity was the carbonate system, total (TOC versus COD), 0.703 (COD versus UV254 ), and 0.783 (TOC
carbonate added to the system was also calculated from pH and versus UV254 ). Both UV254 absorbance correlations, however, were
alkalinity results. As expected, total carbonate of the contact strongly influenced by day 3 results. More work is needed to de-
water was relative to water pH reductions. Turbidity levels were termine the applicability of UV254 absorbance as a surrogate for
only statistically different for the first exposure period: CM evaluating organic contaminant release from PEUU.
(3.0
0.0 NTU), PEUU (2.0
0.0 NTU), control waters
(0.7
0.6 NTU). Although statistically different from one another,
Biological Related Contaminants
turbidity differences in water quality are likely insignificant.
The BOD5 concentration of PECM contact water was statistically
indistinguishable from the control water. The BOD5 concentration
Organic Contaminant Release of PEUU contact water, however, was significantly greater than the
A limited quantity of organic contaminant leached from PECM control (9.2
0.5 mg=L). Although a significant quantity of con-
during the first two periods as detected by TOC and UV absorbance taminant was apparently released by the PEUU coating, most was

Fig. 4. Influence of polymer-enhanced cement mortar and polyurea

Fig. 3. Impact of polymer-enhanced cement mortar (PECM) and poly- coatings on: (a) chemical oxygen demand; (b) total organic carbon
urea (PEUU) coatings on: (a) alkalinity concentration; (b) water pH concentration

752 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / MAY 2013

J. Environ. Eng. 2013.139:746-756.

 150 not readily biodegradable, as indicated by the calculated COD=
COD = 4.7915*TOC BOD5 and COD=TOC ratios (COD=BOD5 ¼ 10.5; COD=TOC ¼
COD, mg/L 100 R² = 0.93
4.9). The COD=BOD5 and COD=TOC ratios for municipal waste-
water are typically between 1.5 to 4.0 and 2.0 to 3.5, respectively
50 (Henze 2008). Interestingly, Bae et al. (2002) also detected an
elevated COD level, and microbial growth in their epoxy coated
0 water tanks was greater than that in their control tank.
0 5 10 15 20 25 The PEUU coating elevated total nitrogen concentration
(a) TOC, mg/L (2.8
0.3 mg=L) for the first exposure period only. PEUU’s resin
MDI hydrolyzes in water to form compounds such as primary amines
120
COD = 924.24*UV254 and ureas (Yakabe et al. 1999). Because the polyamine hardeners also
100 contained nitrogen, the nitrogen source cannot be identified from the
R² = 0.70
COD, mg/L

80 present data. From an environmental fate standpoint however, ureas

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60 react with water to form ammonia and bicarbonate ions. Nitrifying

40 organisms utilize ammonia for respiration and consume DO; it is
20 possible that resin hydrolysis will result in low DO events that
0 negatively affect aquatic life. In contrast, polyamines are relatively
0.00 0.05 0.10 stable and not readily biodegradable in water.
(b) UV254 Absorbance

25 Contaminant Flux
20 TOC = 195.28*UV254
TOC, mg/L

R² = 0.75 Results from the present study were converted into contaminant
15
flux (mass/surface area time) values for each exposure period
10 (Table 3). These results were then applied to predict contaminant
5 concentration if 30.5 cm (12 in.) to 91.4 cm (36 in.) interior
0 diameter pipes were coated, filled with water, and exposed for
0.00 0.02 0.04 0.06 0.08 0.10 three days (Table 4). Once pipes are installed in the field,
(c) UV254 Absorbance new pipes are not typically filled with static water before
commissioning. While Table 4 results likely overestimate field
Fig. 5. Relationship between: (a) total organic carbon and chemical
contaminant levels, calculated results show that contaminant
oxygen demand; (b) chemical oxygen demand and UV254 absorbance;
concentration increased as pipe diameter decreased as a result
(c) total organic carbon and UV254 absorbance characteristics of
of the surface area-to-water volume ratio. Therefore, the greatest
polyurea coating contact waters
water-quality impacts would likely be found for small-diameter

Table 3. Contaminant Flux from Polymer-Enhanced Cement Mortar and Polyurea Coatings, 10−3 mg=cm2 · day
Exposure duration, daysa
Water quality characteristic 3 6 9 12 15 18 21 24 27 30
PECM coating
Alkalinity 983 96.0 70.7 109 85.0 79.1 55.6 55.6 37.0 —
Chemical oxygen demand — — — — — — — — — —
Total organic carbon 8.6 6.4 — — — — — — — —
Total nitrogen — — — — — — — — — —
PEUU coating
Alkalinity — — — — — — — — — —
Chemical oxygen demand 94.6 33.7 20.5 17.0 16.7 18.6 — — 18.9 —
Total organic carbon 6.4 2.0 1.2 1.3 1.3 1.4 1.1 0.9 0.9 1.0
Total nitrogen 2.7 — — — — — — — — —
a
Results were calculated using mean values; dashes indicate that the water quality value was not statistically different from control water.

Table 4. Estimated Aqueous Contaminant Levels for Contact with Newly Installed Polymer-Enhanced Cement Mortar and Polyurea Coated Pipes for a Single
Static 3-Day Exposure Period
Material and contaminant concentration, mg=La
Polymer-enhanced cement mortar Polyurea
Pipe interior diameter Total organic carbon Alkalinity Chemical oxygen demand Total organic carbon Total nitrogen
91.4 cm (36 in.) 621 70,994 6,832 462 195
61.0 cm (24 in.) 860 98,300 9,460 640 270
30.5 cm (12 in.) 1,577 180,217 17,343 1,173 495
a
Results were calculated by applying experimentally measured data to surface area and water volume calculations for each pipe.

JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / MAY 2013 / 753

J. Environ. Eng. 2013.139:746-756.

 pipes coated with one of these materials. A dynamic testing pro- allow infrastructure managers to select low leaching materials and
tocol that examines coating material water-quality impacts would design specifications that limit environmental impacts of rehabili-
better estimate contaminant concentrations that occur in the field. tation operations. For rinse waters suspected to contain elevated
Such a protocol could also address standing water scenarios, levels of contaminants, water collection, testing, and proper dis-
contaminant dilution away from the pipe wall, and the kinetics posal is recommended. If water quality testing is considered,
of contaminant leaching. Also important is that only one formu- knowledge of material ingredients is necessary to effectively select
lation/installation condition for each material was tested in the the water quality characteristics to monitor. Results demonstrated
present study. As Bae et al. (2002) discovered for epoxy drinking that pH, alkalinity, TOC, COD, UV254 , BOD5 , and TN analyses
water pipe coatings, great differences between contaminant leach- were all effective in quantifying contaminant release, but not all
ing can result from different curing conditions and brands. characteristics were applicable for both materials.

Conclusions Acknowledgments
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Despite incidents of fish kills and environmental contamination Sincere thanks are extended to the manuscript’s anonymous peer
caused by CIPP installations, no laboratory or field investigations reviewers for their insightful and greatly appreciative recommenda-
have documented water quality impacts caused by PECM, EP, PU, tions. Appreciation is also extended to Ms. Laura Linn at Dauphin
PEUU, or PU/PEUU storm-water infrastructure coating materials. Island Sea Laboratory, Dauphin Island, Alabama for conducting
Almost all literature reports documented contaminant release from TOC analyses. Specimens were provided by the Virginia Depart-
materials that are approved for potable water coatings. Results of ment of Transportation. Ms. Eddy Colmenarez at the University of
the present experimental study appear to be the first documented South Alabama is also thanked for helping with several water qual-
water quality impacts of storm-water pipe coating materials using ity measurements. Dr. Kevin White (University of South Alabama)
a static leaching experiment. and Ms. Suzanne Lindblom, Mr. Mike Simms, and Mr. Les Brown
Literature review demonstrates that contaminants released (Mobile Area Water and Sewer System) are greatly acknowledged
into waters are specific to the ingredients and impurities of each for their guidance on BOD testing and seed acquisition.
material. Generally, the greatest water quality alterations (e.g., pH,
COD, TOC, metals) have been reported for waters that contact new
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