EPA-560/13-79-013
SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
TASK I: ACRYLAMIDE
, BY
John Going and Ken Thomas
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
Contract No. 68-01-5017
December 1979
Tom .Kopp
Project Officer
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
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EPA-560/13-79-013
SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
TASK I: ACRYLAMIDE
BY
John Going and Ken Thomas
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
Contract No. 68-01-5017
December 1979
Tom Kopp
Project Officer
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
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NOTICE
This report has been reviewed by the Office of Toxic Substances, Environ-
mental Protection Agency, and approved for publication. Approval does not
signify that the contents necessarily reflect the views and policies of the
Environmental Protection Agency. Mention of trade names or commercial products
is for purposes of clarity only and does not constitute endorsement or recom-
mendation for use.
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CONTENTS
Tables iil
Figures iv
1. Summary 1
2. Introduction 2
3. Sampling and Analysis Protocol 3
Sampling protocol 3
Analysis protocol 3
4. Method Development for Sampling and Analysis 5
Literature study 5
Analytical methods 6
5. Selection of Sites and Samples 15
Potable water treatment plants 15
Polyacrylamide samples 17
6. Discussion of Results 21
Sampling 21
Sample analysis 23
References 30
11
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TABLES
Number Page
1 Literature Methods for Determination of Residual Acrylamide Monomer
in Polymers 7
2 Stability Study of Acrylamide 8
3 Results from Analysis of Acrylamide Standards 14
4 Summary of Cities Surveyed for Polyacrylamide Use . . 16
5 Recommended Sites for Sampling 18
6 Polyacrylamides Selected for Analysis 19
7 Water Sampling Data, Kansas City, Missouri, Water Treatment Plant. . 23
8 Polymers Requested and Received 24
9 Summary of Acrylamide Analyses 26
10 Results of Analysis of Polyacrylamide Samples 28
11 Recoveries from Spiked Polymers 29
iii
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FIGURES
Number Page
1 Calibration curve for the HPLC determination of acrylamide n
2 Chromatograms from acrylamide calibration curve 12
3 Chromatogram of Celanese sample 295 13
4 Kansas City, Missouri, Water Treatment Plant 22
iv
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SECTION 1
SUMMARY
The purpose of this program is to provide sampling and analysis capabil-
ities to Environmental Protection Agency's (EPA) Office of Toxic Substances,
so that the levels of suspected toxic substances in air, water, soil, and
sediment at designated locations throughout the United States can be determined.
The first task involved sampling and analysis for acrylamide (AA).
Methods for the determination of acrylamide in water and in polyacryla-
mide were validated. Water samples were reduced in volume by evaporation and
analyzed by GC using a nitrogen selective thermionic detector. The detection
limit was determined to be ^ 1 yg/liter. Polyacrylamide samples were extracted
with 80% methanol/20% pH 3.75 water for 3 hr. The extracts were analyzed by
HPLC with a UV detector set at 200 nm. The monomer limit of detection was
~ 0.5 yg/g.
One potable water treatment plant was sampled at pre- and post-flocculation
points. MRI tap water was analyzed for comparison. No acrylamide above the
detection limit was found in any of the samples.
Thirty-two polymers were analyzed for residual acrylamide. When not ob-
scured by interferences, the observed acrylamide ranged from 0.5 to 600 yg/g.
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SECTION 2
INTRODUCTION
Acrylamide is the most important chemical in the acrylamide group, being
produced at an estimated rate of 63 million pounds per year as of 1976.A/ By
1978, all production should be based on catalytic hydration of acrylonitrile.
The major producers of AA are American Cyanamid, Dow Chemical, and Nalco
Chemical. The principal use of AA (*v> 80%) is in the production of water
soluble polymers, commonly called polyelectrolytes, flocculants, coagulants,
thickening agents, retention aids, and drainage aids. Polymer production con-
sumes nearly all AA production, much of it captively.
Acrylamide release to drinking water could occur from the use of poly-
aery lamide flocculants in water treatment facilities. Residual monomer from
the polymers could migrate into the water being treated. The extent of the
problem would be influenced by the actual level of residual monomer in the
flocculents. The Research Request called for MRI to determine the monomer
level in polymers approved for water treatment and to determine the monomer
level in water treated by these polymers.
The remainder of this report describes the experimental methods employed,
including the validation of the sampling and analysis protocol, the selection
of sampling sites and polymers, and a discussion of the monitoring results.
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SECTION 3
SAMPLING AND ANALYSIS PROTOCOL
SAMPLING PROTOCOL
Water Sampling
.Water samples were collected at various points in the water treatment
process using 1 gal., silanized brown glass bottles with Teflon cap liners.
After collection and during storage, the samples were kept at 4°C.
Polyaerylamides
The polyacrylamides were directly requested from the producer. The re-
quest included a full explanation of their intended use.
ANALYSIS PROTOCOL
Water Analysis
Sample Preparation—
Duplicate 500-ml aliquots were taken from each sample. Each aliquot was
then reduced in volume to less than 5.0 ml by rotary evaporation at 50°C under
reduced pressure. The reduced aliquots were then transferred to graduated
centrifuge tubes and allowed to stand at 4°C for 1 day to allow particulate
matter to settle. The supernatant fluid was drawn off, transferred to gradu-
ated centrifuge tubes, and further reduced to about 1.0 ml by evaporating at
50°C under a stream of prepurified nitrogen. Silanized glassware was used
throughout. The reduced aliquots were then stored at 4°C pending analysis.
Sample Analysis Conditions—
The samples were analyzed by gas chromatography/thermionic selective de-
tection (GC/TSD). The conditions were as follows:
Column: 3 ft x 1/8 in. ID, glass
Packing: 80/100 Chromosorb 101
Injector Temperature: 210°C
Detector Temperature: 250°C
Oven Temperature: 180°C
-------
Carrier: 30 ml/min prepurified nitrogen
H2 Pressure: 17.5 psi
Bead Current: 4.5 amp
Quality assurance was generated by spiking 500-ml aliquots of each sample
and a water blank with 1.0 to 2.0 yg acrylamide. All were prepared and analyzed
as above.
Polyacrylamide Analysis
Sample Preparation—
Duplicate 5-g samples of each polymer were weighed and transferred to 4-oz
bottles. The liquid samples were stirred with a glass rod before sampling to
minimize layering. Fifty milliliters of 80% methanol/20% pH 3.75 water was
added to each bottle. The bottles were capped with polyethylene lined caps
and placed on a wrist.action shaker for 3 hr. A blank was prepared by adding
50 ml of the extracting solution to an empty 4-oz bottle fitted with a lined
cap. This was also shaken for 3 hr. (The blank showed no interfering peaks.)
Approximately 2 to 3 ml of the supernate from each polymer was transferred to
a centrifuge tube and spun for a minimum of 10 min. For most of the polymers,
this produced a clear solution ready for injection onto the HPLC. However,
the five Nalco liquid samples formed emulsions that could not be filtered or
spun down. The clear solutions obtained by centrifuging were transferred to
capped 2-dram vials and taken to the HPLC lab for analysis.
Standards were prepared in 80% methanol/20% pH 3.75 water at concentra-
tion levels of 0.1 ppm, 0.5 ppm, 1.0 ppm, 5.0 ppm, 10.0 ppm, 50.0 ppm, 100.0
ppm, and 500.0 ppm.
Sample Analysis—
The HPLC assay parameters are listed below.
Instrument: Altex Model 100 pump, Waters' Model U6K injector, Schoeffel
Model 770 variable wavelength absorbance detector, Heath Model 255B
single pen recorder
Column: Whatman, Inc., Partisil-10 ODS-2, 4.6 x 250 mm
Solvent: H20 adjusted to pH 3.75 with H2S04
Flow: 2 ml/min
Detection: UV at 200 nm - attenuated as needed
Chart: 10 min/in
Injection: 20 yl using 80% methanol/20% water at pH 3.75
Injections of the Nalco liquid samples caused severe degeneration of the
HPLC column. Therefore, before the final assay could be performed, the column
needed to be cleaned thoroughly with DMF and then methanol. This rejuvenated
the system to the original level of sensitivity.
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SECTION 4
METHOD DEVELOPMENT FOR SAMPLING AND ANALYSIS
LITERATURE STUDY
Following receipt of Research Request No. 1, a survey of the literature
was made to determine the state-of-the-art sampling and analysis techniques
for the assigned tasks, i.e., residual acrylamide monomer in polymer and trace
level acrylamide in.potable water. Since MRI had recently completed a project
involving analysis of acrylamide in water, this part of the literature study
consisted of updating the information.
The literature search was performed by computer and was limited to
Chemical Abstracts, 1977 to 1979 (Vol. 90, No. 6), since the earlier litera-
ture had already been obtained. The search strategy was based on a Boolean
AND of the terms in Columns 1 (items 1-15) and 2 (items 17-24) shown below.
The number in parentheses indicates the number of hits for that particular
term.
Column 1
Column 2
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
(54374)
(68608)
(76810)
(0)
(56943)
(12176)
(14467)
(0)
(0)
(8361)
(15098)
(14680)
(8992)
(2240)
(4761)
(158870)
ANALYSIS
ANAL?
DET?
DETN? S CHROMATOG?
DETN?
SPECTROM?
HYDROL?
SOLVEL?
DISTN7S SAMPL?
ADSORP?
ABSROP?
CROMATOG?
SOLVEN?
DISTIN?
SAMPL?
1-15/OR
17 (435)
18 (0)
19 (2161)
20 (0)
(0)
(2)
(0)
(0)
25 (2301)
26 (604)
27 (360)
21
22
23
24
RN=79-0601
RN=44170-53-8
ACRYLAMIDE
SY=ACRYLAMIDE
2-PROPENAMIDE
PROPENAMIDE
2(W)PROPENAMIDE
MF=C3-H5-N-0
17-24/OR
16*25
26/ENG
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The combination of lines 16 and 25 gave 605 hits. When limited to ar-
ticles in English, 360 hits were made. This list was then printed out, man-
ually inspected, and relevant articles were then obtained.
The most promising methods found in the literature search for the deter-
mination of residual acrylamide in polymers are summarized in Table 1. Vari-
ous polarographic techniques were found but they lack the necessary specific-
ity to be of value.
No methods for trace acrylamide in water other than what was used in the
previous study.?/ were found in the literature study.
ANALYTICAL METHODS
Water Analysis
In the previous project on acrylamide,±) protocols for GC analysis and
GC/MS confirmation were developed and evaluated. The sample was prepared for
analysis by evaporation and then analyzed by GC/Hall detection or by GC/high
resolution mass spectrometry. For this project, the use of a new generation
thermionic bead detector, from Varian, was tested as a replacement for the
Hall electrolytic conductivity detector. The nitrogen-phosphorus selective
thermionic bead detector had comparable sensitivity for nitrogen but much
better stability.
The precision of the chromatographic analysis was determined by replicate
injections (3-5) of 1 and 10 ppm solutions of acrylamide in water. The rela-
tive standard deviations were 11% and 35% at 10 and 1 ppm, respectively.
There was concern about the stability of acrylamide in potable water
treated with chlorine. A limited study was run at 4°C with 25 ppm chlorine
and was designed to include the effect of time on stability. The conditions
and results are summarized in Table 2.
:. Although there was some difference in the initial concentrations, there
was no significant change in any of the three samples over the 6-day test
period. Therefore, it can be concluded that chlorine has no effect on acryla-
mide stability, and the addition of Na2S203 is unnecessary.
Polyacrylamide Analysis
Development of Instrumental Procedure—
The analysis procedure as outlined by Skelly and Husser in Analytical
Chemistry (Vol. 50, No.. 14, p. 1959) was used as a basis for this development.
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TABLE 1. LITERATURE METHODS FOR DETERMINATION OF RESIDUAL ACRYUWIDG MOBOffiR IN POLYMERS
Sample preparation
Analysis method
Limit of detection
Recovery* precision
(spike level)
Application, consents
E. R* Husser, et al.
Anal. Chem. 49, 154(1977)
F. J. Ludwig, Sr., et al.
Anal. Chem. 50, 185 (1978)
N. E. Skelly, et al.
Anal. Chem. 50, 1959(1978)
1. Nonaqueous dispersed polymer
Ten grams of polymer are batch
extracted with 50 ml metHanoi for
2 hr and centrifuged. Benzamide
added as internal standard*
2. Aqueous dispersed polymer
Five grams of polymer are
dropped into a stirred mixture
of 10 ml methylene chloride,
40 ml water, and 0*5 ml cone.
HCl. After 30 min stirring,
the sample is centrifuged,
the supernatant removed, and
reduced to 10 ml.
Four to six grams of poly-
mer emulsion or solution are
added dropwise to stirred ace-
tone (or methanol ). After
stirring 15 min the suspension
is filtered. Benzamide is
added as an internal stan-
dard.
Fifty milliliters of
80-20 methanol water is
added to 5 g polyacrylamide
and stirred 4 hr.
Column: Partisil 10 PAC
(250 x 4.6 mm)
Mobile phase:15% methanol, 85%
methylene chloride
at 1 ml/min
Detector: UV at 240 nm
Volume: 6 nl external sam-
ple loop
Column: Dowex 50 W-X4
(250 x 4 mm)
Mobile phase: 0.01NH2S04,
0.7 ml/min
Detector: UV at 225 nm
Volume: 500 jjl injection
10 ppm (0.001%)
0.1 ppm (0.00001%)
Column: Partisil 10 PAC
(250 x 4.6 tun)
Mobile phase:10% methanol, 90%
methylene chloride
at 1 ml/min
Detector: UV at 240 nm
Volume: 10-15 yl injection
Column: Partisil 10 ODS-2
(250 x 4.6 mm)
Mobile phase:Water at 2 ml/min
Detector: UV at 206 nm
Volume: 200 ;il injection
40 ppm (0.004%)
0.1 ppm (0.00001%)
99 + 4%
86 + 13% (1 ppm).
102 + 12% (20 ppm)
-90% (300 ppm),
aqueous polyacrylamide
-94% (200 ppm),
cationic emulsion
-99% (3 ppt),
anionic emulsion
3.7Z relative standard
deviation at 177 ppm
sample
Ethyl acrylate based polymer
Ethyl acrylate based acrylonitrile
modified polymer
Butyl acrylate based acrylonitrile
modified polymer
Acrylamlde elutes on solvent
tail
Results agreed with ion exclusion
method of Husser above, with
20 polymers
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TABLE 2. STABILITY STUDY OF ACRYLAMIDE
Sample test conditions Acrylamide, mg/liter
ChlorineNa2S203£/ Initial 24 hr 48 hr 144 hr
No
25 ppm
25 ppm
No
No
430 ppm
0.
0.
0.
85
58
82
1.
0.
1.
04
40
16
0.
0.
0.
91
49
71
0.
0.
0.
79
54
96
a/ The ^28203 was added to the mixture of acrylamide and chlorine.
However, substantial difficulty was encountered when MRI tried to duplicate
the chromatographic method. The instrumentation used at MRI included an Altex
Model 100 pump, a Waters U6K injector, a Shoeffel Model 770 variable wave-
length absorbance detector and a Heath Model 255B recorder. This equipment
is equivalent to the instrumentation used by Skelly. A Whatman Inc., Partisil-
10 QDS-2, 4.6 x 250 mm reverse phase column was used to duplicate the C^g
loading and subsequent acrylamide retention volumes. Standards were prepared
in 80% CH^OH as directed. An outline of the development follows:
1. The instrumentation listed above was set up using a Whatman guard
column (2.1 x 60 mm) with 100% H20 from the Milli-0 water system as the eluant
(2 ml/min) . The detector was set at 208 nm 0 -> 0.01 setting. Although Skelly
and Husser reported a retention time of 5.2 min for acrylamide in this system,
at MRI no peaks eluted in 30 min.
2. The eluant was modified with 5%, 4%, 2% and 1% C^CN to reduce reten-
tion times. A peak did elute for acrylamide at 100 ppm and 10 ppm concentra-
tion levels at retention times of 5 to 10 min; however, the response dropped
off almost geometrically instead of linearly. The 1 ppm standard could not be
seen even at the lowest absorbance setting (0 -»• 0.01 range).
3. The monitoring wavelength was dropped to 204 nm and 200 nm and the 3%
CH^CN eluant injections were repeated. Although the 100 ppm and 10 ppm
standards increased slightly in response, the 1 ppm standard could not be
seen.
4. All of the work in B and C was repeated using Q^OH as the modifying
solvent. The results were similar.
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5. After consulting with Skelly to insure that nothing had been over-
looked, Waters Associates applications lab was contacted for additional sug-
gestions. They recommended buffering the H20 to an acidic pH. This presented
another problem since most buffers would be opaque at 208 nm. The only choice
seemed to be a nonhalide mineral acid. I^SO^ was added to the water pump to
a pH 3.75 and the work in 2 and 3 was repeated. The baseline was very erratic
and 1 ppm could not be detected. The guard column was removed with no effect.
6. To alter the approach, a system was tested that did not include any
organic solvents. The standards were remade using H20 adjusted to pH 3.75
with I^SO^. The eluant of the system was changed to H20 adjusted to pH 3.75.
This dramatically changed the chromatography so that standards from 100 ppm to
0.1 ppm were detectable with good linearity. The baseline was excellent even
at 200 nm (0 -> 0.01 range).
7. A fresh set of standards was prepared in 80% CH30H/20% H20 at pH
3.75. Although these samples do not chromatograph as well as the water stan-
dards, the analysis will be possible so long as injection volume is consistent
and not less than 20 yl.
Final HPLC Procedure--
Instrument: Altex Model 100 pump, Waters Model U6K injector, Schoeffel
Model 770 variable wavelength absorbance detector, Heath Model 255B
single pen recorder
Column: Whatman Inc., Partisil-10 ODS-2, 4.6 x 250 nm
Eluting Solvent: H20 adjusted to pH 3.75 with H2S04
Flow: 2 ml/min
Detection: UV at 200 nm - attenuated as needed.
Chart: 10 min/in
Injection: 20 yl using 80% CH30H/20% H20 at pH 3.75
Twenty milliliters of each of the following standards of acrylamide were
injected onto the system to test linearity.
(Adjusted absorbance)
Cone, in sol'n. Peak height Abs. range Abs. Abs./Conc.
0.1 ppm 11 nm 0 -»• 0.01 0.11 1.10
0.5 ppm 37 nm 0 -> 0.01 0.37 1.35
1.0 ppm 76 nm 0 + 0.01 0.76 1.32
5.0 ppm 93 nm 0 ->- 0.01 3.72 1.34
10.0 ppm 181 nm 0+0.04 7.24 1.38.
50.0 ppm 87.nm 0 ->- 0.4 34.80 1.44
100.0 ppm 173 nm 0 + 0.4 69.20 1.45
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The calibration curve generated by these data is shown in Figure 1.
Copies of typical chromatograms are shown in Figure 2.
Optimization of Extraction Procedure—
Optimum extracting solvent—Dry 5-g samples of one polymer were extracted
in 4-oz bottles on a wrist action shaker using the following solvents:
50 ml 20% CH30H/80% pH 3.75 H20
50 ml 50% CH3OH/50% pH 3.75 H20
50 ml 80% CH3OH/20% pH 3.75 H20
100 ml 80% CH3OH/20% pH 3.75 H20
The 20% and 50%' CH30H would not wet the polymer. Fifty milliliters of
80% MeOH shook well with the least dilution.
Minimum extraction time—A 5-g sample of Celanese 295 was weighed and
transferred to a 4-oz bottle. Fifty milliliters of 80% CH30H/20% pH 3.75 H20
was added and the bottle was fitted with a lined cap. The sample was placed
on a wrist action shaker for 3 hr. A small aliquot (^ 1 ml) was removed at 15
min, 30 min, 60 min, 90 min, 150 min and 180 min. These samples were assayed
using the HPLC system outlined above. The analysis results follow:
Extraction time Peak height
15 min 19 nm
30 min 20 nm
60 min 22 nm
90 min 22 nm
150 min 29 nm
180 min 29 nm
Figure 3 shows the chromatogram of Celanese 295. Note the peak eluting
after acrylamide.
Several other observations concerning the polymer analysis procedure are:
* Propionamide, a possible internal standard, elutes in the pH 3.75 elu-
ant at 7.0 min compared to 5.5 min for the acrylamide; however, there
is interference from a peak in some of the polymers at 7.0 min. No
internal standard will be used.
* Hydroacrylonitrile does not elute at selected conditions; therefore,
we expect no interference. This was mentioned as a known impurity in
. their polymers by John E. Villaume of American Cyanamid (personal
communication, 1979).
10
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70
60
50
S 40
c
o
JQ
30
20
10
0.2
0.4 0.6
ppm
0.8
1.0
10
50
Acrylamide, ppm
100
Figure 1. Calibration curve for the HPLC determination of acrylamide.
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1
-
Injection-'
1
i
5T
o
o
i/>
o
o
2
1
5
\ 1
^J
1
_o
o
o
V>
o
o
1
Q.
a.
-------
Figure 3. Chromatogram of Celanese sample 295.
13
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* Some of the polymers are wetted into very stiff emulsions which will
make sampling very difficult and the dry weight percents may be in
error.
Standardizations— •
Table 3 is representative of the injections of standards during the
assay.
TABLE 3. RESULTS FROM ANALYSIS OF ACRYLAMIDE STANDARDS
Concentration Date Attenuation Peak height Adj. peak height
0 . 1 ppm
0 . 5 ppm
0.5 ppm
1 . 0 ppm
1 . 0 ppm
1 . 0 ppm
5 . 0 ppm
5 . 0 ppm
5.0 ppm
10.0 ppm
10.0 ppm
10.0 ppm
50.0 ppm
50.0 ppm
500 ppm
8/23
8/23
8/25
8/23
8/24
8/24
8/24
8/24
8/24
8/24
8/24
8/24
8/24
8/25
8/25
0.01
0.01
0.01
0.01
0.01
0.04
0.04
0.04
0.1
0.04
0.04
0.10
0.20
0.20
2.0
8
31
33
68
67
16 .
84
88
36
165
178
74
166
173
171
0.08
0.31
0.33
0.68
0.67
0.64
3.36
3.52
3.60
6.60
7.12 .
7.40
33.2
34.6
342
For these standards, the best fit curve by linear regression is:
(Adj. peak height in mm) = 0.68 (concentration in solution in ppm) - 0.006
corr. = 0.99999
14
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SECTION 5
SELECTION OF SITES AND SAMPLES
POTABLE WATER TREATMENT PLANTS
A recent study of acrylamide use has established that about 1.3 million
pounds ('v. 2.5% of yearly use) is used for potable water treatment .±J As part
of this study a survey of 59 cities was made to establish the use pattern of
polyacrylamide flocculants. A summary of the cities that responded as using
polyacrylamide is given in Table 4. The cities are classified as large (pop-
ulation greater than 250,000), medium (population from 100,000 to 150,000),
and small (25,000 to 50,000). Eleven cities are using polyacrylamides and two
cities—Lancaster, Pennsylvania, and Milwaukee, Wisconsin—reported using
polyacrylamides in the past.
The following is a list of potential factors for consideration as site
selection criteria. Their value is discussed and, if appropriate, they are
applied to the list of users.
* Probability of site having a measurable level of acrylamide,
* Size of population potentially exposed,
* Duration of exposure, and
* Source of polyacrylamide.
Probability of Finding Acrylamides
The probability that a site will have a measurable level of acrylamide is
directly proportional to the level of flocculant used. The best sites by this
criterion are Kansas City, St. Louis, and possibly Los Angeles. It is not
clear from the survey information what flocculant Los Angeles used to reach
the reported 5 ppm level. The next choices would be Las Vegas and Chicago.
None of the remaining cities appear to be using enough polyacrylamide floccu-••
lant to produce a measurable level of monomer.
15
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TABLE 4. SUMMARY OF CITIES SURVEYED FOR POLYACRYLAMIDE USE
City
Large Cities
Chicago, IL
Kansas City, MO
Los Ange Les , CA
St. Louis, MO
Medium Cities
Alexandria, VA
Elizabeth, NJ
Fremont, CA
Las Vegas, NV
Small Cities
Bismark, ND
Fort Collins, CO
Richland, UA
Water supply
Lake Michigan
Missouri River
Owens Valley
(East . Sierras )
through the Mo |ave
or Cottonwood aque-
ducts
Not specified
Reservoir, surface
water
Upland surface
water
Mostly river
6O7. Lake Mead
407, Well
Missouri River
Poudry River
Columbia River
Wells
Polyacry lamlde used
1978: Calga Rat floe A
1979: Cy,lnam1d
1978: Cyanamid Magnl-
floc 990N
now Purl floe N2O
Nalco and Ilercufloc
Not known
Dow Purifloc N17
Nalco Nalcolyte R171
Others
Dow Separan MFIO
Cyanamid 1986 N
Cyanamid 1986 N
Cyanamid 990 N
Nalco Nalcolyte 8184
Cyanamid 1986 N
Dow Separan NPlO
Flocculant
concentration - Amount used per ~ Amount of water
Use pattern (ppm) year (Ib) treated
Continuous use 1.24 (ave. ) 590,000 1 , 000 MCO
Turbid conditions n. 01-0.6 100,000 110 MOD
(6 months /year ) "
Turbid conditions 0.6-5" Not known 1,100MGT1(?)
(6 months/year )
Continuous use 0.6 (coafiulent 84,000 as coagu- Not known
aid) lent aid
F.xper imentat O. Oj Mot known Not known
Very cold weather only 0.01 Not: known Not known
Continuous use 0.012 Not known 8 MGO
Continuous use . 0.4 Not known •-*-• 70 MGD
Not known Not known -^500 5.9 MOO
- 5 mniiths/y
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Size of Exposed Population
All other things being equal (i.e., flocculant level, accessibility of
site, etc.), the size of population potentially exposed may be used as a cri-
terion. This is easily quantified by the size of the plant as expressed in
the millions of gallons per day (MGD) of water that is treated. Considering
only the sites selected above based on flocculant level, Chicago and Los
Angeles are the largest and are nearly equal in size (see Table 4). Although
the volume of water treated at St. Louis is not known, the quantity and concen-
tration of polyacrylamide is similar to that of Kansas City. Las Vegas is
slightly smaller than Kansas City and presumably smaller than St. Louis.
Duration
The differences in duration did not appear to be large enough to use for
selection criteria.
Source of Polyacrylamide
1 The source of the polyacrylamide was not suggested as a criterion for
several reasons. Many cities use various brands singly and in mixtures, and
it was not always possible to know ahead of sampling time exactly what polymer
would be used. Also, all of the polymers were analyzed for residual monomer
and were, in fact, not expected to be significantly different. They were ex-
pected to be generally around 0.05% since government regulations require that
the residual monomer be _<_ 0.05% and that the added polymer level be _< 1 ppm.
Using the criteria discussed above, and giving consideration to the cost
of field sampling, the recommended sites selected for sampling are listed in
Table 5 in decreasing order of priority. However, this list was flexible,
and before any actual sampling, each potential site was to have been contacted
to confirm the information used to establish its ranking. The sites visited
first were those with the highest probability of having detectable acrylamide.
If no acrylamide or a low, but acceptable level of acrylamide was found, then
it was planned to terminate sampling.
POLYACRYLAMIDE SAMPLES
The samples selected for polyacrylamide analysis were primarily those
listed in the Research Request as being approved for treatment of potable
water. Additional samples were later selected that were approved for food
packaging. Table 6 lists the selected samples and their approved use.
17
-------
TABLE 5. RECOMMENDED SITES FOR SAMPLING
Priority
Location
Rationale
1 ...
3-4
Kansas City, MO
St. Louis, MO
Las Vegas, NV
or
Los Angeles, CA
Chicago, IL
High level of flocculant (0.6 ppm)
Large plant
Location
High level of flocculant (0.6 ppm)
Large plant
Closeness to Kansas City
High level of flocculant (0.4 ppm)
Flocculant may be high (0.6 ppm)
Medium level of flocculant (0.24 ppm)
Very large plant
18
-------
TABLE 6. POLYACRYLAMIDES SELECTED FOR ANALYSIS
Polyacrylamide
Approved use
Calgon Coagulant Aid
223(N)
253(A)
Potable water treatment
Potable water treatment
Cyanamid Magnifloc
345(A)
846(A)
847(A)
985(N)
900(N)
990(N)
1849(A)
1986(N)
Potable water treatment,
Potable water treatment,
Potable water treatment,
Potable water treatment,
Food packaging
Potable water treatment,
Potable water treatment,
Potable water treatment,
food packaging
food packaging
food packaging
food packaging
food packaging
food packaging
food packaging
Dow Purifloc
C31
C51
A23P
N17
N20
Potable water treatment, food packaging
Potable water treatment, food packaging
Potable water treatment, food packaging
Potable water treatment, food packaging
Potable water treatment, food packaging
Dow Separan
AP30
NP10
NP10PWG
AP273 premium
Potable water treatment, food packaging
Potable water treatment, food packaging
Potable water treatment, food packaging
Potable water treatment, food packaging
Nalco Nalcolyte
8170
8171
8172
8173
8174
8182
8184
Stein-Hall (Celanese)
M-19
M-295PW
Potable
Potable
Potable
Potable
Potable
Potable
Potable
water
water
water
water
water
water
water
treatment,
treatment,
treatment,
treatment,
treatment,
treatment,
treatment,
food packaging
food packaging
food packaging
food packaging
food packaging
food packaging
food packaging
Potable water treatment, food packaging
Potable water treatment, food packaging
(continued)
19
-------
TABLE 6 (continued)
Polyacrylamide Approved use
Hercules Reten
210 Food packaging
220 Food packaging
420 Food packaging
421 Food packaging
423 Food packaging
423 Food packaging
20
-------
SECTION 6
DISCUSSION OF RESULTS
SAMPLING
Water Samples - Kansas City, Missouri, Water Treatment Plant
Field Sampling—
Presampling survey—A presampling survey of the Kansas City, Missouri,
Water Treatment Plant was conducted on July 24, 1979. The plant is located
near the junction of Missouri Highway 9 and 32nd Avenue immediately north of
North Kansas City, Missouri.
The Kansas City, Missouri, Water Department takes its water from the
Missouri River and processes about 130 million gallons per day (MGD) through
six lines acting as three units. While polymer was not used at this time of
year, the Kansas City, Missouri, Water Department volunteered to run Nalco
8173 through one-third of the .system for 24 hr to accommodate our sampling.
The use of polymer was started on July 24, 1979.
Sampling—Sampling was conducted on the morning of July 25, 1979, between
0930 and 1100 local time. Six 1-gal. water samples were taken at three loca-
tions (Figure 4) representing raw water influent (W-l), post-floe, prechlori-
nation (W-2), and chlorinated final effluent (W-3). The water is chlorinated
to provide 1 ppm residual chlorine. Additionally, a sample of the polymer mix
used to treat the water and a sample of the Nalco 8173 were also obtained.
The polymer mix was 0.5% by volume. The sampling locations are described in
Table 7. Due to the fact that polymer was only being added to one-third of
the system during a 2-day period, no tap water samples were taken.
21
-------
NJ :
N3 |
GRAVEL
DISTRIBUTION GATE
DISTRIBUTION BLDG.
2B I ^FINAL FLOCCULATORS
DISTRIBUTION GATES
It
FIN
1
i &
AL S
y/;
E T T L
•
|
£<5
N G B
A:
.IN ;
N 3
S 3
PHOSPHATE
BLDG.
o
WATER SAMPLING LOCATIONS
(W
^
-a
_^
i
A
C
\)
LTI
ALL
R
:RIE
B
B
j
PUMP BUI I
LI
—
IN (
GAL
1
C
.DING
RY
BASIC DESIGNATION & LOCATION
Figure 4. Kansas City, Missouri, Water Treatment Plant.
-------
TABLE 7. WATER SAMPLING DATA, KANSAS CITY, MISSOURI. WATER TREATMENT PLANT
Description of location
Sample No. of sampling points Sample type Sample size
W-l Raw water valve in Grab water 2, 1-gal.
chemical building
W-2 Sluice from sedimentation Grab water 2, 1-gal.
basins 1 and 2, prior
to chlorination
W-3 Valve in filter gallery A, Grab water 2, 1-gal.
after chlorination
prior to pumping out for
distribution
Sample Handling and Preservation—
The water samples were taken in silanized, brown glass bottles with
Teflon liners and transported directly to MRI where they were stored at 4°C.
Polyacrylamides
All requested polymers that are currently available were received. Table
8 summarizes the requested and received samples.
SAMPLE ANALYSIS
Water Samples
The water samples were analyzed for acrylamide by GC/TSD using the condi-
tions listed in Section 3. The results of the analysis plus the OA studies
are summarized in Table 9. Two of the samples spiked a 1 yg/liter showed
76% recovery while no acrylamide was found in the other two samples. In these
cases, however, the detection limit was extremely close to the expected acryla-
mide level of ^ 0.75 yg/liter (1 yg/liter spike at ^ 75% recovery). Two
blanks, however, spiked at 2 yg/liter recovered well. All the results, taken
together, indicate that the practical detection limit is more on the order of
1 yg/liter and that the samples do not contain acrylamide at or near that
level.
23
-------
TABLE 8. POLYMERS REQUESTED AND RECEIVED
Polymer requested
Calgon Coagulant Aid
233 (N)
253 (A)
Cyanamid Magnifloc
845 (A)
846 (A)
847 (A)
985 (N)
990 (N)
1849 (A)
1986 (N)
_
Polymer received
233
253
845A
846A
847A
985N
990N
1849A
1986N
900N
Lot number
8 B422
8 A478
12885
12937
13081
13123
130109
13011
12993
13141
Dow Purifloc
C31
C51
A23P
N17
N20
C31
Out of production
A-23-P
AP10PWG
XD-7817.00
7A12268A6N
MM 03306SI33
Dow Separan
AP30
NP10
NP10PWG
AP273 premium
Nalco Nalcolyte
8170
8171
8172
8173
8174
8182
8184
Stein-Hall
M-19
M-295PW
(Celanese)
AP30
NP10
NP10PWG
AP273 premium
8170
8171
8172
8173
8173
8182
8184
Out of production
M-295PW
540PW
361
24
MM 07078SI30
MM 02I09SIIO
MM 02089NIIO
MM 06II7SI32
B-7251
G-8319
B-7355
B-9065
B-8305
(continued)
-------
TABLE 8 (continued)
Polymer requested Polymer received Lot number
Hercules, Inc.
Reten 210 Reten 210 8201
Reten 220 Reten 220 8200
Reten 420 Reten 420 7338
Reten 421 Reten 421 5651
Reten 422 Reten 422 6815
Reten 423 Reten 423 6667
25
-------
TABLE 9. SUMMARY OF ACRYLAMIDE ANALYSES
Sample
K.
K.
K.
K.
K.
K.
K.
K.
K.
K.
K.
K.
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
W-l(A)
W-l(B)
W-l spiked
W-2(A)
W-2(B)
W-2 spiked
W-3(A)
W-3(B)
W-3 spiked
TW(1)
TW(2)
TW spiked
Blank spiked at
Blank spiked at
at 1 yg/£
at 1 yg/£
at 1 yg/S,
at 1 yg/£
2 yg/X,
2 yg/S.
Sample reduction
500 — •
500 — >
500 — -
500 — -
500 —
500 —
500 —
500 — -
500 — -
500 — -
500 — -
500 — -
500 — -
500 — -
1
2
1
1
0
1
1
0
1
1
0
1
1
1
.5
.0
.0
.0
.6
.0
.0
.6
.0
.1
.8
.0
.0
.0
0
< 0
< 0
< 0
0
0
0
< 0
0
0
< 0
< 0
2
2
Results
.4 yg/£
.5 yg/A
.5 yg/*,
.26 yg/8,
.16 yg/&
.76 yg/£
.92 yg/t
.16 yg/£
.76 yg/Jl
.68 yg/Jl
.21 yg/«,
.6 yg/£
.6 yg/&
. 9 y s/JL
No recovery
76% recovery
76% recovery
No recovery
130% recovery
150% recovery
Water blank
500
1.0
< 0.6 yg/J,
26
-------
Polyacrylamide Samples
The results of the analysis for residual acrylamide monomer are given in
Table 10. Note that Dow Puriflox N17 is now supplied as NP10PWG, and Dow
Purifloc N20 is now XD-7817.00. All of the polymers designated for analysis
by the Research Request were received and analyzed.
Analytical quality assurance was achieved by spiking at three concentra-
tion levels in duplicate. In each case an aliquot of the original solution
from the extraction bottle was reinjected and the response noted. A known
amount of acrylamide was then added to the extract in 2 ml of 80% methanol/
3.75 pH water to make up the volume taken out for the analysis. The polymer
and solution was then put on the wrist action shaker for 1 hr and then was
reinjected. The results follow in Table 11.
Federal regulations require that polyacrylamides used for potable water
treatment have less than 0.05% (500 pptn) residual monomer. Of the 32 polymers
analyzed, only one, Dow Separan NP10, had residual monomer above that level.
The Nalco 8173 polymer used by the Kansas City Water Treatment Plant during
MRI's sampling had a residual monomer level of 72 ppm. At this level, and
considering that the maximum permissible flocculant level is 1 ppm, the maxi-
mum possible acrylamide concentration in the water would be:
72 yg acrylamide x 10 3 g polyacrylamide = 0>07 yg/liter
1 g polyacrylamide liter of water
This level is less than the expected detection limit and indicates that the
use of polyacrylamide flocculants did not result in the addition of detectable
acrylamide to potable water. In fact, in the worst case of 500 ppm residual
monomer, the maximum water level would be 0.6 yg/liter.
27
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__TABLE 10. RESULTS OF ANALYSIS OF POLYACRYLAMIDE SAMPLES
Polymer requested
Calgon Coagulant Aid
233 (N)
253 (A)
Cyanamid Magnifloc
845 (A)
846 (A)
847 (A)
985 (N)
990 (N)
1849 (A)
1986 (N)
-
Dow Purifloc
C31
C51
A23P
N17
N20
Dow Separan
AP30
MP10
NP10PWG
AP273 Premium
Malco Malcolyte
8170
3171
8172
8173
3174
3132
8184
Stein-Hall (Celanese)
M-19
M-295PW
Hercules, Inc.
Reten 210
Seten 220
Reten 420
Reten 421
Reten 423
Reten 425'
Polvmer received
233
253
845A
846A
847A
985N
990N
1849A
1986N
900N
C31
Out of production
A-23-P
MP10PWG
XD-7817.00
AP 30
MP 10
MP10PWG
AP 273 Premium
8170
8171
8172
8173
8174
8182
8184
Out of production
M-295PW
540PW
351
Lot number
8 B422
8 A478
12885
12937
13081
13123
13109
13011
12993
13141
7A12268A6N
MM 03306SI33
MM 07078SI30
MM 02109SI10
.MM 02089NI10
MM 06117S132
B-7251
G-8319
B-7355
B-8340
-
B-9065
B-8305
-
-
-
3201
8200
7338
5651
6815
6667
Sample form
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Clear liquid
Clear liquid
Solid
Dark liquid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
•Liquid
Liquid
Solid
Liquid
Liquid
Liquid
Solid
-
-
Solid
Solid
Solid
Solid
Solid
Solid
Acrylamide concentration
25
19
0.5
6.5
46
102
189
2.3
< 0.5
214
<
See results
229
'5.4
608
34
112
355
184
.28
73
1.6
14
54
197
133
20
<
, 23
, 17
, 0.5
, 7.1
, 49
, 107
, 189
, 2.4
, < 0.53/
, 219
50^
<~S£/
for NP10PWG
, 230
, 6.5
, 6Q&
, 31
< 5i/
, 112
, 358
, 18Z«/
, 30.
, 71—'
5.9e-/
3.2S/
5.9£/ '
, 1.2
-
-
, 16
, 54
, 197
, 136
, 21
200A/
a/ Sample had no detectable response at lowest setting.
^/ Sample was a dark, honey-like liquid. Extraction was really only dilution. Sample gave a very large
peak which interfered with AA quantitation. Sample solution was spiked with 20 ppm and a side-peak
of 20 nm appeared. Therefore, sample concentration is given as < 50 ppm.
c/ Sample had interfering peak. A 2 mm shoulder peak could be seen at (0.1).
d_/ Extraction solution is slightly yellow in color but there were no interfering peaks.
_£/ Solutions would not centrifuge or filter. They were allowed to stand in centrifuge tubes and a thin
layer of clear liquid formed on the surface. An aliquot of this solution was injected for the assay.
{_/ Sample obtained from Kansas City Water Treatment Plant.
£/ Sample has interfering peak. An injection of this sample solution spiked at 20 ppm was detectable;
therefore, sample concentration is given as < 200 ppm.
28
-------
TABLE 11. RECOVERIES FROM SPIKED POLYMERS
No.
No.
No.
No.
No.
No.
No.
No.
No.
Sample
1 (Magnifloc 845A)
1 + 0.4 ppm
2 + 0.4 ppm
31 (Purifloc NP10PWG)
31 + 4.0 ppm
32 -f 4.0 ppm
15 (Magniflox 900N)
15 + 20 ppm
16 + 20 ppm
Peak
height
(mm)
8
38
38
53
128
124
142
208
212
Atten.
0
0
0
0
0
0
0
0
0
.01
.01
.01
.04
.04
.04
.2
.2
.2
Adj.
peak Cone.
height (mm) (ppm)
0.
0.
0.
2.
5.
4.
28.
41.
42.
08
38
38
12
12
96
4
6
4
0.
0.
0.
3.
7.
7.
41.
61.
62.
13
57
57
.13
54
30
7
2
3
% Recovery
—
107
107
_
106
102
—
99
101
29
-------
REFERENCES
1. "Assessment of the Need for and Character of Limitations on Acrylamide and
Its Compounds," Draft Final Report, EPA Contract No. 68-01-4308, July
1977.
2. "Environmental Monitoring Near Industrial Sites: Acrylamide," Final Re-
port, EPA Contract No. 68-01-4115, March 1978.
30
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TECHNICAL REPORT DATA
(Please read lnunictions on the reverse before completing)
1. REPORT NO.
EPA-560/13-79-013
3. RECIPIENT'S ACCESSION»NO.
4. TITLE AND SUBTITLE
Sampling and Analysis of Selected Toxic Substances
Task I: Acrylamide
5. REPORT DATE
December 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHORISI
John E. Going, Ken Thomas
8. PERFORMING ORGANIZATION REPORT NO,
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-5017
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Task Final 9/78 - 9/79
14. SPONSORING AGENCY CODE
EPA-OTS
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A sampling and analysis program was conducted to determine the level of residual
acrylamide monomer in selected polymers and to determine if the use of those polymers
in water treatment leads to measurable levels of acrylamide in the water.
Methods for the determination of acrylamide in water and in polyacrylamide were
validated. Water samples were reduced in volume by evaporation and analyzed by GC
using a nitrogen selective thermionic detector. The detection limit was determined
to be ^ 1 yg/liter. Polyacrylamide samples were extracted with 80% methanol/20% pH
3.75 water for 3 hr. The extracts were analyzed by HPLC with a UV detector set at
200 ran. The monomer limit of detection was ^ 0.5 vg/g.
One potable water treatment plant was sampled at pre- and post-flocculation points
MRI tap water was analyzed for comparison. No acrylamide above the detection limit was
found in any of the samples.
Thirty-two polymers were analyzed for residual acrylamide. When not obscured by
interferences, the observed acrylamide ranged from 0.5 to 600 yg/g.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
COSATl Field/Group
Acrylamide
Water
Polymers
Sampling
Analysis
Environmental Monitoring
Water Treatment Plants
Organic
Chemistry
3. DISTRIBUTION STATEMENT
Release unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
36
20. SECURITY CLASS (THispagel
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
31
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