United States
                   Environmental Protection
                   Agency	
Risk Reduction
Engineering Laboratory
Cincinnati OH 45268
                   Research and Development
 EPA/600/S2-88/066  Mar. 1989
x°/EPA         Project Summary
                   Proposed Test Protocol  to
                   Determine  Toxicant
                   Leaching  into Potable Water

                   Ronald Rossi, Craig R. Turner,  and Dipak K. Basu
                     A simple  apparatus was con-
                   structed  from  Teflon*  to test
                   teachability of contaminants. Plates
                   coated with  coal-tar-based mate-
                   rial were placed  In the Teflon test
                   chamber of the apparatus, and water
                   of controlled parameters was con-
                   tinuously passed through the
                   chamber at a velocity of 2 L/min for a
                   period of 24 hr.
                     The test apparatus was unique in
                   its ability to perform an accelerated
                   leaching  test under flowing  water
                   conditions.  These tests  showed
                   migrations of various component
                   polynuclear aromatic hydrocarbons
                   (PNA) with no detectable aging effect
                   in three successive 24-hr leachates
                   in results that fell in the range of 30
                   to 400 pg/L.
                     The possibility  of PNA migration
                   from the  coal-tar-based  material
                   lining pipes in the field was tested at
                   three utilities. No quantitative corre-
                   lation could be established between
                   the leaching  observed under labora-
                   tory and  field tests. However,  the
                   leaching pattern from the field pipes
                   can be quantitatively explained from
                   the results of  laboratory  leaching
                   tests.
                     This Project Summary was devel-
                   oped by EPA's Risk Reduction Engi-
                   neering Laboratory, Cincinnati, OH, to
                   announce  key  findings  of the
                   research project   that Is fully docu-
                   * Mention of trade names or commercial products
                    does not  constitute endorsement or recom-
                    mendation for use.
mented In a separate report of the
same  title  (see Project  Report
ordering information at back).

Introduction
  Potable water used by large segments
of the  U.S.  population is exposed to
direct and indirect additives. The direct
additives are  chemicals  that  are
deliberately added during the treatment
of raw water for  coagulation, softening,
corrosion  control, disinfection,  fluorida-
tion, and  other purposes. As  a  result,
finished water may contain both intended
and  unintended  residuals from  direct
additives.  Indirect additives are defined
as contaminants  that are inadvertently
introduced into the potable water through
paints,  coatings, liners, sealants, pumps,
and other items used during storage and
distribution of  potable water to con-
sumers. The change in potable water
quality  as a result  of the presence of
direct and indirect additives necessitates
an  evaluation  of the possible  health
hazards arising from these  additives.
Through  a  memorandum  of  under-
standing signed by the U.S.  Food and
Drug Administration  and  the U.S.
Environmental Protection Agency (EPA)
in 1979, the responsibility for monitoring
and  controlling  these additives  was
vested in EPA (44FR42775,  July 20,
1979). As one of the initial steps towards
meeting  this responsibility,  EPA, in
cooperation with the National Research
Council, produced a Water Treatment
Chemicals Codex for  direct additives
only. The Codex recommends a mini-
mum acceptable purity specification as it

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related to health for about 25 commonly
present additives in potable water.
  Indirect additives, on the other hand,
have been monitored through a voluntary
program and through the  issuance of
advisory  opinions  by  EPA  or its
predecessor agencies. Obstacles to the
development  of a safety evaluation
program for indirect additives  include  a
lack  of established maximum contami-
nant levels in several instances, absence
of suitable laboratory simulation data and
field  studies, and the  lack  of  a general
consensus  regarding  the target  param-
eters to be monitored as  indicators of
indirect additives.  The present investi-
gation was undertaken  to provide support
for Codex  development methodology for
indirect additives.  The purpose  of  this
research was (1) to develop a compre-
hensive and  realistic laboratory  test
protocol that would simulate contaminant
migration  from  coal-tar-based mate-
rials  similar to those  that  line potable
water pipes and tanks in the field, and (2)
to correlate the laboratory test  results
with  actual  field  studies.  Coal-tar-
based materials  were  used to represent
sources of  secondary  additives for
developing the  test  protocol because
leachates  from  these  materials  are
known to  contain  a  large number of
compounds,  some of which  are  sus-
pected to be carcinogenic.

Experimental

Laboratory Apparatus
  The laboratory leaching apparatus was
fabricated and  assembled  inhouse.  It
consisted  of four  parts:  (1) a leaching
compartment of  Teflon  having  a  well
20-1/2  by  1-1/2  by  9/20 in.  in the
midsection  and  a removable  Teflon top
plate for the insertion  of test plates; (2)
Teflon connecting fittings and  tubes; (3)
a variable speed circulating pump with all
Teflon wetable parts; and (4) a flowmeter.
A diagram of the laboratory apparatus  is
shown in Figure  1.
  Test  plates were fabricated from  a
stainless steel sheet 0.05 in. thick.  Each
plate had  a dimension of 20  x 1.5 in.
These plates  were sand-blasted before
being  coated. Each plate was cleansed
with purified deionized  distilled water
(DDW) and acetone and was dried before
the application of the  coating material. A
one-coat  Bitumastic  Super  Tank
Solution  (Type I) was  used  in the
experiments  as  a coating  system. The
test  plates  were  coated  with  the
suction-feed spraying  system  at  a
delivery pressure  adjusted to about 60
psi at the gun, as recommended by the
manufacturer of the  coating  material.
Two  coats of the coating material  were
evenly applied on both sides of the test
plates. The test plates were air dried for
10 days and  those plates with total dry
thickness ranging from 0.040 to 0.060 in.
were selected for further leaching tests.
  The  leaching test with coated plates
began  by pre-exposing the plates  in  a
solution  of  sodium  hypochlorite  con-
taining 50 ppm of free chlorine at a pH of
10.5. The plates were allowed to stand in
this  solution  overnight  and  were
subsequently washed with purified DDW.
Two  plates  were placed inside  the
leaching compartment, and it was sealed.
The  compartment  was  filled with  test
water of  controlled parameters,  and the
flow  rate  of  the circulating  water  was
maintained at the desired value.   The
entire leaching apparatus was transferred
to an environmental chamber  where the
temperature at  which the  test   was
conducted could  be  controlled.  It  was
experimentally determined that for a flow
rate  of 2  L/min, the temperature of the
environmental chamber had to be set at
12.8°C for the circulating water  to attain
an equilibrium  temperature of 21.5°C
and at 25.6 °C to attain a temperature of
28.5°C. The system was allowed to
for the desired length of time.
  At the end  of the run, all of the w
from the leaching apparatus was drai
into a  measuring  cylinder. An aliquc
the water  ( = 70 mL) was  kept sepa
for  performing alkalinity, hardness,
and residual chlorine tests. The resii
leachate was solvent  extracted  \
methylene chloride  (6 mL of methyl
chloride for every 100 mL  of water).
extract was  concentrated  to  a  f
volume of 1  mL using a Kuderna-Dai
apparatus  and subsequent  blowdi
using prepurified N2 gas at 30 °C.

Field Sampler
  The field sampler consisted  of
following three main components: (1)
containing a  two-stage resin  coli
system; (2) variable water pumping
consisting of  a  Masterflex  pump  i
appropriate  pumpheads   and   f
controller;  and (3) flowmeter. Chroma
extender-type columns of 150  x 25  x
mm were used to  hold the resin bed.
resin  bed  consisted of equal volumes
XAD-2 and XE-348  resins  separa
by glass wool. The length of the s<
resin bed was set at 13 cm. The end
the Chromaflex columns  were plug
        Flowmeter
                                            Pyrex®/Teflon® _ Ajf B,egd
                                               Stopcocks,{.
                                                                     Teflon®
                                                                     Tubing
             Teflon®
                                    Teflon®
                                                               .
                                                       Teflon® Male Fitting
           Male Fitting    Steel Plate  Leaching Compartment


 Figure  1.    Schematic diagram of leaching apparatus (not to scale).

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with  clean  glass  wool  and  were
connected  to  two  tapered  column
adaptors by "0" rings and clamps. Two
such  resin columns were connected  in
parallel to the water to be sampled
through a  Pyrex glass Y-tube. The other
end  of the  column was  connected
individually  to  a variable  Masterflex
pump. The  pump  units  with their flow
controllers allowed water to pass through
the resin  bed at the desired rate.  The
outlets of  the pumps  were connected  to
calibrated  flowmeters to measure the
flow  rate  that  was  maintained  at  40
mL/min. The effluent water was collected
in  calibrated collapsible plastic  carboys.
Measurement of the total water collected
in  each carboy over  a known period  of
time  permitted the gross water  flow rate
through the resin beds to be estimated.
All connections  along   the  different
components  were  made  with  the
custom-made 8-mm  Pyrex  glass tub-
ing of convenient shape and length, and
minimum  lengths of Tygon tubing were
used for interconnecting the Pyrex glass
tubing.

Field Sampling Analyses
  Potable  water samples from  three
water supply systems on the West Coast
of  the United States  were analyzed as
 ield  samples. The rationale for selecting
these systems was that they represented
three large public water  utilities and all
contained  transmission pipes lined with
coal-tar-based material.  The  expected
occurrence of secondary additives in this
water make it well suited to test whether
or  not the designed laboratory  leaching
apparatus, upon which the proposed test
protocol is based, could be successfully
used.
  At  each water supply,  water  samples
were collected at three points.  The  first
point was the water at the treatment plant
before it was exposed  to  lined trans-
mission pipes or tanks. The second and
third  sampling points were near  the
beginning and  near the  end of  a
transmission system that had  pipes lined
with  coal-tar-based materials.
  The  sampling unit was  transported  to
each sampling location by packing the
individual  components in  suitcases. For
the convenience of transportation,  the
Masterflex  pumps   with  the  flow-
controllers and pumpheads were carried
in  a  separate suitcase provided by the
manufacturer. A total of  20  L  of water
was collected from  each sampling point.
At  the  end of the sampling, the ends  of
'he resin  columns  were  sealed with
.jolyurethane  foam  plugs, parafilm,  and
masking  tape.  The  columns were
wrapped  in  aluminum foil, cooled with
non-wetable  ice  packs,  and then
transported  to  the laboratory.  In  the
laboratory the resin beds were warmed
and  separated,  and only the  XAD-2
portions  were  spiked with  a  known
amount  of  C14-fluorene.  Only  the
XAD-2 resins  were  subjected  to  the
elution  method.  The  XE-348 beds
containing more  polar compounds were
not further analyzed.
  The  XAD-2  resin  bed was washed
with about 20 to  25 mL of acetone. The
vacuum  from  an  aspirator  removed
excess acetone  from  the resin bed. The
dry XAD-2 bed was removed to  a clean
thimble,  and the  resin  was Soxhlet-
extracted for  24  hr with  methylene
chloride.  The acetone wash was diluted
with  purified DDW and  extracted with
methylene chloride. The two  methylene
chloride  layers  were  combined and
concentrated to  1  mL for radioactive
counting  and  analysis  using  a gas
chromatography-mass  spectrometry-
data  system  combination   (GC-MS-
DS). Before  the  radioactive counting, a
solvent exchange of methylene chloride
to toluene was performed on 500 pL of
the above concentrated extract. The
collection efficiency of seven PNA's with
this sampling apparatus averaged 84% in
the laboratory.
  To increase the sensitivity of the GC-
MS-DS analysis, several  modifications
were made  in  the  original system. The
injection  port  of the original packed
column GC  was replaced according to
the manufacturer's  instructions with  an
on-column (capillary) injection system.
The  interface  of the exit end  of  the
column with the  MS was also altered; the
jet separator   and  its  associated
accessories  were completely removed
and the exit  end of the  capillary  column
was  introduced  directly  into  the  ion
source. The conditions  used for  the
operation  of  the GC-MS   were  as
follows:
                                        Analyzer
                                         temperature:
                                        MS delay:

                                        Scan:
                                        Scan time:
                 200°C
                 4  min  following
                 sample injection
                 50 to up to 500 amn
                 1.2 sec/scan
Column:


Column
 program:
                 30  m  x  0.25 mm
                 DB-1  fused  silica
                 capillary
                 50°C  for  4  min;
                 8°C/min  to 270°C;
                 Hold at 270 °C  for 20
                 min
Carrier gas He
 linear velocity:    35 to 45 cm/sec
Source
 temperature:     170°C
  In the specific ion mode, the parent ion
and two  other fragment ions  with  the
highest intensities were monitored for a
period of  150 millisec each.
  The performance characteristics of the
MS were verified by frequently injecting
50  ng decafluorotriphenylphosphine
(DFTPP)  into the GC-MS system. When
the performance characteristics fell below
the recommended levels, the source of
the unacceptable  performance charac-
teristics  were corrected  either  by
cleaning  the ion source, plugging  pos-
sible leaks, or changing the sorbent traps
for the carrier gas.
  The GC-MS  system produced a  total
ion chromatogram of each sample. Since
the chromatograms contained  large
numbers  of peaks, the MS data system
was used to identify the peaks and locate
the individual  peaks when  necessary.
The tentative identification of each peak
was by NBS Spectral Library search. The
final  identification  of  a  compound  was
made by matching the relative retention
time (with respect to anthracene-d-io)
and the MS fragmentation pattern with an
authentic  standard. A peak was quantified
by comparing  its  area with  that  of  the
anthracene-dio  internal  standard.  This
method of quantification assumes a linear
response  of   peak  area  with   the
concentration.

Results and Discussion
  The  24-hr   laboratory  leaching
experiments  conducted  with plates
coated with  a  coal-tar  based material
and  water  of  controlled parameters
(aggressive  index, 8.6; free  residual
chlorine,  3.3 ± 0.03;  and temperature
21.5 ± 0.5°C) showed the migration of
the following components at the specified
concentrations (iig/L);  indene,   73;
naphthalene, 36; quinoline, 213;  indole,
45; acenaphthalene,  77; fluorene,  79;
phenanthrene/anthracene,  298; carba-
zole, 399; pyrene, 117; and triphenylene/
chrysene, 81. The  results of  three
consecutive 24-hr washings,  each  per-
formed to determined the aging effect of
the coated  plates, failed to  show  any
difference in the  concentrations of  the
individual PNA's  in  the  successive
leachates. The  increase  of  residual
chlorine level in water from 0.93  to 3.3
mg/L, resulted in decreased  concen-

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trations  of  some  of  the  PNA's,
particularly the  levels of  phenanthrene/
anthracene, purene, and fluorene in the
leachates, possibly  because of  the
formation of more  chlorinated  PNA's at
higher  chlorine  level. No  clear  trend
resulting from the  teachability  of PNA's
was  observed  by  changing the  water
temperature from 21.5°C to 28.4°C.
  Field test results of water  collected
from  one utility  showed  that  the
concentrations of a few PNA's noticeably
increased  as a  result of  finished  water
passing through  transmission pipes/tank
lined with  coal-tar-based  material.  For
example, the concentration  of indene,
fluoranthene, and pyrene increased from
0.12 pg/L, 0.06 pg/L, and  none detected
to  0.17,  0.11,  and  <0.05   jig/L,
respectively. No noticeable difference in
the level of PNA's in water originating
from pipes lined  with  coal-tar-based
material was  observed, however,  when
compared with levels from the  other two
utilities. This  is  probably because the
transmission  pipe  used  for  sampling
water in  one utility was  relatively new
( = 5 yr) and the transmission  pipes in the
other two utilities were older  ( = 10 years
old). Probably   a  difference  of  PNA
concentrations in the two  other systems
would  have  been  observed  if  the
detection limit  for  the PNA's had  been
lower  (<0.05 ng/L). No quantitative
correlation could be established between
the leaching observed under laboratory
and  field  tests.  This  is not surprising
considering that,  among  the   many
differences between the  two cases,
laboratory plates leach at  about 4 orders
of magnitude higher  than do  the field
pipes.  However, the leaching pattern
from the field pipes can be  qualitatively
explained  from  the results of laboratory
leaching tests.

Summary and Conclusions
  The Laboratory leaching apparatus and
the  test  protocol developed  in the
present study  have been successfully
used to determine the teachings of major
individual  components from  plates lined
with  coal-tar-based  material. The test
protocol was developed to identify and
quantify the  major individual contam-
inants  in  the  leachates.  This  is  an
important  improvement over the pre-
viously available protocols because it will
permit the assessment of possible health
hazards  arising  from  the  individual
leached components. The developed test
protocol  accelerates the  leaching of
components from  coated  surfaces  and
permits measurement of  the level of
major leachables  in short-term leaching
tests.
  The leaching study shows that PNA's
are the major contaminants that will leach
into water from surfaces lined with coal-
tar-based  material.  Evidence  is pro-
vided that PNA concentrations in leach-
ates  depend on the free residual chlorine
in the  water and  that  an increase in
chlorine level will decrease the level of
some PNA's in the leaching water. The
study also demonstrates that short-term
laboratory leaching tests are not suitable
for studying the aging effect in the field
of pipes  lined  with coal-tar-based
materials.
  Results of a few field tests with  potable
water after their passage through  pipes
lined  with   coal-tar-based  material
demonstrate  that  no  quantitative corre-
lation  can  be  made  between  the
laboratory and  field  leaching tests. The
leaching of components from  lined pipes
in the field will be about four orders of
magnitude lower than laboratory leaching
from coated plates.  To  establish the
possible PNA leaching in  the field from
transmission  pipes lined with coal-tar-
based material older than 5 yr, therefore,
the detection limit for PNA quantification
should be  s50 ng/thousand liters. The
results of laboratory  leaching tests are
useful  in field tests aimed at predicting
and  rationalizing the  observed  leaching
of contaminants from  transmission pipes
lined with coal-tar-based  material.

Recommendations
   Based on our  experience with the
present project, we recommend  that the
following ideas be considered for imple-
mentation of further research:
1.  Proper  interlaboratory verification I
   undertaken  so that the test apparat
   and the test protocol developed in tl
   study can  be  used  by  EPA  as
   standard  method for the approval
   materials intended  to  be  used
   contact with drinking water.
2.  The verified test protocol  be used
   identify  and  quantify  the  maj
   individual components for  subseque
   toxicological testing to  determii
   which of those identified  are causati
   factors in leachates found to be toxic
3.  The verified test protocol  be used
   further  establish the effect  of  wal
   quality parameters on the migration
   contaminants into the water.
4.  A guideline  based on the toxicity
   the  individual  contaminants  I
   established  to specify the minimi.
   acceptable  detection  limit of t
   contaminants for  the verified  te
   protocol.
5.  Further  research  be conducted
   verify the applicability of the prese
   test protocol to other materials used
   the transmission of potable water.
6.  Further  research  be conducted
   establish  a possible   correlate
   between the leaching observed  unc
   laboratory conditions and those  unc
   field conditions.

  The full  report was submitted in f
fillment  of  Cooperative Agreement f>
CR-811083 by  Syracuse  Resear
Corporation, Syracuse,  NY  13210-40*
under the  sponsorship  of  the   U.
Environmental Protection Agency.

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Ronald Rossi, Craig R. Turner, and Dipak K. Basu are with Syra.      —
  Corporation, Syracuse, NY 13210-4080.
Alan A. Stevens is the EPA Project Officer (see below).                 —"
The complete report, entitled "Proposed  Test Protocol  to  Dete>            I   R;'K-J ^   /;'"!">jsi ~  fj  7 C   !*
  Leaching into  Potable  Water," (Order No. PB 89-125 9591 AS;       ""    v          /:    *' ~"       "  '"'"
  subject to change) will be available only from:
        National Technical Information Service
        5285 Port Royal Road
        Springfield, VA22161
        Telephone:  703-487-4650
The EPA  Project Officer can be contacted at:
        Risk Reduction Engineering Laboratory
        U.S. Environmental Protection Agency
        Cincinnati, OH 45268
United States                  Center for Environmental Research                                      BULK RATE
Environmental Protection        Information                                                    POSTAGE & FEES PAID
Agency                        Cincinnati OH 45268                                                     EPA
                                                                                              PERMIT No. G-35

Official Business
Penalty for Private Use $300

EPA/600/S2-88/066
                                   0000329    PS

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