MIDWEST RESEARCH INSTITUTE
MRI
EPORT
SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
Task 2 - Acrylamide
Contract No. 68-01-4115
Dr. Vincent J. DeCarlo
Supervisor, Special Actions Group
Office of Toxic Substances
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, B.C. 20460
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MRI-NORTH STAR DIVISION 10701 Red Circle Drive, Minnetonka, Minnesota 55343 • 612 933-7880
MRI WASHINGTON, D.C. 20006-Suite 250,1750 K Street, N.W. • 202 293-3800
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SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
Task 2 - Acrylamide
Contract No. 68-01-4115
Dr. Vincent J. DeCarlo
Supervisor, Special Actions Group
Office of Toxic Substances
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, D.C. 20460
Prepared for
Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20460
MIDWEST RESEARCH INSTITUTE 425 VOLKER BOULEVARD, KANSAS CITY, MISSOURI 64110 • 816753-7600
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NOTICE
This report has been reviewed by the Office of Toxic Substances,
Environmental 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 con-
stitute endorsement or recommendation for use.
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CONTENTS
Section Page
I Summary 1
II Introduction 4
III Experimental Methods 6
Sampling Protocol 6
Analysis Protocol 8
Method Development for Sampling and Analysis .... 10
IV Selection of Sampling Sites 24
V Discussion of Results ' 30
Hercules, Inc., Hopewell, Virginia 30
Calgon Corporation, Ellwood City, Pennsylvania ... 43
Nalco Chemical Company, Garyville, Louisiana .... 51
American Cyanamid, Fortier, Louisiana 58
St. Regis Paper Company, Sartell, Minnesota 68
Dow Chemical, Midland Michigan 71
References.
78
ii
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FIGURES
No. Title Page
1 Vaporization of acrylamide for air sampling studies .... 16
2 Recovery of acrylamide versus level of acrylamide 19
3 Location of sampling sites 29
4 Sampling locations at Hercules, Inc., Hopewell, Virginia. . 34
5 Mass spectrum of acrylamide 42
6 Selection ion current plots, m/e = 71.0371 44
7 Sampling locations at Calgon Corporation, Ellwood City,
Pennsylvania 46
8 Sampling locations at Nalco Chemical Company, Garyville,
Louisiana 54
-^
9 Sampling locations at American Cyanamid, Fortier,
Louisiana 63
10 Sampling locations at St. Regis Paper Company, Sartell,
Minnesota 72
11 Map of sampling sites for acrylamide at Midland, Michigan . 74
iii
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TABLES
No. Title Page
1 Analysis Data Summary for Task 2 3
2 BMI's Sampling and Analysis Protocol 11
3 Recovery of Acrylamide Following Evaporation 17
4 Percent Recovery of Acrylamide 18
5 Percent Recovery Versus Volume of Air 20
6 Recovery of Acrylamide in Water Following Direct
Evaporation 21
7 BMI's List of Acrylamide Production and User Sites .... 25
8 Recommended Sampling Sites 27
9 Sampling Schedule 31
10 Field Sampling Summary 32
11 Summary of Air Sampling Parameters 32
12 Air Sampling Data for Hercules, Inc., Hopewell, Virginia . 36
13 Water and Sediment Sampling Data for Hercules, Inc.,
Hopewell, Virginia 37
14 Weather Conditions During Sampling at Hercules, Inc.,
Hopewell, Virginia: Source of Data, Byrd Airport,
Richmond, Virginia 39
15 Acrylamide Concentrations in Air Samples from Hercules,
Inc., Hopewell, Virginia 40
iv
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TABLES (continued)
No. Title Page
16 Acrylamide Concentrations in Water Samples from
Hercules, Inc., Hopewell, Virginia 40
17 Acrylamide Concentrations in Soil and Sediment Samples
from Hercules, Inc., Hopewell, Virginia 41
18 Air Sampling Data for Calgon Corporation, Ellwood City,
Pennsylvania 47
19 Water and Sediment Sampling Data for Calgon Corporation,
Ellwood City, Pennsylvania 49
20 Weather Conditions During Sampling at Calgon Corporation,
Ellwood City, Pennsylvania: Source of Data, Pittsburgh
International Airport, Pittsburgh, Pennsylvania 50
21 Acrylamide Concentrations in Air Samples from Calgon
Corporation, Ellwood City, Pennsylvania 52
22 Acrylamide Concentrations in Water Samples from Calgon
Corporation, Ellwood City, Pennsylvania 53
23 Acrylamide Concentrations in Soil and Sediment Samples
from CAlgon Corporation, Ellwood City, Pennsylvania. . . 53
24 Air Sampling Data for Nalco Chemical Company, Garyville,
Louisiana 56
25 Water Sampling Data for Nalco Chemical Company,
Garyville, Louisiana 57
26 Soil Sampling Data for Nalco Chemical Company, Garyville,
Louisiana 57
27 Weather Conditions During Sampling at Nalco CHemical,
Garyville, Louisiana: Source of Data, New Orleans
International Airport, New Orleans, Louisiana 59
28 Acrylamide Concentrations in Air Samples from Nalco
Chemical, Garyville, Louisiana 60
v
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TABLES (concluded)
No. Title Page
29 Acrylamide Concentrations in Water Samples from Nalco
Chemical Company, Garyville, Louisiana 61
30 Acrylamide Concentrations in Soil Samples from Nalco
Chemical Company, Garyville, Louisiana 61
31 Air Sampling Data for American Cyanamid, New Orleans,
Louisiana 64
32 Water and Sediment Sampling Data for American Cyanamid,
New Orleans, Louisiana 65
33 Soil Sampling Data for American Cyanamid, New Orleans,
Louisiana 66
34 Weather Conditions During Sampling at American Cyanamid,
New Orleans, Louisiana: Source of Data, New Orleans
International Airport, New Orleans, Louisiana 67
35 Acrylamide Concentrations in Air Samples from American
Cyanamid, Fortier, Louisiana 69
36 Acrylamide Concentrations in Water Samples from American
Cyanamid, Fortier, Louisiana 70
37 Acrylamide Concentrations in Soil and Sediment Samples
from American Cyanamid, Fortier, Louisiana 70
38 Water Sampling Data for St. Regis Paper Company, Sartell,
Minnesota 73
39 Acrylamide Concentrations in Water Samples from St. Regis
Paper Company, Sartell, Minnesota 73
40 Analytical Data for Water Samples from Midland, Michigan . 75
41 Analytical Data for Air Samples from Midland, Michigan . . 76
42 Analytical Data for Soil Samples for Midland, Michigan . . 77
VI
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SECTION I
SUMMARY
The purpose of this program is to provide sampling and analysis cap-
abilities to Environmental Protection Agency's (EPA) Office of Toxic Sub-
stances, so that the levels of suspected toxic substances in air, water,
soil, and sediment at designated locations throughout the United States
could be determined. The second task was the sampling and analysis for
acrylamide (AA).
Methods for sampling and analyzing AA in air, water, soil, and sed-
iments were developed or modified.
Air samples were collected on Ghromosorb 101 and desorbed for anal-
ysis with methanol. Water samples and methanol extracts of soil and sed-
iment samples were concentrated by evaporation prior to analysis. All
extracts were analyzed by gas chromatography with nitrogen selective de-
tection. The detection limits of environmental samples varied but were
*\
generally 0.2 y,g/m for air, 0.8 }j,g/liter for water, and 0.02 M-g/g for
soil and sediment.
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Five industrial sites were selected for sampling. Two plants were
producers of AA, two plants were producers of AA and polyacrylamide and
one plant was a polyacrylamide user. A sixth site, for which some results
are reported, was sampled previously by another contractor.
A summary of the analytical results from the six industrial plants
is given in Table 1. No AA was found in any air samples in either the
vapor or particulate form. Acrylamide was detected in the aqueous dis-
charge stream for one plant sampled by MRI. The level found was 1,500 ppb
and the identification of AA was confirmed by GC/MS. No AA was detected
in any of the soil or sediment samples.
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Table 1. ANALYSIS DATA SUMMARY FOR TASK 2
Air (ug/m5)!? Water (yig/^)£/ Soil (ug/g")g7 Sediment
Site Process High Low High Low High Low High Low
Hercules, Inc. Producer of
Hopewell, Virginia polyacrylamide < 0.4-1.1 1,500 <0.8 <0.08 <0.08
Calgon Corporation Producer of
Ellwood City, Pennsylvania polyacrylamide <0.1 < 0.8 <0.02 <0.02
Nalco Chemical Company Producer of
Garyville, Louisianna acrylamide and
polyacrylamide < 0.1-0.3 < 0.8 < 0.02 < 0.02
American Cyanamid Producer of
Fortier, Louisianna acrylamide and
polyacrylamide < 0.1 < 0.8 < 0.02 < 0.02
St. Regis Paper Company User of
Sartell, Minnesota polyacrylamide - < 0.8
Dow Chemical-
Midland, Michigan < 1.0 25-125 < 25 < 0.02
al When no acrylamide was detected, the detection limits have been given.
b/ Data from Reference 1.
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SECTION II
INTRODUCTION
Acrylamide is the most important chemical in its group, being pro-
duced at an estimated rate of 63 million pounds per year as of 1976.2.' By
1978, all production should be based on catalytic hydration of acryloni-
trile. The major producers of AA are American Cyanamid, Dow Chemical, and
Nalco Chemical. The principal use of AA (~- 80%) is in the production of
water soluble polymers, commonly called polyelectrolytes, flocculants, co-
agulants, thickening agents, retention aids, and drainage aids. Polymer
production consumes nearly all AA production, much of it captively.
Acrylamide release to the environment occurs at monomer and polymer
manufacturing sites, polymer application sites, and in transportation and
handling. Air levels of AA would not be expected to be high due to its low
vapor pressure. Aqueous discharge is a more likely route of release be-
cause of its extremely high water solubility and the major use of poly-
acrylamides in aqueous systems, e.g., flocculants, grouts. The only avail-
able monitoring data for the discharge of AA into the environment is from
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Croll's study in Great Britain during which levels as high as 42 |j,g/liter
K A 3/
were observed.~
The environmental concern about AA results principally from its re-
ported neurotoxicity. The acute LDcg in rodents— is 200 mg/kgj however,
lower dosages have shown a cumulative toxicity.—' The carcinogenicity of
AA is unknown.
In 1976, MRI Project No. 4280-C, entitled "Sampling and Analysis of
Selected Toxic Substances" was initiated. The objective of this program
is to provide the EPA with sampling and analysis capabilities to determine
the levels of selected toxic substances in air, water, soil, and sediments
from designated sources and ambient locations throughout the United States.
The first task on this program, vinylidene chloride, has been completed.
The second task on the program, which is the subject of this report, is
AA. A requirement of the program is the development of a sampling and anal-
ysis protocol that is sensitive and reliable at the low parts per billion
range. Appropriate industrial sites are then selected and monitored for
AA using the protocol.
The remainder of this report describes the experimental methods em-
ployed, including the development of the sampling and analysis protocol,
the selection of sampling sites, and a discussion of the monitoring re-
sults.
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SECTION III
EXPERIMENTAL METHODS
SAMPLING PROTOCOL
Air Sampling
Air was sampled at four to five stations deployed upwind, downwind,
and crosswind of the industrial sites. Duplicate samplers were placed at
some of the stations. The sampling probes were set at 1.5 m above ground
and air was sampled at 0.5 to 1 liters/rain continuously for up to 24 hr.
The meteorological conditions that existed during each test were ob-
tained from the nearest National Weather Station. Wind speed and direc-
tion, temperature, and precipitation were included in the data log.
The sampling train for the collection of AA from ambient air con-
sisted of the following components assembled in the order given: (a)
Millipore filter (AAWP03700), directed into the wind; (b) top Chromosorb
101 tubej (c) bottom Chromosorb 101 tube; and (d) 24-v DC vacuum pump.
The adsorbent tubes were constructed of glass and were 8 mm OD x 6 mm
ID x 18 cm in length. Prior to use the internal surfaces were silanized.
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The tubes were packed with 0.7 g 60/80 mesh Chromosorb 101 that had been
Soxhlet extracted with methanol overnight and then dried at 150°C for 4 hr
under a stream of nitrogen. Minimum lengths of natural tubing were used
to connect the sampling tubes to the pumps. No critical orifice was used
as the pressure drop of the two tubes was sufficient to keep the flow rate
under 1 liters/min. The actual flow in the field was monitored by cali-
brated rotameters every 3 to 4 hr. Power was supplied to the DC pump by
two 24-v lantern batteries connected in parallel. The pump and batteries
were encased in a cardboard-polystyrene shipping box which was then an-
chored at the sampling site. The reliability of this system has been dem-
onstrated in previous OTS studies••2*I/ After sampling was completed, the
tubes were capped with rubber slip-on septa, wrapped in aluminum foil and
stored over dry ice for shipment to MRI. At MRI, the tubes were kept on
dry ice until analyzed.
Water Sampling
Grab water samples at the outfalls were collected periodically dur-
ing the air sampling period and composited in 1 gal. brown silanized bot-
tles with Teflori®-lined caps. Upstream and downstream samples were collected
concurrently. After collection the samples were placed on wet ice for ship-
ment to MRI. At MRI, the samples were stored at 2 to 4°G.
Soil Sampling
Soil samples from the top 10 mm were collected at the air sampling
stations and placed in 16-oz jars with aluminum foil-lined caps. The jars
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were then stored over dry ice for shipment to MRI. At MRI, the samples
were kept on dry ice until analyzed.
Sediment Sampling
Sediment samples were collected by use of an Eckman dredge. The sam-
ples were placed in 16-oz jars with aluminum foil-lined caps. After col-
lection the samples were placed and shipped on wet ice to MRI. At MRI, the
samples were stored at 2 to 4°C.
ANALYSIS PROTOCOL
Air Samples
The Chromosorb 101 tubes were inverted and eluted with 10 ml of meth-
anol. The methanol extract was then reduced in volume to approximately 0.5
ml by evaporation with a nitrogen stream. The Millipore particulate fil-
ters were extracted for 0.5 hr in an ultrasonic bath with 2.0 ml water.
The extracts were analyzed by GC with electrolytic conductivity
(Hall) detection. The operating parameters were as follows:
Column: 1.8 m x 2 mm ID silanized glass
Packing: 80/100 mesh Chromosorb 101
Carrier: Helium at 30 ml/rain
Reaction tube: Quartz with Ni catalyst, hydrogen at 35 ml/min
Electrolyte: 157= isopropanol/water, 0.5 ml/min
Injector temperature: 240°C
Column temperature: 220°C
Reaction furnace temperature: 820°C
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A limited number of sample extracts were spiked with a known quantity of
AA and reanalyzed. The results were used to establish limits of detection.
Water Samples
A 250-ml aliquot of the water sample was reduced in volume to about
10 ml by rotary evaporation. The sample was then further reduced in vol-
ume to 0.5 to 8 ml using a nitrogen stream. Any solid which formed dur-
ing the evaporations was removed by centrifugation and extracted with
methanol. The two fractions were analyzed separately by GG using the con-
ditions outlined above. A limited number of samples were spiked with a
known amount of AA and reanalyzed in order to establish the detection
1 imi t s •
Soil Samples
Fifty-gram aliquots of the soil samples were extracted twice with
50 ml portions of methanol using ultrasonic agitation. The extracts were
combined and evaporated to 5 ml. Any solid which precipitated was removed
by centrifugation. Separate soil samples were dried at 110°C for 4 days
in order to determine the moisture content. The sample extracts and spiked
sample extracts were analyzed by GC using the conditions outlined above.
Se diment Samp 1e s
Sediment samples were first centrifuged to separate the water which
was then removed. A 50-g sample was then prepared and analyzed in the same
manner as the soil samples.
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GC/MS Confirmation
Samples were confirmed by GC/MS using the same column and conditions
described above. In order to eliminate a column bleed problem, the MS was
operated in a high resolution selected ion monitoring mode. Although only
one mass was monitored, the selectivity provided by high resolution MS
virtually eliminated all compounds except a CoHj-NO. The matching of reten-
tion times then confirms the presence of AA. The instrument operating con-
ditions were as follows:
0
Instrument: Varian MAT 31lA mass spectrometer with Varian 2700 gas
chromatograph
Data system: Varian Spectrosystem 100 MS
Separator: Watson-Bieman
Mass monitored: 71.0371
Resolution: ~ 7,000
lonization potential: 70 ev
Emission current: 1 mA
Multiplier gain: 4 x 106 - 2 x 107
METHOD DEVELOPMENT FOR SAMPLING AND ANALYSIS
A protocol for sampling and analysis of AA was under development by
Batelle Memorial Institute (BMI). The techniques which were proposed and
used at one site are summarized in Table 2. Also included is the extent
to which the method was validated. In discussing the protocol with OTS
10
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Table 2. BMI'S SAMPLING AND ANALYSIS PROTOCOL^'
I/
Media
Air
Vapor
Particulates
Water
Sampling technique
Midget impinger with 35 ml of
40% methanol-water. Sample
1-1.5 1pm for 24 hr. Store
in a refrigerator.
Extract 3 times for 10 min with
7 ml methanol.
Grab sample of 1 liter.
Sample treatment and preparation
Evaporate to 1 ml. Analyze as a
water sample by direct
injection.
Evaporate to 0.5 ml or less.
Analyze as a water sample by
direct injection.
Evaporate 20 ml to 0.5 ml or less
by Kuderna Danish or slow nitro-
gen stream with heat. Analyze
by direct injection.
Verification
or recovery
None reported.
None reported.
10 ml of 1 ppm
evaporated
and reconsti-
tuted gave
total recov-
ery in silyl-
ated vessels.
Soil
Dry and extract a 50-g sample
with 70 ml methanol. Repeat
and filter the combined
extracts.
Evaporate to 0.5 to 1 ml. Analyze
as a water sample by direct
injection.
None reported.
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personnel, it was decided that some modifications might be worth investi-
gating. The development of MRI's final protocol is discussed below.
GC Analysis Conditions
The procedure used by BMI was based on direct injection of the aque-
ous or methanolic sample onto a Chromosorb 101 column. A nitrogen sensi-
tive thermionic detector was used to achieve the necessary selectivity for
AA in the presence of hydrocarbons. Initially, the acrylamide analyses at
MRI were performed on a Perkin-Elmer Model 3920 instrument equipped with
a nitrogen/phosphorus selective flame ionization detector. A 5 ft x 1/8
in. OD glass column packed with 80/100 mesh Chromosorb 101 was used with
a helium carrier flow rate of 20 ml/min. The operating conditions were:
injection temperature, 220°C; column temperature, 220°C; transfer line/
detector temperature, 250°C; hydrogen flow, 3 ml/min; air flow, 65 ml/
min. At these conditions AA elutes in 3.8 min. The sensitivity of the de-
tector was monitored periodically by measuring the bead current. A con-
stant bead current of 30 picoamperes was maintained by adjustment of the
bead heating current with a jet potential control setting of 3. However,
because of difficulties in maintaining sensitivity levels on that system,
it was decided to investigate a different detection system. A Varian 3700
gas chromatograph equipped with a Hall Electrolytic Conductivity Detector
(Tracor, Inc.) in the nitrogen mode was investigated. A 6 ft x 2 mm ID glass
column packed with 80/100 mesh Chromosorb 101 was used with a helium car-
rier flow rate of 30 ml/min. Other operating conditions were: injector
12
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temperature, 240°C; column temperature, 220°Cj detector base temperature,
240°C; detector furnace temperature, 820°C; hydrogen reactor gas flow, 35
ml/min; 157, isopropanol/water electrolyte flow rate, 0.5 ml/min. Under
these conditions, AA eluted in 5.1 min. A calibration curve using AA in
methanol is shown in Figure 2. The sensitivity and stability of the Hall
detector appear to be better than that of the nitrogen/phosphorus selec-
tive AFID.
This system was then used for most of the method development studies
and all of the sample analyses. In operation, the solvent was vented for
3 to 4 min following sample injection.
Air Samples
Recovery from Charcoal - The sampling method proposed but untested by BMI
used water filled midget impingers that were preceded by a glass fiber fil-
ter. It was agreed at the project meeting that the impinger train had sev-
eral disadvantages and that it would be worth investigating the use of
solid adsorbents, e.g., charcoal, as the trapping medium. Accordingly,
our work concentrated on evaluating several alternate air sampling trains.
In the first set of experiments, activated charcoal was tested as an
adsorbent. The charcoal, Fisher Coconut charcoal, 8/15 mesh, was extracted
with methanol and activated at 100 or 250°C under a flowing stream of ni-
trogen for 1 hr. A preliminary recovery experiment was made by packing two
glass tubes, 8 mm OD x 6 mm ID x 60 mm length, with about 1 g of charcoal
activated at 100 or 250°C. Acrylamide, 100 pi of 1 ppt in methanol, was
injected onto the top of the two columns. The tubes were eluted directly
13
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with methanol and successive 4-ml aliquots were collected for analysis.
In both cases, the AA that was desorbed completely eluted in the first 12
ml of methanol. The total recoveries were 57% and 30% for charcoal acti-
vated at 100 and 250°C, respectively. The results suggested that AA was
being irreversibly adsorbed on highly reactive sites and that the high
temperature charcoal had more reactive sites. A reverse desorption exper-
iment was made by adding 5 ml of 10 ppm AA in methanol to 2 g of the 100°C
charcoal. The solution level of AA was monitored periodically for 40 min.
At that time, the "free" AA had dropped from 100 to 62%, indicating that
the charcoal was actually adsorbing AA from the methanol. Thus, while
charcoal might be a good trap for AA, the low recovery by methanol elu-
tion encouraged the search for another adsorbent.
Recovery from Tenax® and Ghromosorb 101 - The same reverse desorption
experiment was repeated using 80/100 mesh Chromosorb 101 and 60/80 mesh
Tenax®-GC. After 40 min, the "free" AA was 93 and 98%, respectively. An-
other set of experiments with the glass tubes was run, using charcoal
(100°C activation), Tenax® and Chromosorb 101. The tubes held about 1, 0.6,
and 0.7 g of adsorbent, respectively. Each adsorbent was spiked with 100
|jil of 1 ppt AA in methanol and air was drawn through at 0.5 liter/min for
30 min. The tubes were inverted and eluted with two 10-ml aliquots of meth-
anol. The recoveries were 65, 110 and 90%, respectively, and all the AA
was found in the first 10 ml of methanol.
14
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A related experiment was then performed in an attempt to transfer
the AA to the adsorbent as a vapor rather than a solution. Acrylamide was
vaporized using the apparatus shown in Figure 1.
Air was pulled through the system for 1 hr at 0.5 liter/min. The in-
side temperature of the U-tube was measured at ~ 100° C. Acrylamide was re-
moved from the Chromosorb 101 by elution with 10 ml methanol and an 83%
recovery was achieved. This level of recovery was felt to be within exper-
imental error of the 9070 recovery achieved following the direct application
of the AA in methanol. Subsequent recovery experiments were done by direct
injection of AA in methanol onto the adsorbent. Chromosorb 101 has been
tentatively chosen over Tenax® for the sampling train for reasons of avail-
ability and cost.
In the next experiment, Chromosorb 101 was spiked with 200 p,g AA and
air was drawn through the tube for 16 hr at 0.6 liters/min. After elution
with 10 ml methanol, a 90% recovery of AA was found. Additional experiments
run with longer sampling times and higher flow rates are discussed below.
Evaporation of Methanol Extracts - The size of the adsorbent traps being
evaluated required 10 ml of methanol for quantitative elution. The possi-
^
bility of reducing this volume to 1 ml or less by evaporation was investi-
gated. The objective of the study was to lower the air level limit of de-
tection by increasing the analyte concentration through evaporation. Four
25-ml aliquots of 10-ppm acrylamide in methanol were evaporated to 1 ml
at 25 and 50°C in silylated and unsilylated vials, under a stream of ni-
trogen. The recoveries are given in Table 3.
15
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Vacuum Pump
Pyrex Tubing
Hoi- Air Gun
t
Glass Wool
Chromosorb 101
•Glass Wool
•Teflon Coupling
Acrylamide in Methanol
Figure 1. Vaporization of acrylamide for air sampling studies
16
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Table 3. RECOVERY OF ACRYIAMIDE FOLLOWING EVAPORATION
Temperature Silylated vial Unsilylated vial
25° C 837, 74%
50° C 83% 83%
Thus solutions of AA in methanol can be effectively evaporated at 50°C in
silylated or unsilylated glassware. As a precaution, however, silylated
glassware was used routinely*
Recovery at Various Loading Levels - To determine the percent recovery at
various levels of loading, 2.9 to 214 ^g of AA was loaded by injection
onto 0.7 g 60/80 mesh Chromosorb 101 packed into silanized glass tubes.
The larger mesh adsorbent was used to reduce the pressure drop across the
sampling tube. Each tube was connected to a small pump and air was drawn
through the tube at a rate of 325 to 450 ml/min. After 24 hr, each tube
was inverted and eluted with 10 ml methanol. The eluates from the tubes
loaded with 100 to 200 (j,g AA were analyzed directly. The eluates from the
tubes loaded with 2.9 to 29 y,g AA were evaporated from 10 ml volume to
approximately 1 ml using a 50°C water bath and a gentle stream of nitrogen.
In order to calculate the exact volumes of the evaporated samples, a known
amount of benzonitrile in methanol was added to each. The samples were then
analyzed and quantitated using a mixed AA-benzonitrile standard. The per-
cent recovery for each sample was determined and is listed in Table 4.
The data are also graphed in semi-log form in Figure 2. The four points
were averaged to obtain a 99% recovery level.
17
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Table 4. PERCENT RECOVERY OF ACRYLAMIDE
Acrylamide ^g Acrylamide Percent
loaded recovered recovery Average
2.90 3.01 104 104%
29.0 38.7 133 )
29.0 39.7 137 > 121%
29.0 26.6 92 )
107 96.0 90 90%
214 156 73 )
214 171 80 > 77%
214 168 79 )
18
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140
120
100
0£.
LU nn
> 80
O
U
^ 60
40
20
n
"*™
_ <
i
' J
—
-
•
1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
10
20 30 100
ACRYLAMIDE LOADED
200 300
1000
Figure 2. Recovery of acrylamide versus level of acrylamide
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Recovery at Various Air Volumes - An experiment was then performed to de-
termine the effect on recovery of the volume of air sampled in a 24-hr
period. Pour silanized glass tubes packed with 0.7 g Chromosorb 101 were
loaded with 214 (j.g AA by injection of a methanolic standard. Each tube
was connected to a small vacuum pump and air was drawn through at a rate
of 250 to 600 ral/min. At the end of the 24-hr period, each tube was in-
verted and eluted with 10 ml methanol and analyzed. The percent recovery
was determined and is listed in Table 5.
Table 5. PERCENT RECOVER? VERSUS VOLUME OF AIR
yg Acryl- yg Acryl-
-amide amide Air flow Total air Percent
Sample loaded recovered rate (ml/min) volume (£) recovery
1
2
3
4
214
214
214
214
168
171
156
123
250
370
380
600
360
540
600
880
79
80
73
57
It appears that the percent recovery is decreasing at the higher
flow rate. It was concluded that air sampling should be done at 500 ml/
min or less for best recovery. If a high flow rate is desired, the use of
a backup tube is mandatory.
Water Samples
Recovery from Charcoal - The procedure first proposed by BMI-=-' was based
upon the adsorption of AA from water with a column of activated charcoal.
It was reported that 1,000 ml of water, 1 ppm in AA, could be passed
through 2 g of petroleum-based charcoal (30/60 mesh, SKC, Inc.) and the
20
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AA eluted with 20 ml methanol with a 76% recovery. A greater concentra-
tion factor could be achieved by evaporating the methanol to 1 ml or less.
The experiment was repeated at MRI with less success. Two grams of
the Fisher charcoal activated at 100° C were packed into a column and 1,000
ml of water, 1.07 ppm in AA, was passed through at 10 ml/min. The charcoal
was dried with a nitrogen gas stream and eluted with 25 ml methanol. Only
16% of the expected AA was recovered. It was not established whether the
low recovery was due to breakthrough or incomplete desorption with metha-
nol.
Direct Evaporation - It was also reported by BMlI/ that aqueous AA solu-
tions could be preconcentrated by direct evaporation.
Several direct evaporation experiments were conducted using conven-
tional rotary evaporator equipment. Increasing volumes of water with de-
creasing AA concentrations were evaporated with a 50° C heated bath, to
less than 1 ml. At the higher levels, the concentrate was diluted to 10.0
ml and analyzed directly. At the lower concentrations, a known amount of
benzonitrile was added to the ~ 1 ml of concentrate as an internal stan-
dard. The percent recoveries of the low level samples are given in Table
6.
Table 6. RECOVERY OF ACRYLAMIDE IN WATER
FOLLOWING DIRECT EVAPORATION
Original
volume (ml)
100
100
1,000
Acrylamide
(ppm)
1.00
0.100
0.010
Final
volume
10.0
2.2
0.89
Percent
recovery
92
74
71
21
-------
It was concluded that direct evaporation could be used on the real
samples with an acceptable recovery.
Soil Samples
Two 10-g samples of Kansas City garden soil were spiked with 107 |j,g
of AA. The first was packed into a chromatography column and eluted with
methanol. Five successive 5-ml aliquots were collected and analyzed. The
first 5-ml fraction was found to contain all of the added AA. The second
10-g sample was covered with 10 ml methanol in a vial and sonicated for
5 min. The sample and methanol were then centrifuged and the extract re-
moved and analyzed. The recovery of AA was 75%. An unspiked 10-g sample
was also eluted with 5 ml methanol and found to contain no AA.
For analysis of field soil samples, an elution with methanol will be
used*
Sediment Samples
The sediment sample collected from the Calgon site was used for the
development of the sediment analysis protocol. Six sediment samples of
approximately 10 g each were centrifuged and the supernatant water was
removed. Four of the samples were spiked with 100 y,g of AA. Two of the
spiked samples were transferred to columns and eluted successively with
three 5-ml aliquots of methanol. The total recoveries of AA from the sam-
ples were 83 and 65%.
The other two spiked samples were sonicated 1 hr with 10 ml methanol.
In this case, 76 and 81% of the added AA were recovered. No AA was recov-
ered from the unspiked sediment using either elution technique.
22
-------
The sonication technique will be used for the analysis of real sam-
ples due to its experimental simplicity and slightly better precision. Ap-
proximately 50 g of sediment will be sonicated successively with two 50-ml
aliquots of methanol. The methanol extracts will be combined and evaporated
to 5 ml prior to analysis.
23
-------
SECTION IV
SELECTION OF SAMPLING SITES
A meeting was held at the Office of Toxic Substances, EPA, in June
1977 to discuss the selection of sampling sites. Present were Dr. J.
Hillman and Dr. P. Hilgard of OTS, and Dr. J. Going from MRI.
Table 7 lists the production and user sites that had been proposed
for sampling by BMI. Standard Oil of Ohio was eliminated as it no longer
produces AA. American Cyanamid, New Orleans, was eliminated based on the
remarks of Dr. Bikales, National Science Foundation, that the plant would
be difficult to monitor because of its location. It was suggested that
Du Pont probably uses AA as a thickening agent for gelled explosives.
Table 7 also lists the user sites proposed by BMI. Betz was estab-
lished to be a minor user and Celanese no longer uses AA. The paper mills
were eliminated on the suggestion of Dr. Bikales.
With the assistance of Bob Peterson of MRI's North Star Division, ad-
ditional information was gathered about the producers and users of AA. A
new list of recommended sampling sites was developed and discussed with
24
-------
Table 7. BMI'S LIST OF ACRYLAMIDE PRODUCTION AND USER SITES-
II
Acrylamide production sites
Dow Chemical, USA, Midland, Michigan
DuPont, Belle, West Virginia
Bio-Rad Laboratories, Richmond
California
American Cyanamid, Linden,
New Jersey
American Cyanamid, Fortier
Louisiana
Standard Oil of Ohio, Lima, Ohio
Acrylamide user sites
Hercules, Inc., Hopewell, Virgina
Nalco Chemical Company, Chicago,
Illinois
Calgon Corporation, Pittsburgh,
Pennsylvania
Pascagoula, Mississippi
(soil stabilization)
Wenatchee, Washington
(soil stabilization)
Betz Laboratory, Trevase,
Pennsylvania
Celanese, Charlotte,
North Carolina
Kimberly-Clark, Appleton,
Wisconsin
Mead Paper, Chillicothe, Ohio
Recommended production sites
Dow Chemical, Midland, Michigan
DuPont, Belle, West Virginia
Bio-Rad Laboratories, Richmond,
California
American Cyanamid, Linden,
New Jersey
Recommended user sites
Hercules, Inc., Hopewell, Virginia
Nalco Chemical Company, Chicago,
Illinois
Calgon Corporation, Pittsburgh,
Pennsylvania
Soil stabilization site to be
specified
Soil stabilization site to be
specified
25
-------
J. Hillman and P. Hilgard of OTS. This list, given as Table 8, differs in
the following ways.
The Dow Chemical plant at Midland, Michigan, had been sampled by EMI
and was eliminated. The Bio-Rad plant is a minor producer and user and is
unlikely to have significant emissions of AA. The American Cyanamid plant
at Linden, New Jersey, was not recommended for several reasons. The plant
will be switching to the catalytic conversion of acrylonitrile as the pro-
duction process by 1978. The physical location of the plant makes off-
plant air sampling extremely difficult. Furthermore, the aqueous wastes
are barged out into the Atlantic Ocean and dumped.
It was recommended that the American Cyanamid plant at Fortier,
Louisiana, be sampled instead. It is representative of the most commonly
used production process and is both a producer and a user. It was also
recommended that the Nalco plant at Garyville, Louisiana, be sampled as
a producer and a user. This plant was not on the BMI producers list.
Among the polymer producers, Nalco at Garyville (as a monomer and poly-
mer producer) rather than at Chicago, Illinois, was recommended.
A paper manufacturer, in the category of a polymer user, was added
to the recommended list. The St. Regis plant at Sartell, Minnesota, would
be monitored for aqueous discharges only.
The Hercules plant in Hopewell, Virginia, the Calgon plant in
Pittsburg, Pennsylvania, as well as a soil stabilization site, were recom-
mended by both MRI and BMI. In the course of attempting to locate a suit-
able soil stabilization site, MRI was advised by Mr. David Withers,
26
-------
Table 8. RECOMMENDED SAMPLING SITES
to
—I
Site
Location
Monomer and polymer producers
American Cyanamide Fortier, Louisiana
Nalco
Garyville, Louisiana
Polymer producers
Calgon Pittsburgh, Pennsylvania
Hercules
Polymer users
St. Regis
Hopewell, Virginia
Unidentified
Sartell, Minnesota
Category
Monomer producer
Polymer producer
Monomer producer
Polymer producer
Polymer producer
Polymer producer
Soil stabilization
Polymer user
Type of operation/process, comments
Catalytic conversion of acrylonitrile
Catalytic conversion of acrylonitrile
Manufacture of paper
-------
Regional Manager, Mining and Industrial Chemicals, American Cyanamid,
that he was not aware of any suitable ongoing projects.
The locations of the sampling sites are shown in Figure 3.
28
-------
D Acrylamide, Polyacrylamide Producer
A Polyacrylamide Producer
O Polyacrylamide User
Figure 3. Location of sampling sites
-------
SECTION V
DISCUSSION OF RESULTS
The five selected industrial sites were sampled between August 8,
1977, and October 6, 1977. The actual sampling schedule is shown in Table
9; presampling site visits were generally conducted on the day prior to
sampling. A summary of the air and water samples collected at the five
sites is given in Table 10 and a summary of the air sampling parameters
follows in Table 11. The results obtained from the five industrial sites
are discussed below. A sixth site was sampled previously by another con-
tractor and these results are also given for comparison.
HERCULES, INC., HOPEWELL, VIRGINIA
Field Sampling
A presampling survey was conducted on August 8, 1977. The plant lies
within the city limits of Hopewell, Virginia, south of the junction of
state highways 10 and 156. Allied Chemical operates a large complex ap-
proximately 0.75 miles to the north-northeast of the Hercules plant. Ap-
proximately 0.75 miles to the northwest is a Firestone polymer plant. The
30
-------
Table 9. SAMPLING SCHEDULE
Date
8/8/77-8/10/77
8/30/77-8/31/77
9/12/77-9/14/77
Company
Hercules, Inc.
Calgon Corporation
Nalco Chemical Company
9/14/77-9/16/77 American Cyanamld
Location
Hopewell, Virginia
Ellwood City, Pennsylvania
Garyville, Louisiana
Fortier, Louisiana
Product or operation
Polyacrylamide producer
Polyacrylamide producer
Acrylamide producer
Polyacrylamide producer
Acrylamide producer
Polyacrylamide producer
10/6/77
St. Regis Paper Company
Sartell, Minnesota
Polyacrylamide user
-------
Table 10. FIELD SAMPLING SUMMARY
Site
Hercules
Calgon
Nalco
American Cyanamid
Air samples Total samples
(stations x components) (number/type)
5x2 10 Air
4 Soil
4 Water
1 Sediment
4x2 8 Air
4 Soil
4 Water
1 Sediment
4x2 8 Air
3 Soil
3 Water
4x2 8 Air
4 Soil
3 Water
2 Sediment
St. Regis
a/
Dow Chemical—
2 Water
a.1 Samples collected and analyzed by separate contractor. See Ref. 1,
Table 11. SUMMARY OF AIR SAMPLING PARAMETERS
Site
Hercules
Calgon
Nalco
American Cyanamid
Dow Chemical^'
Average sample
volume (j0)
(no. of samples)
402 (5)
1,008 (4)
722 (4)
893 (4)
Average
sampling time
(hr)
25.9
25.5
20.1
23.4
Average
sampling rate
(&/min)
0.26
0.66
0.60
0.64
_§/ Samples collected and analyzed by separate contractor. See Ref. 1.
32
-------
municipal sewage treatment facility is located in the city landfill im-
mediately south of the plant adjacent to Bailey Creek into which it dis-
charges.
The NPDES permit application shows four discharge points, 001 through
004, which are labeled accordingly in Figure 4. All four flow into Bailey
Creek which then discharges into the James River. These discharges receive
some treatment before being discharged. At the present time a regional
sewage treatment facility is nearing completion at the junction of Bailey
Creek and the James River. We were informed by Mr. Burnett of the State
Water Control Board that the facility is being funded by the industrial
sites, the City of Hopewell, and the U.S. Environmental Protection Agency
and when completed will receive treated waste from the city and each in-
dustrial site. Discharge into Bailey Creek from Hercules will still occur
during heavy rains.
The Hercules plant manufactures various celluloses, chlorine, chlo-
roacetic acid, ethyl ether, hydrochloric acid, sodium sulfate, and poly-
acrylamide.
Local winds were reported to come primarily out of the southeast at
this time of year.
Field sampling was carried out during the period from 0900 August 9,
1977, to 1300 August 10, 1977. Five air samplers were deployed at four
sites upwind, downwind, and laterally with respect to the plant. Soil sam-
ples were taken from the air sampling sites, water samples were taken
33
-------
rPT-.-VXb,. ^ \-.^r/f •*:-
^^
U '• -vfe^-
Figure 4. Sampling locations at Hercules, Inc., Hopewell, Virginia
34-
-------
upstream and downstream from the point of discharge, and a sediment sample
was taken below an outfall believed to be No. 004.
Air Sampling - Air sampling was conducted using five samplers at four sites.
The sites were established upwind, downwind, and laterally with respect to
the plant with two samplers located at the downwind site. Samplers were
positioned at a height of 1.5 m on public land such as rights-of-way. Sam-
plers were located at 0 and 1/8 mile from the plant perimeter. Locations
of the five stations are shown in Figure 4. Site descriptions and air sam-
pling data are given in Table 12.
Water Sampling - Four water samples were taken; two grab samples and two
composite samples. The first composite sample, W-l, was taken over a 14-
hr period from 1900 August 9, 1977, to 0900 August 10, 1977, from the
bridge where Highway 156 passes over Bailey Creek upstream of the plant
and municipal sewage treatment facility. The second composite sample, W-4,
was taken over a 14-hr period from 2400 August 9, 1977, to 1400 August 10,
1977, from the bridge where Highway 10 passes over Bailey Creek downstream
of the plant. Grab samples were taken at locations W-2 and W-3. The water
sampling locations are shown in Figure 4 and described more thoroughly
in Table 13.
Soil Sampling - Four soil samples were taken on August 10, 1977, one from
each of the air sampling sites (see Table 12). Soil samples were taken by
removing approximately the top 12 ram of soil from the area close to the
air sampler.
35
-------
Table 12. AIR SAMPLING DATA FOR HERCULES. INC., HOPEWELL. VIRGINIA
Area
Northwest transect,
0 km
North transect,
0 km
North transect,
0 km
South transect,
0.3 km
Northeast transect,
0 km
Sample^'
No.
A-l
(So-1)
A- 2
(So-2)
A- 3
(So-3)
A-4
(So-4)
A- 5
(So-5)
Total Sampling
sampling rate
Exact location, USGS coordinates (hr) (£/min)
0 km north-
west at plant
gate
0 km north
on plant road
0 km north
on plant road
0.3 km south-
west at Hopewell
sewage plant
0 km east at
northeast corner
of plant
4129450 m
297560 m
4129320 m
298150 m
4129320 m
298150 m
4128120 m
297310 m
4128880 m
298830 m
N 25.3 0.52
E
N 26.9 0.29
E
N 26.9 0.40
E
N 25.1 0.18
E
N 25.1 0.62
E
Total Sample
volume height
(m3) (m)
0.79 1.5
0.46 1.5
0.65 1.5
0.28 1.5
0.93 1.5
jj/ Soil samples were collected at these air sampling stations.
-------
Table 13. WATER AND SEDIMENT SAMPLING DATA FOR HERCULES, INC.,
HOPEWELL. VIRGINIA
Sample
No.
W-l
W-2
W-3
W-4
Se-1
Exact location, USGS coordinates
Highway 156 at
Bailey Creek
Bailey Creek below
Outfall 002
4127320 m N
296950 m E
4128140 m N
297330 m E
Bailey Creek below 4128050 m N
Outfall 003 298240 m E
Highway 10 at
Bailey Creek
Bailey Creek below
Outfall 004
4129050 m N
297810 m E
4128430 m N
298380 m E
Sample
type
Composited water
Grab water
Grab water
Volume
collected
1,000 ml
1,000 ml
1,000 ml
Composited water 1,000 ml
Sediment
1,000 cm3
37
-------
Sediment Sampling - A sediment sample was taken from below an outfall be-
lieved to be No. 004 which, according to the NPDES permit application,
should contain process waste from noncellulose polymer production. The
sample was taken by scraping up some of the clay soil beneath the water
level. The sampling data are given in Table 13.
Meteorological Conditions
The wind conditions existing at Byrd Airport, Richmond, Virginia,
between 0800 August 9, 1977, and 1300 August 10, 1977, are summarized in
Table 14. Locally winds blew predominantly from the southwest.
Sample Analysis
Air Samples - The results of the analysis of the five air samples and two
blanks are listed in Table 15. No AA was found in the Chromosorb 101 ex-
tracts or in the filter extracts. The minimum detectable concentration,
which was dependent upon the volume of air collected, ranged from 0.3 to
3
1 |J.g/m . The absence of AA in air sample No. 3 was later confirmed by
GC/MS (vide infra).
Water Samples - The results of the analysis of the water samples are
given in Table"16. No AA was found in Samples W-l, W-2, or W-3. The limit
of detection for these samples, taking into account the 500-fold increase
in concentration by evaporation, was approximately 0.8 (jtg/liter. Sample
4, however, was found to contain 1.5 ppm AA. This was the only sample
taken downstream of outfall No. 004. The presence of AA in the sample was
confirmed by GC/MS (vide infra).
38
-------
Table 14. WEATHER CONDITIONS DURING SAMPLING AT HERCULES, INC,
HOPEWELL, VIRGINIA: SOURCE OF DATA,
BYRD AIRPORT* RICHMOND, VIRGINIA
Wind
Time (EOT)
August 9. 1977
0800
0900
1000
1100
1 200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
August 10, 1977
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1200
1300
Direction
W
NW
N
NE
NNW
N
NE
E
S
SW
S
E
ENE
E
E
SE
SE
ESE
E
SE
SE
SSW
S
S
SW
SW
SW
WSW
W
Speed (knots)
5
3
3
3
6
8
5
4
5
3
3
5
5
6
7
5
5
4
4
4
4
3
3
3
5
5
6
9
9
Precipitation
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
39
-------
Table 15. ACEYLAMIDE CONCENTRATIONS IN AIR SAMPLES FROM
HERCULES, INC., HOPEWELL. VIRGINIA
Sample
No.
A-l
A- 2
A- 3
A-4
Blank 1
Blank 2
Sampling
8/9/77
8/10/77
8/9/77
8/10/77
8/9/77
8/10/77
8/9/77
8/10/77
_
_
period
1049-
1207
0924-
1219
0924-
1219
1035-
1144
Volume Type of
(cu m) sample
0.79 Aic§/
Particulate^/
0.46 Air
Particulate
0.65 Air
Particulate
0.28 Air
Particulate
Air
Particulate
Air
Particulate
yg
found
< 0.3
< 0.8
< 0.3
< 0.8
< 0.3
< 0.8
< 0.3
< 0.8
< 0.3
< 0.8
< 0.3
< 0.8
Ug/m3
< 0.4£/
< 1.1
< 0.6
< 1.6
< 0.5
< 1.3
< 1.1
< 0.8
_
-
_
_a/ Chromosorb 101 extracts.
_b/ Millipore filter extracts.
_c/ Based on instrumental detection limit and volume of air sampled.
Table 16. ACRYLAMIDE CONCENTRATIONS IN WATER SAMPLES FROM
HERCULES, INC., HOPEWELL, VIRGINIA
Sample
No.
W-l
W-2
W-3
W-4
Aliquot
volume
(ml)
250
250
250
250
Final
volume
(ml)
0.5
0.5
0.5
8.3
yg
found
< 0.2
< 0.2
< 0.2
383
ys/£
< o.as/
<0.8
< 0.8
1,500
_a/ Based upon instrument detection limit and sample size.
40
-------
Soil and Sediment Samples - The results of the analysis of the soil and
sediment samples are listed in Table 17. No AA was found in any of the sam-
ples. The limit of detection was approximately 0.08 |j,g/g.
Table 17. ACBYLAMIDE CONCENTRATIONS IN SOIL AND SEDIMENT SAMPLES
FROM HERCULES, INC., HOPEWELL, VIRGINIA
Sample
No.
So-1
So-2
So- 4
So- 5
Se-1
Sample size
wet
(a)
50
50
50
50
50
Final
volume
(ml)
5
5
5
5
5
yg
found
< 4
< 4
< 4
< 4
< 4
US/R
-------
100-
90-
70-j
60-1
40-j
304
£04
'I
20
- 30
r £0
0 10 20 30 40 50
SPECO 15490 Jtl fiCRYLfltUDE 30C J. 6.
"I""!""1""!""1""! "
60 70 80 90 100
•£S-?7 STEP hfl3S=l/ ixBxS
Figure 5. Mass spectrum of acrylamide
-------
Data system: Varian Spectrosystem 100 MS
Separator: Watson-Biemann
Mass monitored: 71.0371
Resolution: 7,000
lonization potential: 70 ev
Emission current: 1 mA
Multiplier gain: 4 x 106 - 2 x 107
The resolution chosen, 7,000, was that necessary to provide baseline
resolution of the AA 71 peak from the background 71 peak.
The presence of AA in water sample No. W-4 was first confirmed as
shown by the ion current plots in Figure 6. The raw sample rather than
the concentrated sample was analyzed. No attempt was made to quantitate
the AA in W-4 by GC/MS.
The absence of AA in the concentrated air sample No. A-3 was also
confirmed by this technique. The ion current plot is also shown in Fig-
ure 6 with the expected elution time of AA noted. The sensitivity of the
GC/MS system in the high resolution mode was comparable to that of the
GC/Hall detector. Thus, the limit of detection was about 0.5 M«g/m3 for
air sample No. A-3.
CALGON CORPORATION, ELLWOOD CITY, PENNSYLVANIA
Field Sampling
A presampling survey was conducted on July 25, 1977. The Calgon plant
lies in Frisco Township of Beaver County, Pennsylvania, just east-southeast
of Ellwood City, Pennsylvania. The plant is located in a semi-rural area
43
-------
X 188
RE40Y
MU- -2.2KU
MOng
Acrylomide
W-4
!"!1
s 10 is 20
MINUTES
97/ MI/ HERCULES W 4 RAW J GOING 6 23 77
a* Water sample W-4
23
RE>
X 188
DY
-r- J • I | i I | I I |—i I | I I | r
1 2 34 S 6 7
MINUTES
98/ MI/ HERCULES A IR 3 CONC J GOING 6 25 77
b. Air sample A-3
Figure 6. Selection ion current plots, m/e = 71.0371
e
44
-------
near a bend in the Connoquenessing Creek, which lies to the north and west
of the plant. The east side of the plant lies near an abandoned roadbed.
There is a small chemical company adjacent to the plant on the south side
which reportedly supplies Calgon with chlorine for water treatment.
The NPDES permit for this plant indicates that there are four dis-
charge points to an unnamed tributary of Connoquenessing Creek. The trib-
utary was found 200 yards east of a railroad trestle over River Road. This
point is marked W-2 on the map shown in Figure 7. It was assumed that pro-
cess water came from the local supply as no other source was located. This
Calgon facility manufactures slowly soluble phosphates, water soluble poly-
mers, and water treatment compounds.
Field sampling was carried out from 0800 (EOT) August 30, 1977, to
1300 (EOT) August 31, 1977. Four air samplers were deployed at four sites
upwind, downwind, and laterally with respect to the plant. Soil samples
were taken from each air sampling site; water samples were taken at vari-
ous locations upstream and downstream from the points of discharge; sedi-
ment samples were taken below two discharge points.
Air Sampling - Air sampling was carried out from 0800 (EDT) August 30,
1977, to 1100 (EDT) August 31, 1977, using four samplers at four sites.
The sites were located upwind, downwind, and laterally with respect to
the plant. Samplers were positioned at a height of 1.5 m from the ground
on public land such as rights-of-way. Locations of the samplers are shown
in Figure 7. Site descriptions and air sampling data are given in Table
18.
45
-------
* f.*\. V.
••.•at =i.,». \
Air & Soil Sampling Site
W^) Water Sampling Site
SE ^ Sediment Sampling Site
Figure 7. Sampling locations at Calgon Corporation,
Ellwood City, Pennsylvania
46
-------
Table 18. AIR SAMPLING DATA FOR CALGON CORPORATION. ELLHDOD CITY, PENNSYLVANIA
Area
North transect,
0 km
South transect,
0 km
East transect,
0 km
West transect,
0 km
Sample^/
No.
A-l
(So-1)
A- 2
(So- 2)
A- 3
(So-3)
A- 4
(So-4)
Exact location, USGS
0 km north on
River Road
0 km south on
Main Street
0 km east on
Forest Grove Avenue
0 km west on
Hazen Avenue
coordinates
4522420 m N
561320 m E
4522280 m N
561210 m E
4522360 m N
561330 m E
4522160 m N
560920 m E
Total
sampling
(hr)
25.6
25.5
25.5
25.5
Sampling
rate
(Jt/min)
0.80
0.63
0.58
0.61
Total
volume
(m3)
1.22
0.97
0.89
0.95
Sample
height
(m)
1.5
1.5
1.5
1.5
jj/ Soil, samples were collected at these air sampling stations.
-------
Water Sampling - Five water samples were taken at various points upstream
and downstream of the discharge points. All were composite samples taken
during the period 0800 (EOT) August 30, 1977, to 1300 (EOT) August 31,
1977. Although the NPDES permit describes four discharge points into an
unnamed tributary of the Connoquenessing Creek, only two outfalls were ob-
served from the edge of the creek. One, W-4, is known to come from the
plant and the other, W-3, may come from the plant. Both outfalls were
large diameter concrete pipes which passed under River Road and flowed
down the rocky bank of the Connoquenessing. Samples W-3 and W-4 were
taken directly from outfalls; the remaining samples were taken from
Connoquenessing Creek. Sampling locations are shown in Figure 7 and de-
scribed in Table 19.
Soil Sampling - Soil samples were taken on August 31, 1977, at each of
the air sampling sites (see Table 18) by scraping up the top 10 mm of
soil.
Sediment Sampling - Sediment samples Se-3 and Se-4 were taken with water
samples W-3 and W-4, which are at plant outfalls. Samples were taken by
scraping some sediment up into jars. Sampling data are given in Table 19.
Meteorological Conditions
The wind conditions existing at Pittsburgh International Airport be-
tween 0800 (EOT) August 30, 1977, and 1100 (EDT) August 31, 1977, are sum-
marized in Table 20. Locally the winds appeared calm during the period.
48
-------
Table 19. WATER AND SEDIMENT SAMPLING DATA FOR CALGON CORPORATION, ELLWOOD CITY, PENNSYLVANIA
v£>
Sample
No.
W-l
W-2
W-3
Se-3
W-4
Se-4
W-5
Exact location, USGS
0.5 km upstream
of Outfall 001
West side of
railroad trestle
East side of rail-
road trestle, di-
rectly from Out-
fall 001
0.3 km east of
railroad trestle,
directly from Out-
fall 002
0.6 km east of
railroad trestle
coordinates
4521950 m N
560930 m E
4522390 m N
560950 m E
4522380 m N
561010 m E
4522480 m N
561300 m E
4522750 m N
561720 m E
Sample type
Composite water
Composite water
Composite water
Sediment
Composite water
Sediment
Composite water
Volume
collected
1,000 ml
1,000 ml
1,000 ml
1,000 cm3
1,000 ml
1,000 cm3
1,000 ml
-------
Table 20. WEATHER CONDITIONS DURING SAMPLING AT GALGON CORPORATION,
ELLWOOD CITY, PENNSYLVANIA: SOURCE OF DATA, PITTSBURGH
INTERNATIONAL AIRPORT, PITTSBURGH. PENNSYLVANIA
Wind
Time (EOT)
Aueust 30, 1977
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
August 31, 1977
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
Direction
WNW
N
WSW
NE
N
NNE
N
-
NW
N
N
E
SE
E
-
-
S
—
-
-
-
-
-
_
SE
_
SE
S
Speed (knots)
3
5
3
4
4
4
4
0
3
6
5
4
3
3
0
0
3
0
0
0
0
0
0
0
3
0
3
3
Precipitation
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
50
-------
Sample Analysis
Air Samples - The results of the analysis of the four air samples are
listed in Table 21. No AA was found in the Chromosorb 101 extracts or fil-
ter extracts. The limits of detection, which are dependent upon the vol-
ume of air actually sampled, were about 0.1 p,g/m^ for air and 0.4 (j,g/m-^
for particulates. No AA was found in the field blanks.
Water Samples - The results of the analysis of the five water samples are
listed in Table 22. No AA was found in any of the samples after evapora-
tion of 250 ml to 1 ml. The limit of detection was 0.8 (jtg/liter.
Soil and Sediment Samples - The results of the analysis of the soil and
sediment samples are summarized in Table 23. No AA was found above the
detection limit of 0.02 |J
-------
Table 21. AGRYLAMIDE GONCENTRA.TIONS IN AIR SAMPLES FROM GALGON CORPORATION,
ELLWOOD CITY. PENNSYLVANIA
Sample No.
A-l
A-2
A-3
A-4
Sampling
(hr)
8/30/77
8/31/77
8/30/77
8/31/77
8/30/77
8/31/77
8/30/77
8/31/77
period
0845-
1030
0823-
0945
0843-
1014
0909-
1040
Volume
(m3)
1.22
0.97
0.89
0.95
Type of
sample
Air*/
Particulate—'
Air3/
Particulate^'
Particulatek/
Air^/
Particulate—
M-8
found
< 0.1
< 0.4
< 0.1
< 0.4
< 0.1
• < 0.4
< 0.1
< 0.4
/m3
< O.l£/
< 0.4£/
< 0.1
< 0.4
< 0.1
< 0.4
< 0.1
< 0.4
al Chromosorb 101 extracts.
b_/ Millipore filter extracts.
c_/ Based upon instrument detection limit and sample size.
-------
Table 22. AGRYLAMIDE CONCENTRATIONS IN WATER SAMPLES FROM
CALGON CORPORATION. ELLWOOD CITY, PENNSYLVANIA
Sample No.
W-l
W-2
W-3
W-4
W-5
Aliquot
volume
(ml)
250
250
250
250
250
Final
volume
(ml)
1
1
1
1
1
M-g
found
< 0.2
< 0.2
< 0.2
< 0.2
< 0.2
/
UB/lS/
< 0.8
< 0.8
< 0.8
< 0.8
< 0.8
a/ Based upon instrumental detection limit and sample size.
Table 23. ACRYLAMIDE CONCENTRATIONS IN SOIL AND SEDIMENT SAMPLES
FROM CALGON CORPORATION, ELLWOOD CITY. PENNSYLVANIA
Sample
No.
So-1
So- 2
So- 3
So-4
Se-1
Se-2
Sample size
wet
(e)
50
50
50
50
50
50
Final
vo lume
(ml)
5
5
5
5
0.5
0.5
yg
found
< 1
< 1
< 1
< 1
< 1
< 1
ys/s
< 0.022/
< 0.02J/
< 0.02J/
< 0.022/
< 0.02-2/
< 0.022/
_a/ Based upon instrument detection limit and wet sample size.
53
-------
A-l ) Air & Soil Site
001 !-»• Discharge Point
W-1 ) Water Site
K» a :
\/i :! IS'
Figure 8. Sampling locations at Nalco Chemical Company, Garyville, Louisiana
54
-------
Field sampling was conducted during the period 0900 September 13,
1977, to 1900 September 14, 1977» Four air samples and three water samples
were collected at that time. Water samples were collected later.
Air Sampling - Air sampling was conducted using four samplers at four sam-
pling sites which were positioned upwind, downwind, and laterally with re-
spect to the plant. Samplers were located at 0 and 1/8 mile from the plant
property and were positioned at a height of 1.5 m on adjacent property,
a railroad right-of-way, and a levee.
Sampling was carried out during the period 0930 (GDI) September 13,
1977, to 1830 (GDI) September 14, 1977, and was often interrupted by rain.
The four sampling locations are shown in Figure 8. Site descriptions and
air sampling data are given in Table 24.
Water and Sediment Sampling - Due to the extreme difficulty in obtaining
a boat and the inclement weather, no water or sediment samples were taken.
Arrangements were then made with the Jefferson Parish Sheriff's Office to
have one of their personnel collect water samples; these samples were re-
ceived and analyzed. This office was involved in the collecting of a water
sample from the American Cyanamid site at Fortier. For this reason, it is
felt that samples of acceptable quality were collected. Sampling data are
given in Table 25.
Soil Samples - Soil samples were taken September 14, 1977, at three of the
four air sampling sites by removing the top approximately 10 mm of topsoil
from the area by each sampler. Sampling data are given in Table 26.
55
-------
Table 24.. AIR SAMPLING DATA FOR NALCO CHEMICAL COMPANY, GARYVILLE. LOUISIANA
Area
JJorth transect,
0 km
South transect,
0.2 km
Southeast transect,
0 km
West transect,
0 km
Samp le
No. Exact location, USGS
A-l Plant spur and main
line Illinois Cen-
tral Railroad
A-2 0.2 km south on
levee
A- 3 0 km east along
State Highway 44
A-4 0 km west along
fenceline
coordinates
3327400 m N
728720 m E
3325960 m N
728300 m E
3325810 m N
728710 m E
3326320 m N
728160 m E
Total
sampling
(hr)
24
23.1
10.6
23.5
Sampling
rate
(Jl/min)
0.65
0.49
0.63
0.62
Total
volume
(m3)
0.93
0.68
0.40
0.88
Sample
height
(m)
1.5
1.5
1.5
1.5
-------
Table 25. WATER SAMPLING DATA FOR NALCO CHEMICAL COMPANY
GARYVILLE. LOUISIANA
Sample
No.
W-l
W-2
Exact location, USGS coordinates
30 m upstream of
Discharge 001,
20 m offshore
At Discharge 001
3325820 m N
728270 m E
3325770 m N
728290 m E
Vo lume
Sample type collected
Grab
Grab
1,000 ml
1,000 ml
W-3 150 m downstream
of Discharge 001,
20 m offshore
3325650 m N
728390 m E
Grab
1,000 ml
Table 26. SOIL SAMPLING DATA FOR NALCO CHEMICAL COMPANY
GARYVILLE. LOUISIANA
Sample
No.
So-1
So-2
So-4
Exact location, USGS coordinates
Percent
Sample size moisture
Plant spur and main
line Illinois Cen-
tral Railroad
0.2 km south on
levee
0 km west along
fenceline
3327400 m N
728720 m E
3325960 m N
728300 m E
3326320 m N
728160 m E
250 cm3
250 cm3
250 cm3
89
64
75
57
-------
Meteorological Conditions - The meteorological conditions that existed dur-
ing the sampling period were obtained from the National Weather Service,
New Orleans International Airport, and are summarized in Table 27.
Sample Analysis
Air Samples - The results of the analysis of the four air samples and the
blank are listed in Table 28. No AA was found in the Chromosorb 101 ex-
tracts or filter extracts. The limits of detection were about 0.15 pg/m?
for air and 2 Mig/m for particulates* This level was established using
spiked samples* No AA was found in the field blanks*
Water Samples - The results of the analysis of the three water samples are
listed in Table 29. No AA was found above a limit of detection of about
0.8 |4/g/liter, established with spiked samples.
Soil Samples - The results of the analysis of the three soil samples are
summarized in Table 30. No AA was present above the detection limit of
0.02 (Jig/g» established with spiked samples.
AMERICAN CYANAMID, FORTIER, LOUISIANA
Field Sampling
A presampling survey of the American Cyanamid Company plant, Fortier,
Louisiana, was conducted on September 14, 1977. The plant is located in
Jefferson Parish, Louisiana, in South Kenner along State Highway 18 about
6 miles east of Luling, Louisiana. The plant lies in a semi-rural area
with the Mississippi River to the north. The NPDES permit shows two out-
falls which discharge wastewater into the Mississippi River. Both are
58
-------
Table 27. WEATHER CONDITIONS DURING SAMPLING AT NALCO CHEMICAL,
GARYVILLE, LOUISIANA: SOURCE OF DATA, NEW ORLEANS
INTERNATIONAL AIRPORT, NEW ORLEANS, LOUISIANA
Time (GOT)
September 13. 1977
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
September 14, 1977
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
Direction
S
S
S
S
S
SSW
S
S
0
NNE
0
NW
E
E
ESE
ESE
ESE
SSE
S
S
SSW
NW
W
E
SSW
SSE
S
S
SW
S
S
S
S
SSE
S
Wind
Speed (knots)
6
9
9
3
10
11
11
8
0
3
0
4
3
4
4
2
5
4
7
5
8
12
8
2
7
11
10
6
7
10
9
7
6
7
5
Precipitation^/
None
None
None
None
None
None
None
Rain
Rain
Rain
None
None
None
None
None
None
None
Rain
None
None
None
Rain
None
None
Rain
None
None
None
None
None
None
None
None
None
None
a] Precipitation data from sampling site.
59
-------
Table 28. AGRYLAMIDE CONCENTRATIONS IN AIR SAMPLES FROM NALCO CHEMICAL, GARYVILLE. LOUISIANA
a*
o
Sample No.
A-l
A-2
A-3
A-4
Sampling period
(hr)
9/13/77
9/14/77
9/13/77
9/14/77
9/13/77
9/14/77
9/13/77
9/14/77
0930-
1714
1010-
1806
1037-
1045
1111-
1740
Volume
(m3)
0.93
0.68
0.40
0.88
Type of
sample
Air*/
Particulatek'
Air3/
Particulatek/
Particulate^
Air*/
Part icu latell/
M-S
found
< 0.1
< 0.4
< 0.1
< 3.2
< 0.1
< 1.6
< 0.1
< 1.6
ue/m
< O.llS/
< 0.43£/
< 0.15
< 4.7
< 0.25
< 4.0
< 0.12
< 1.8
a/ Ghromosorb 101 extract.
b/ Millipore filter extract.
c_/ Based upon instrument detection limit and sample size.
-------
Table 29. ACRYLAMIDE CONCENTRATIONS IN WATER SAMPLES FROM
NALCO CHEMICAL COMPANY. GARYVILLE. LOUISIANA
Sample
No.
W-l
W-2
W-3
Aliquot
volume
(ml)
250
250
250
Final
volume
(ml)
1
1
1
yg
found
< 0.2
< 0.2
< 0.2
vz/a
< o.ss/
< 0.8
< 0.8
_a/ Based upon instrument detection limit and sample size,
Table 30. ACRYLAMIDE CONCENTRATIONS IN SOIL SAMPLES
NALCO CHEMICAL COMPANY. GARYVILLE. LOUISIANA
Sample
No.
So-1
So- 2
So- 3
Sample size
wet
(a)
50
50
50
Final
volume
(ml)
1
1
1
yg
found
< 1
< 1
< 1
us/g
< 0.02J/
< 0.02
< 0.02
_a/ Based upon instrumental detection limit and wet sample size.
61
-------
readily visible passing over the highway. The locations are shown in Fig-
ure 9. This plant produces AA and polyacrylamide through catalytic conver-
sion of acrylonitrile»
Field sampling was conducted during the period 2000 September 14,
1977, to 0700 September 16, 1977. Four air samples, three water samples,
four soil samples, and two sediment samples were collected.
Air Sampling - Air sampling was carried out from 2000 (CDT) September 14,
1977, to 0700 (CDT) September 16, 1977, at four sampling sites located
upwind, downwind, and laterally with respect to the plant. Samplers were
located at 1/8 and 3/4 mile from the plant perimeter and were positioned
at a height of 1.5 m on street rights-of-way, a railroad right-of-way,
and on a levee. Sampling was interrupted by rain. The four sampling loca-
tions are shown in Figure 9. Site descriptions and air sampling data are
given in Table 31.
Water and Sediment Sampling - Water and sediment samples were collected
on September 16, 1977, from upstream, downstream, and between the two dis-
charge points shown in Figure 9. Sampling data are given in Table 32.
Soil Sampling - Soil samples were taken on September 16, 1977, at each of
the four air sampling sites by removing approximately the top 10 mm of
soil from the area near each sampler. Sampling data are given in Table 33.
Meteorological Conditions - The meteorological conditions that existed
during the sampling period were obtained from the National Weather Service,
New Orleans International Airport, and are summarized in Table 34.
62
-------
Air i Soil Site
Water Site
Sediment Site
Figure 9, Sampling locations at American Cyanamid, Fortier, Louisiana
63
-------
Table 31. AIR SAMPLING DATA FOR AMERICAN CYANAMID. NEW ORLEANS. LOUISIANA
North
0.2
South
1.2
East
0.4
West
0.2
Area
transect,
km
transect,
km
transect,
km
transect,
km
Samp le
No. Exact location, USGS
A-l 0.2 km north on
levee
A- 2 1.2 km south on
Texas and Pacific
Railroad right-of-
way
A-3 0.4 km east on
Moss Lane
A-4 0.2 km west on
Fortier Heights
coordinates
3317850
763350
3315260
762950
3317650
764380
3317220
762870
m
m
m
m
m
m
m
m
N
E
N
E
N
E
N
E
Total
sampling
(hr)
23.3
24.2
23.0
23.2
Sampling Total
rate volume
(£/min) (m3)
0.64 0.89
0.69 1.01
0.69 0.95
0.52 0.72
Sampling
height
(m)
1.5
1.5
1.5
1.5
Road
-------
Table 32. WATER AND SEDIMENT SAMPLING DATA FOR AMERICAN CYANAMID, NEW ORLEANS, LOUISIANA
Sample
No.
W-.l
W-2
W-3
Se-1
Se-2
Exact location, USGS
50 m upstream of
Discharge 001
Midway between
Discharge Points
001 and 002
50 m downstream of
Discharge 002
50 m upstream of
Discharge 001
50 m downstream of
Discharge 002
coordinates Sample type
3317850 m N Grab water
762940 m E
3317910 m N Grab water
763330 m E
3317970 m N Grab water
763560 m E
3317850 m N Sediment
762940 m E
3317970 m N Sediment
763560 m E
Volume
collected
1,000 ml
1,000 ml
1,000 ml
500 cm3
500 cm3
Percent moisture
by weight
-
••
-
47
64
-------
Table 33. SOIL SAMPLING DATA FOR AMERICAN CYANAMID
.... NEW ORLEANS, LOUISIANA
Sample
No.
So-1
So-2
So-3
So-4
Exact location, USGS coordinates
0.2 km north on
levee
1.2 km south on
Texas and Pacific
Railroad right-of-
way
0.4 km east on Moss
Lane
3317850 m N
763350 m N
3315260 m N
762950 m E
3317650 m N
764380 m E
0.2 km west on 3317220 m N
Fortier Heights Road 762870 m E
Percent
Sample size moisture
250 cm3
250
250 cm3
250 cm-
78
78
70
67
66
-------
Table 34. WEATHER CONDITIONS DURING SAMPLING AT AMERICAN CYANAMID,
NEW ORLEANS, LOUISIANA: SOURCE OF DATA, NEW ORLEANS
INTERNATIONAL AIRPORT. NEW ORLEANS, LOUISIANA
Time (GOT)
September 14, 1977
2000
2100
2200
2300
2400
September 15, 1977
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
September 16, 1977
0100
0200
0300
0400
0500
0600
0700
Direction
SW
0
0
S
0
0
0
0
0
0
0
0
NE
0
NNW
W
0
WNW
W
W
ENE
E
N
ENE
E
E
ESE
0
E
0
ESE
E
E
0
ESE
ESE
Wind
Speed (knots)
5
0
0
4
0
0
0
0
0
0
0
0
3
0
3
13
0
6
5
3
4
6
2
6
6
9
3
0
2
0
3
2
4
0
2
2
Precipitation^/
None
None
None
None
None
None
None
None
None
None
None
Rain
Rain
Rain
Rain
Rain
Rain
Rain
Rain
Rain
Rain
Rain
None
None
None
None
None
None
None
None
None
None
None
None
None
None
a/ Precipitation data from sampling site.
67
-------
Sample Analysis
Air Samples - The results of the analysis of the four air samples and the
blank are listed in Table 35. No AA was found in the Chromosorb 101 ex-
tracts or filter extracts. The limits of detection of about 0.12 |ig/nr for
o'
air and 0.8 |ig/m for particulates were established using spiked samples.
No AA was found in the field blanks.
Water Samples - The results of the analysis of the three water samples are
given in Table 36. No AA was found above the detection limit of 0.8 ^g/liter
established using spiked samples.
Soil and Sediment Samples - The results of the analysis of the six soil
and sediment samples are summarized in Table 37. No AA was present above
0.02 M>8/8 as established using spiked samples.
ST. REGIS PAPER COMPANY, SARTELL, MINNESOTA
Field Sampling
A presampling survey of the St. Regis Paper Company plant in Sartell,
Minnesota, was conducted on October 6, 1977. The plant is located in
Benton County, Minnesota, just east of the corporate limits of Sartell,
Minnesota. The plant is bounded on the west by the Mississippi River and
on the east by State Highway 152. The DeZurik Company plant is located
on the opposite side of the Mississippi River. Wastewater is discharged
into the Mississippi River at the points shown in Figure 10. Only water
and sediment samples were scheduled to be taken at this site.
68
-------
Table 35. ACRYLAMIDE CONCENTRATIONS IN AIR SAMPLES FROM AMERICAN CYANAMID. FORTIER. LOUISIANA
Sample No.
A-l
A-2
A-3
A-4
Sampling
period Volume
(hr) (m3)
9/14/77
9/16/77
9/14/77
9/16/77
9/14/77
9/16/77
9/14/77
9/16/77
2025- 0.89
0538
2145- 1.01
0658
2100- 0.95
0625
2045- 0.72
0609
Type
of
sample
Air*/
Particulate— '
Alra/
ParticulateV
AlrS/
ParticulatelJ/
Aira/
Particulate^.'
U>
g
found
<
<
<
<
<
<
<
<
0
0
0
0
0
0
0
0
.1
.4
.1
.8
.1
.8
.1
.8
y.g/m3
<
<
<
<
<
<
<
<
0
0
0
0
0
0
0
1
,12£/
.45£/
.10
.80
.11
.85
.14
.12
a/ Ghromosorb 101 extract.
b/ Millipore filter extract.
c_/ Based on instrumental detection limit and volume of air sampled.
-------
Table 36. ACRYLAMIDE CONCENTRATIONS IN WATER SAMPLES FROM
AMERICAN CYANAMID. FORTIER. LOUISIANA
Sample
No.
W-l
W-2
W-3
Aliquot
volume
(ml)
250
250
250
Final
volume
(ml)
1.0
1.0
1.0
yg
found
< 0.2
< 0.2
< 0.2
us /«.
< 0.&2/
< 0.8
< 0.8
_a/ Based upon instrument detection limit and sample size.
Table 37. ACRYLAMIDE CONCENTRATIONS IN SOIL AND SEDIMENT SAMPLES
FROM AMERICAN CYANAMID* FORTIER, LOUISIANA
Sample
No.
So-1
So- 2
So-3
So-4
Se-1
Se-2 ,
Sample size
wet
(g)
50
50
50
50
50
50
Final
volume
(ml)
1
1
1
1
1
1
yg
found
< 1
< 1
< 1
< 1
< 1
< 1
yg/g
< 0.022/
< 0.02
< 0.02
< 0.02
< 0.02
< 0.02
_a/ Based upon instrumental detection limit and wet sample size.
70
-------
Due to the rocky nature of the river bottom, sediment samples were
not obtained. Grab water samples were taken on October 6, 1977, from two
locations, upstream and downstream from the discharge points, as shown in
Figure 10. Water sampling data are given in Table 38.
Sample Analysis
The results of the analysis of the two water samples are given in
Table 39. No AA was found above the detection limit of 0.8 jig/liter estab-
lished using spiked samples.
DOW CHEMICAL, MIDLAND, MICHIGAN
The environmental samples from the Dow plant were collected and ana-
lyzed by another contractor,— using in some instances, different metho-
dologies. Some of the results are included in this report so that all of
the environmental measurements will be available in a single document.
Grab 1,000 ml water samples were collected from the points indicated
in Figure 11. The results of the analyses are given in Table 40. The re-
ported detection limit was 25 ppb.
Air samples were collected at the six stations shown in Figure 11.
The results of the analysis for both vapor and particulate AA are given
in Table 41. No AA was reported above the 1 p-g/nH detection limit.
Soil samples, collected at the six air sampling stations, were ana-
lyzed with the results given in Table 42. No AA was reported above 20 ppb.
71
-------
UNITED STATES
DEPARTMENT OF THE INTERIOR
GEOLOGICAL SURVEY
•03«lo-£. 1 94000O FCET (
STATE OF MINNESOTA
DEPARTMENT OF ADMINISTRA
Tin „ HW ,11 •• .'
"07 ILITTLC &<>'.* I AXEI •*>''.
Water Site
•* Discharge Point
S500CO
'SOUTH
Figure 10. Sampling locations at St. Regis Paper Company,
Sartell, Minnesota
72
-------
Table 38. WATER SAMPLING DATA FOR ST. REGIS PAPER COMPANY,
S ARTELL.MINNE SOTA
Sample
No.
W-l
W-2
Exact location, USGS
0.6 km north on
152 from bridge
State Highway 152
bridge over
coordinates
5052750 m N
406230 m E
5052150 m N
406270 m E
Sample type
Grab water
Grab water
Volume
collected
1,000 ml .
1,000 ml
Mississippi River
Table 39. ACRYLAMIDE CONCENTRATIONS IN WATER SAMPLES FROM ST. REGIS
PAPER COMPANY, SARTELL. MINNESOTA
Sampling
station
W-l
W-2
Aliquot
volume
(ml)
250
250
Final
volume
(ml)
1
1
yg
found
< 0.2
< 0.2
U2/£
< 0.8S/
< 0.8
_a/ Based upon instrumental detection limit and sample size.
73
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#SITE NUMBER
HIGHWAY
I ! I I I I I I I I I I I I I I I I I I Kl
RAILROAD
PLANT SITE
RESIDENTIAL
AREA
SOIL/AIR SAMPLE
KILOMETER
0 .5 1
A WATER SAMPLE
Figure 11. Map of sampling sites for acrylamide at Midland, Michigan
74
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Table 40. ANALYTICAL DATA. FOR WATER SAMPLES FROM MIDLAND. MICHIGAN!/
Sampling Acrylamide
station analysis
letter Exact location. USGS coordinates (ppb)—'
A Tittabawassee River, upstream 4832000 m N < 25
of chemical plant 722442 m E
B Tittabawassee River, down- 4827500 m N < 25
stream of chemical plant 726231 m E
C Effluent from outfall at 4829692 m N 25-125
Lingle Drain near Dow 725308 m E
Corning
D Tap water samples from < 25
Holiday Inn
E Snow sample taken at air 4832910 m N < 25
sampling site No. 3 723591 m E
a/ Detection limit 25 ppb, quantitation limit 125 ppb.
75
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Table 41. ANALYTICAL DATA FOR AIR SAMPLES FROM MIDLAND. MICHIGAN^-'
i/
Weather conditions
Samp 1 Ing
Station
1
2
3
4
5
6
U.S. Geological
Survey
coordinates
722448 m E
482819 m N
722417 m f.
4831905 m N
723591 m E
4832910 m N
725810 ra E
4831445 m N
725793 m E
4831088 ra N
726286 m E
4831833 ra N
Wind (av)
Direction
(degree)
360
245
300
360
245
300
360
245
300
360
245
315
360
245
330
360
245
285
(7 hr)
(13 hr)
(4 hr)
(6 hr)
(13 hr)
(4 hr)
(5 hr)
(13 hr)
(7 hr)
(3 hr)
(13 hr)
(8 hr)
(2 hr)
(13 hr)
(9 hr)
(8 hr)
(13 hr)
(2 hr)
Velocity
Temp.
(m/sec) (°F)
4
1
3
4
1
3
4
1
3
3
1
3
1
I
3
5
I
3
.80
.80
.00
.80
.80
.00
.40
.80
.40
.00
.80
.30
.20
.80
.80
.00
.80
.00
30-35-25
25-20-30
30-45
31-35-25
25-20-30
30-47
33-35-25
25-20-30
30-49
35-25
25-20-30
30-46
32-25
25-20-30
30-38
28-35-25
25-20-30
30-33
Sampling period
General
Partly
Clear
Partly
Partly
Clear
Partly
Partly
Clear
Partly
Partly
Clear
Partly
Partly
Clear
Partly
Partly
Clear
Partly
cloudy
cloudy
cloudy
cloudy
cloudy
cloudy
cloudy
cloudy
cloudy
cloudy
cloudy
cloudy
(total 24 hr)
4/6/77
4/7/77
4/6/77
4/7/77
4/6/77
4/7/77
4/6/77
4/7/77
4/6/77
4/7/77
4/6/77
4/7/77
1308-2025
2025-900
900-1323
1408-2025
2025-900
900-1417
1533-2025
2025-900
900-1583
1667-2025
2025-900
900-1683
1792-2025
2025-900
900-1820
1100-2025
2025-900
900-1122
Acrylamide analysis
Partlcu-
lateS/ Vaoork/
(|te/m3 ) ppb ue/m
< 1.0 < 1.0 < 1.0
< 1.0
< 1.0 < 1.0
< 1.0 < 1.0 < 1.0
< 1.0 < 1.0
< 1.0
< 1.0 < 1.0
< 1.0
< 1.0 < 1.0
< 1.0
a/ Detection limit =1.0 ug/m .
b/ Detecionn limit =1.0 ppb.
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Table 42. ANALYTICAL DATA FOR SOIL SAMPLES
FOR MIDLAND, MICHIGAN
Acrylamide
U.S. Geological analysis
Sampling Station Survey coordinates (ppb)—
1 722448 m E < 20
4828198 m N
2 722417 m E
4831905 m N
3 723591 m E < 20
4832910 m N
4 725810 m E < 20
4831445 m N
5 725793 m E < 20
4831088 m N
6 726286 m E < 20
4831833 m N
a./ Detection limit 20 ppb, quantitation limit 100 ppb.
77
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REFERENCES
1. "Determination and Evaluation of Environmental Levels of Selected
Toxic Substances," Acrylamide, EPA Contract No. 68-01-1983, July
1977.
2. "Assessment of the Need for and Character of Limitations on Acryl-
amide and Its Compounds," Draft Final Report, EPA Contract No.
68-01-4308, July 1977.
3. Croll, B. T., G. M. Arkell, and R. P. J. Hodge, Water Research, 8_:
989 (1974).
4. Norris, M. V., "Acrylamide," in Encyclopedia of Industrial Chemical
Analysis. F. D. Snell and C. L. Hilton, eds., Vol. 4, pp. 160-168
(1967).
5. Thomann, P., W. P. Koella, G. Krinke, H. Petermann, F. Zak, and R.
Hess, Agents and Actions, 4:48 (1974).
6. "Sampling and Analysis of Selected Toxic Substances," Final Report
No. EPA-560/6-76-021, Ethylene Dibromide, EPA Contract No. 68-01-
2646.
7. "Sampling and Analysis of Selected Toxic Substances," Final Report
No. EPA-560/6-77-026, Vinylidene Chloride, EPA Contract No. 68-
01-4115.
78
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
5. REPORT DATE
Environmental Monitoring Near Industrial Sites:
Acryl amide
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
John E. Going
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.
68-01-4115
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 6/77-10/77
14. SPONSORING AGENCY CODE
EPA-OTS
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A sampling and analysis program was conducted to determine the levels of
acrylamide in air, water, soil, and sediment 'around five industrial sites. The
industrial sites included monomer producers, polymer producers, and polymer users.
Air was collected at the plant perimeters using Chromosorb 101 adsorp-
tion tubes. Soil samples were collected at the air sampling stations. Water and
sediment samples were taken upstream and downstream and at the plant discharge.
No acrylamide was found in any of the air, soil, or sediment samples.
Acrylamide was found in only one water sample. The level was 1,500 ppb. The
identification of acrylamide was confirmed by GC/MS.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATl Held/Croup
Acrylamide
Air
Water
Soil
Sediment
Sampling
Analysis
Monomer Plants
Polymer Plants
Environmental Monitoring
Industrial Plants
Organic
Chemistry
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
79
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