Preparation of the Components of the Modified Method 5 (Method 0010)
Sampling Train for Analysis by SW-846 Method 8270
Radian Corp., Research Triangle Park, NC
Prepared for:
Environmental Protection Agency, Research Triangle Park, NC
Dec 93
amwr
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service

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TECHNICAL REPORT DATA I
1. REPORT HO.
EPA/600/A-94/098
2.
3 I
4. TITLE AHD SUBTITLE
PREPARATION OF THE COMPONENTS OF THE MODIFIED
METHOD 5 (METHOD 0010) SAMPLING TRAIN FOR ANALYSIS
BY SW-846 METHOD 8270
5. RE PORT DATE
6. PERFORMING ORGANIZATION CODE
7. AUTBOR(S)
James F. McGaughey, Raymond G. Merrill, Jr., Joan T.
Bursey, and Denny E. Wagoner, Radian Corporation,
Merrill D. Jackson and Larry D. Johnson, EPA
8.PERFORMING ORGANIZATION REPORT HO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
10.PROGRAM ELEHENT NO.
1 P.O. Box 13000
I Research Triangle Park, North Carolina 27709
11. CONTRACT/GRANT NO. I
68-D1-0010
12. SPONSORING AGENCY HAKE AHD ADDRESS
U. S. Environmental Protection Agency
SMRB, MRDD, AREAL, ORD
Research Triangle Park, North Carolina 27711
13.TYPE OF REPORT AHD PERIOD COVERED
Conference Proceedings,
12/92-12/93
1*. SPONSORING AGENCY CODE
	 	
IS. SUPPLEMENTARY BOTES
16. ABSTRACT
I To validate a source test method for EPA use, data on the method's accuracy and
precision must he obtained at, at least, two different locations. While evaluating
a new method for measuring source emissions of semivolatile halogenated compounds,
data at one source were significantly different from previous laboratory and field
measurements. Recoveries at this source, a chemical manufacturing facility with
substantial moisture in the exhaust stream, were unacceptably low, ranging from 4
to 63 percent. Because these results were at variance with previous results, the
sampling and analysis procedures were evaluated in detail. The quality control
samples isolated the problem to the analysis procedures associated with transfer
and extraction of the XAD-2 adsorbent, which was wet when it returned from the
field test at this site. Sample preparation procedures had generally followed those
specified by the Semi-Volatile Organic Sampling Train method (Semi-VOST; SW-846
I Method 0010), but additional procedures, not specifically prohibited by the
standard method, were utilized to extract the wet XAD-2 from the sample train
before extraction and analysis. These techniques changed the nature of the
resulting extract and suppressed recovery of the target compounds. A new protocol
has been developed to address sample handling for XAD-2 under such conditions.
17. KEY WORDS AKD DOCUMENT ANALYSIS
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b.IDENTIFIERS/ OPEN ENDED TERMS
c.COSATI


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18. DISTRIBUTION STATEMENT
Public
19. SECURITY CLASS (This Report)
Unclassified
21. HO. OF PAGES |
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EPA/600/A-94/098
PREPARATION OF THE COMPONENTS OF THE MODIFIED METHOD 5
(METHOD 0010) SAMPLING TRAIN FOR ANALYSIS BY SW-846 METHOD 8270
James F, McGaughey, Raymond G. Merrill, Jr., Joan T. Bursey, and Denny E. Wagoner,
Radian Corporation, P.O. Box 13000, Research Triangle Park, North Carolina 27709
Merrill D. Jackson and Larry D. Johnson, Atmospheric Research and Exposure
Assessment Laboratory, U. S, Environmental Protection Agency, Research Triangle Park,
North Carolina 27711
ABSTRACT
In a field evaluation study for semivolatile halogenated organic compounds listed in
Title III of the Clean Air Act Amendments of 1990, dynamic spiking experiments using a
liquid solution were performed in the field. Two of four quadruple sampling trains were
spiked for eight sampling runs. Method 0010 train components were prepared and
analyzed in three parts: filter/front half rinse, XAD-2® resin, and
condensate/condensate rinse. In sixteen spiked trains, spiked analytes were detected
with reasonable recoveries (>50%) in only four runs. In general, surrogate compounds
spiked during preparation of the samples showed low recoveries from XAD-2®, and
recoveries of spiked analytes which were observed ranged from 4 to 63 percent>Because
these results were at variance with results obtained for analytes spiked in laboratory
studies and a previous field study, the sample preparation process was investigated in
detail. Sample preparation procedures had followed Method 0010, but use of some
procedures which were not specifically prohibited by Method 0010 had depressed
compound recoveries." Laboratory studies were performed to evaluate the effects of
various sample preparation parameters on compound recoveries..-To ensure that the
sample preparation procedures for Method 0010 train components were clear and
unambiguous, a new protocol to address preparation of Method 0010 train components
for Method 8270 analysis was written. The new protocol has been used in a subsequent
field study with excellent results.
INTRODUCTION
In order to evaluate the performance of SW-846 Method 0010 for sampling and
Method 8270 for the analysis of semivolatile halogenated organic compounds listed in
Title HI of the Clean Air Act Amendments of 1990, a field study was performed using
dynamic spiking techniques to establish the precision and bias of the overall
methodology. Using the guidelines of EPA Method 301 (Protocol for the Field
Validation of Emission Concentrations from Stationary Sources) for statistical design of
the field testing experiments, quadruple Method 0010 sampling trains with four
collocated probes were used. Dynamic spiking equipment and procedures had been
developed and evaluated to allow dynamic spiking of a methylene chloride solution of
the compounds of interest for the duration of each Method 0010 sampling run.

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According to the guidelines of Method 301, two trains were spiked and two trains were
unspiked.
EXPERIMENTAL
The field evaluation study was conducted at a chemical manufacturing facility where
waste chemicals were incinerated in a coal-fired boiler. A "biosludge" consisting of
10 percent organic matter and 90 percent water was fed continually to the indnerator. A
site presurvey, when preliminary samples were taken, showed that none of the proposed
analytes was present in the background emissions from the boiler, and that the emissions
were wet (approximately 10 percent moisture). Method 0010 sampling trains were
recovered in the field, and components were shipped to the laboratory for preparation
and analysis. Extracts (three per sampling train) were generated from methylene
chloride extractions of the following train components:
•	Filter/front half rinse;
•	XAD-2® sampling module; and
•	Condensate/condensate rinse.
The final extract volume for these sampling train components was 5 mL, rather than the
1 mL final volume specified by Method 8270.
Results for the GC/MS analysis are summarized in Table I. To perform a thorough
statistical analysis according to Method 301 procedures, results from six paired spiked
runs are required. Eight sampling runs using quadruple trains had been performed in
the field; acceptable results were obtained for only four runs (1,2,3,6). For those four
runs, most compounds results appear generally comparable to laboratory and field results
obtained previously (Table II). However, results from other sampling runs showed very
low recoveries for the surrogate compounds and many of the spiked compounds were not
detected.
PLACE TABLE I HERE
PLACE TABLE II HERE
RESULTS AND DISCUSSION
Careful examination of the data for all of the sampling runs showed that, in general:

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Table I
Summary of Results for All Eight Runs and All Sampling Trains,
Using Surrogate-Corrected Data
r:.-
Run.
wipasgw
;;HS;::;:sinked;v:^«.Sv
Unsplked

Jnspltod®:^
:<.:S-Y t?.'
. c

x
c


. c

ISIS
*.*•>.s-' V V.'. - >.*%
iil
F
1
y
y
y
y
y
y
y
y
y
y
y
y
2
y
y
y
y
y
y
y
y
y
n
y
y
3
y
y
y
y
y
y
y
y
y
y
y
y
4
n
y
n
n
y
n
y
y
0
y
y
y
5
Z
y
y
Z
y
a
y
y
y
y
y
y
6
y
y
n
y
n
Q
z
y
y
z
y
y
?
a
n
n
y
y
y
z
y
z
y
y
z
8
n
y
Z
y
y
y
z
y
y
y
y
z
Note: Recoveries for C and D Trains refer to recoveries of surrogate compounds and Lsotopically-labeled
analogs.
X =	XAD-2* module.
C =	Condensate fraction.
F =	Filter fraction.
Z =	Partial success; some but not all analytes detected,
y =	All analytes detected,
n =	No analytes detected.

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Table H
Comparison of Percent Recoveries of Semivolatile Ha\^genated
Organic Target Compounds in Laboratoiy and Field Studies
(Uncorrected for Surrogate Recoveries)

Mean Results

Compound .
Laboratory1,
f field I2
' ;Held'2* -1
Bis(chloromethyl)ether
183
0.0
0.0
Epichlorohydrin
75.2
6.0
13.4
cis-l,3-Dichloropropene
21.9
49.1
50.3
trans-l,3-Dichloropropene
20.4
52.0
79.8
1,1,2-Trichloroethane
53.1
56.4
60.3
1,2-Dibromoethane
663
58.9
62.5
Tetrachloroethene
49.7
53.2
49.4
Chlorobenzene
76.0
62.3
65.1
Bromoform
993
59.8
69.3
1,1,2,2-Tetrachloroethane
81.1
64.0
73.9
Dichloroethyl ether
75.8
60.9
77.0
1,4-Dichlorobenzene
68.2"'
56.2
73.5
Benzyl chloride
78.7
67.4
73.9
Hexachloroethane
85.4
74.0
70.9
l,2-Dibromo-3-chloropropane
662
44.8
73.8
1,2,4-Trichlorobenzene
58.2
59.5
76.1
Hexachlorobutadiene
583
65.4
77.1
Benzotrichloride
67.0
60.1
72.4
2-Chloroacetophenone
79.7
56.0
795
Hexachlorocyclopentadiene
513.0
423
59.6
2,4,6-Trichlorophenol
45.6
49.8
75.4
2,4,5-Trichlorophenol
52.7
62.7
76.6
Hexachlorobenzene
32.9
44.6
56.5
Pentachlorophenol
8.9
42.4
603
Pentachloronitrobenzene
38.2
43.4
58.5
Chlorobenzilate
43.6
40.7
61.8
3,3'-Dichlorobenzidme
86.4
4.4
0.6
1Mean of 16 replicates.
2Mean of 12 replicates.
3Mean of 4 replicates.

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•	Recoveries of the surrogate compounds spiked in the laboratory were low
for the XAD-2®, where most of the organic compounds were expected to
be retained;
•	Isotopically-labeled compounds spiked in the laboratory to track recovery
were frequently not observed at all; and
•	The majority of the analytes spiked in the field were not observed.
Recoveries for field-spiked analytes that were observed ranged from
4 percent to 63 percent.
Since the surrogate compounds and isotopically-labeled compounds are spiked in the
laboratory after return of the sampling train components, problems were obviously
encountered in the laboratory preparation rather than in the field spiking.
The critical parameter is recovery of spiked compounds from XAD-2®. Recovery results
for these field samples were sufficiently at variance with previous recovery results from a
laboratory study1 and a field study2 that an explanation for the low recoveries was
pursued. Quality Control results from Method Blanks were examined. Method Blanks
consist of sampling train media (filters, water, solvents, XAD-2®) that are spiked with
surrogate compounds in the laboratory, extracted, and analyzed. Recoveries from
Method Blanks were acceptable to high, indicating that general laboratory sample
preparation and analysis procedures were done properly.
Method Spike recovery data were also examined. Method Spikes consist of train
components spiked with analytes and surrogate compounds in the laboratory. The
Method Spikes are extracted and analyzed with the field samples. The results obtained
for the XAD-2® Method Spikes are typical (Table HE): acceptable to high recoveries
indicated that surrogate and sample spiking, preparation, and analysis procedures were in
control.
PLACE TABLE 3 HERE
From an examination of the Quality Control samples, we concluded that a systematic
error in sample spiking, sample preparation, or analytical procedures did not appear to
be the cause of the low recoveries: Method'Blanks and Method Spikes were prepared
and analyzed with the field samples, using the same_spiking solutions and the same
procedures. The original extracts, which had been archived after mass spectral analysis,
were next examined visually to determine if .the appearance of these extracts was
qualitatively or quantitatively different from the appearance of the Quality Control
samples. Several key differences were observed:

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Table in
Spiked Compounds and Surrogates Recovered
from Dry Method 0010 XAD-2® Traps
Compound ;
. , Surrogate,
2-Fluorophenol
Phcnol-d;
Nitrobenzene-ds
2-Fluorobiphenyl
2,4,6-Tribromophenol
Terphenyl-d14
Epiclilorohydriii-dj
ChJorobcnzenc-dj
l,l,2,2-Tetrachlorotthanc-d2
Bis(cUorocthyl)ether-dg
Benzyl chloridc-d7
2,4,5-Trichlorophenol-d2
Theoretical
Amount ,

991
1010
509
490
997
501
250
350
254
333
244
129
% Recovery >
MS-A.
107
112
112
119
67
135
99
94
114
104
103
ND
MS:B
99
106
95
115
74
112
68
91
93
91
122
ND
MS-C
108
113
104
122
73
115
76
106
99
95
130
106
MS-D
102
108
98
111
66
108
71
93
91
87
117
ND
Targets
(«)
% Recovery
Epichlorohydrm
ds-l,3-Dichloropropene
trans-l,3-DichIoropropene
1,1,2-TrichIoroethane
1,2-DIbromoetbane
Tetrachloroethenc
Chlorobcnzcnc
Bromofonn
l,lA2-Tetrachloroc thane
Bis(chloromethyl)ether
1,4-Dichlorobenzeiie
Benzyl chloride
Hexachloroethane
l,2-Dibromo-3-chIoropropane
1.2.4-TrichIorobenzene
HexacUorobutadiene
Bcnzotrichloride
2-ChIoroaceiophenone
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2.4.5-Trichlorophenol
Hexachlorobcnzene
Pentachlorophenol
Pentachloronitrobenzene
Chlorobenzilate
3,3'-DichIorobenzjdine
199
991
68
72
74
159
87
67
71
76
34
365
77
80
86
195
98
77
84
86
196
95
84
94
95
195
86
82
92
92
200
99
92
96
100
202
101
104
120
127
200
101
84
91
92
252
80
70
72
74
226
96
119
125
131
202
102
95
105
104
185
107
103
112
114
272
103
109
118
121
198
104
120
132
135
200
107
126
139
148
199
106
126
141
142
229
112
108
116
120
204
135
133
133
133
237
109
121
129
129
194
101
127
130
139
222*
"102
110
124
121
202
83
100
87
54
216
101
106
113
114
200
116
110
123
130
190
142
140
171
158

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Method Blanks and Method Spikes were light yellow in color and had the
appearance of several mL of clear organic solvent. The color of field
sample extracts ranged from clear to nearly brown.
Some of the field extracts were clearly completely aqueous, with only small
pools of organic liquid floating on top;
Two phases were clearly visible in some of the field extracts; and
Many of the field samples were not methylene chloride extracts, since only
a slight odor of methylene chloride was detected when vials were opened.
Laboratory sample preparation procedures and observations were carefully reviewed with
laboratory staff. The observation was reported that many of the field samples required
far longer (3-4 hours) than the usual amount of time (20-30 minutes) to achieve
concentration to 5 mL using Kuderna-Danish concentration procedures.
The obvious difference between the Quality Control samples and the field samples was
that the laboratory-generated sampling train media were dry, while the field XAD-2®
samples were wet because of the moisture content of the source. Dry XAD-2® can
simply be poured from the sampling module to the Soxhlet extraction apparatus. Wet
XAD-2® does not pour: the wet resin sticks to the glass walls of the sampling module
and is not readily moved from the sampling module with methylene chloride rinses.
Typical procedures used for the removal of wet XAD-2® from the sampling module
include repeated rinses with methylene chloride, which frequently leaves significant
amounts of the wet XAD-2® in the sampling module, or tapping the sampling module
against the laboratory bench top, which often results in breakage of the sampling
module. Laboratory staff had tapped the XAD-2® from the modules to remove as much
as possible, rinsed the walls of the module with methylene chloride to remove as much
of the remaining wet XAD-2® as possible, and performed a final rinse of the sampling
module with methanol to remove all of the remaining XAD-2®. If a sufficiently large
amount of methanol is present when sample concentration is performed, methylene
chloride will be driven off rather than methanol, and the final extract will consist of a
methanol solution with significant losses of surrogate compounds and analytes.
The rinses used in the field recovery of Method 0010 train components consist of 50:50
methylene chloride: methanol, which form a homogeneous solution. The methanol can
be separated from the methylene chloride only if sufficient water is added to create two
distinct phases. However, 100 mL of methylene chloride can hold up to 15 mL of water
without separating into two distinct phases. According to the method, sample extracts
are dried by filtering through a bed of dry sodium sulfate. If sufficient water is present,
the sodium sulfate will cake and will not dry.the extract efficiently. Thus, after drying, if
the sodium sulfate cakes, an extract may consist of methylene chloride, water, and
methanol, all in one phase. If a solution of this composition is concentrated, methylene
chloride will be lost before the water and methanol are lost, resulting not only in a

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water/methanol solution if sufficient quantities of water and methanol are present in the
original extract but also in lost of target compounds due to higher concentration
temperatures. However, if sufficient water (50-100 mL) to effect separation of phases is
added prior to extraction, the methanol will be driven into the aqueous phase and
excellent recoveries of spiked surrogate compounds and analytes can be obtained.
Laboratory experiments were conducted to reproduce the conditions under which the
field samples had been extracted. Replicate samples of dry XAD-2® were spiked with
surrogate compounds and analytes to provide a baseline for recovery. Excellent
recoveries and good reproducibility were obtained. Next, wet XAD-2® was prepared and
spiked with surrogate compounds and analytes. The 40 g quantity of XAD-2® which is
contained in the sampling module of the Method 0010 train retains approximately 50 mL
of water when water is poured through the resin bed. This 50 mL of retained water does
not produce a distinct water layer when the spiked wet XAD-2® is extracted and
analyzed. When the extracts from the wet XAD-2® were concentrated and analyzed,
recoveries were slightly lower than the recoveries obtained with dry XAD-2® and
reproducibility was slightly poorer, but both recovery and reproducibility were
acceptable. The wet XAD-2® was prepared and spiked in the Soxhlet extractor, so no
transfer of wet XAD-2® was required. Wet XAD-2® alone does not depress recoveries
significantly.
The major problem appeared to occur in the transfer-of the wet XAD-2®. A procedure
was therefore developed to transfer the wet XAD-2® without the use of methanol. The
apparatus shown in Figure 1 is used to transfer the XAD-2® if the resin is too wet to
pour. The glass wool is removed from the end of the sampling module and placed in the
Soxhlet extractor to ensure extraction. A small piece of pre-cleaned glass wool is placed
in the arm of the Soxhlet extractor to ensure that no XAD-2® enters the side-arm. The
XAD-2® sampling module is inverted (glass frit up) over the Soxhlet extractor,
approximately 5-10 mL of methylene chloride is added above the glass frit, and air
pressure created by squeezing the rubber bulb shown in Figure 1 is used to gently but
firmly push the methylene chloride through the frit, forcing the XAD-2® out of the
sampling module. This process is repeated 3 to 5 times, and a Teflon® wash bottle
containing methylene chloride is used to rinse the walls of the sampling module to
transfer XAD-2® which adheres to the walls of the sampling module. After 3-5
methylene chloride rinses, no more than a monolayer of XAD-2® usually remains in the
sampling module. This XAD-2® transfer procedure has been used successfully to
transfer XAD-2® from sampling modules used in sampling a source with 55 percent
moisture: excellent recoveries of both surrogate compounds and spiked analytes were
obtained. In addition, this procedure is far more efficient than the procedure of tapping
the resin out of the sampling module: three transfers using the rubber bulb can be
performed in one or two minutes.
PLACE FIG. 1 HERE

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Rubber
Bulb
W5
MeCI2& added to XAD-2® Trap
Glass
Frit
XAD-2®

Glass Wool
Soxhlet
Precleaned
Glass
Wool
Round
Bottom
Flask
Teflon®
Tube
Sovirel®
Fitting
Ground Glass
Ball Joint
(z
Figure 1. Transfer of Wet XAD-2®

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The investigation with subsequent laboratory study illustrates the value of sufficient
Quality Control data in determining the cause of a problem with data quality. A new
procedure for the preparation of Method 0010 train components for analysis by SW-846
Method 8270 has been written. A flowchart for the overall method is shown in Figure 2.
In this procedure, the use of methanol in the laboratory is directly and specifically
prohibited to ensure that the final extracts consist of methylene chloride, not a mixture
of methylene chloride and methanol. Also, addition of sufficient water to ensure that
two distinct phases are produced when both water and methanol are components of the
solution (for example, in the sampling train rinses of the front half and the condensate)
is a required part of the procedure. This procedure is being subjected to EPA review.
PLACE FIG. 2 HERE
REFERENCES
1.	Laboratory Validation of VOST and SemiVOST for Halogenated Hydrocarbons
from the Clean Air Act Amendments. Volume 1 and 2. EPA 600/R-93/123 and
b. NTIS PB93-227163 and PB93-227171. U. S, Environmental Protection Agency.
July, 1993.
2.	Field Test of a Generic Method for Halogenated Hydrocarbons.
EPA 600/R-93/101. NTIS PB93-212181. U. S. Environmental Protection Agency.
June, 1993.

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Weigh in the Raid
Extract Water Layer with
CH2CI2; Adjust pH and do
Acid/Base or Base/Acid Extraction j
Combine CH2Ci2 Extracts
Concentrate to 5mL
Analyze by GC/MS
XAD-2®
(Containers)
XAD-2®
Extract
Archive
Add Sufficient Water
to Separate Into Two
Phases; Separate
Remove Moisture
with Na»SO„
Spike with Surrogates (and
IsotopicaJIy-Labeled Analogs)
Soxhtet Extraction
Silica Gel
(Impinger4)
(Container 6)
Rinse ail of Glassware Between
Back Half of Filter Holder and
XAD-2® (Filter Holder Back Half
Connector, and Condenser)
with CH2CyCH3OH
(Container 5)	
Figure 2. Sample Preparation Scheme for Method 0010 Train Components

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Combine CH2CI2 Extracts
Combine
Combine CH2CI
Extracts
Separate
CH2C'2
Extract
Remove Moisture with
Na3S04
Concentrate to 5mL
Rinse of Implnger 1
CH CI/CH .OH
Analyze by GC/MS
Concentrate to 5mL
Analyze by GC/MS
Save CH^Ij Layer
(Bottom)
Soxhlet Extraction
CH-Cl,
Spike with Surrogates,
laotopically-Labeled
Analogs
Particulate Matter
Filter
(Container 1)
Fitter; Add Fitter to
Particulate Matter Filter
Separatory Funnel Extraction
(Add H20 if necessary to
separate phases)
Spike with Surrogates and
Isotopically-LfibelQd Analogs
Remove Moisture
with Na.SO.
Extract Water Layer with
CH2CIj ; Adjust pH and do
Acid/Base or Baae/Acid Extraction
Extract Water Layer with
CH2C^; Adjust pH and do I
Acid/Baae or Base/Acid Extraction
Separatory Funnel
Extraction of Filtrate
(Add H2Q if necessary to
separate phases)
Front Half Rinse,
Front Half of Filter
Holder, Probe and Nozzle
ch2ci2/ch3oh
	(Container 2)	
Figure 2. (Continued)

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Disclaimer
The information in this document has been funded wholly by the United States
Environmental Protection Agency under contract 68-D1-0010 to Radian Corporation. It
has been subjected to the Agency's peer review and administrative review, and it has
been approved for publication as an EPA document. Mention of trade names or
commercial products does not constitute endorsement or recommendation for use.

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