&EFA
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EMB Report 85-FPE-05
July 1986
Air
Hazardous Waste
Treatment, Storage, and
Disposal Facilities
Site-Specific Test Report
Burlington Northern
Paradise, Montana
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SITE-SPECIFIC TEST REPORT
BURLINGTON NORTHERN, PARADISE AND SOMERS, MONTANA
ESED 85/12
EMB 85 FPE 05
Prepared by:
Entropy Environmentalists, Inc.
Post Office Box 12291
Research Triangle Park, North Carolina 27709
.Contract Nos. 68-02-3852 and 68-02-4336
Work Assignment Nos. 24 and 1
PN: 3024 and 3501
EPA Task Manager
Clyde E. Riley
U. S. ENVIRONMENTAL PROTECTION AGENCY
EMISSION MEASUREMENT BRANCH
EMISSIONS STANDARDS AND ENGINEERING DIVISION
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27709
July 1986
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Disclaimer
This document has been reviewed by the Emission Standards and
Engineering Division, Office of Air Quality Planning and Standards, Office
of Air, Noise and Radiation, Environmental Protection Agency, and approved
for publication. Mention of company or product names does not constitute
endorsement by EPA. Copies are available free of charge to Federal
employees, current contractors and grantees, and nonprofit organizations -
as supplies permit - from the Library Services Office, MD-35.
Environmental Protection Agency, Research Triangle Park, NC 27711-
Order: EMB Report 85-FPE-05
11
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CONTENTS
Page
Figures iv
Tables v
1.0 INTRODUCTION - 1-1
2.0 SUMMARY AND DISCUSSION OF RESULTS 2-1
2.1 Soil Storage Pile (Somers, MT) 2-3
2.2 Surface Impoundment (Paradise, MT) 2-7
2.3 Conclusions 2-8
3.0 PROCESS DESCRIPTION AND OPERATION 3-1
4.0 SAMPLING AND ANALYSIS 4-1
4.1 Soil Storage Pile (Somers, MT) 4-1
4.2 Surface Impoundment (Paradise, MT) 4-6
5.0 QUALITY ASSURANCE 5-1
APPENDICES
A ANALYTICAL DATA A-l
EMB Split Sample Inventory A-3
Moisture Determination Data Sheets A-4
Weight Loss Data Sheets A-10
Screening Data Sheets A-13
Percent PM1f, Determination Data Sheets A-19
Metals Analysis Results A-23
Organic Extract Cleanup Data Sheet A-24
Dilution Factors A-25
Organics Analysis Results A-26
Quality Assurance Data A-34
B ANALYTICAL PROCEDURES B-l
Drying and Sieving Procedures B~3
Chemical Analyses B-6
Quality Assurance (QA) Procedures B-12
C SAMPLING PROGRAM PARTICIPANTS AND OBSERVERS C-l
D PROCESS OPERATIONS DATA D-l
Summary of Processes Sampled During Site Survey D-3
Summary of Equipment for Processes Sampled During Site Survey D-4
111
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FIGURES
Number Page
3-1 Schematic of expected operations for management of K001
wastes at the Paradise and Somers, MT facilities. 3-2
IV
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TABLES
Number Page
2.1 Sampling Plan for Burlington Northern 2-2
2.2 Analytical Results of Silt Screening, Weight Loss on
Drying, and PM1f. Sieving, Fugitive Particulate from
TSDF (85/12) 2-5
2.3 Analytical Results for Metals, Cyanide, and Semivolatile
Organic HSL Compounds, Fugitive Particulate from
TSDF (85/12) 2-6
4.1 Sample Drying Procedure Summary 4-2
4.2 Metals, Measurement Methods, and Detection Limits 4-3
4.3 Semivolatile Organic Compounds for Analysis 4-5
5-1 Quality Assurance Results For Metals Analysis 5~2
5-2 Quality Assurance Results For Semivolatile
Organics Analysis 5~3
B.I Metals and Measurement Methods B-7
B.2 Semivolatile Organic Compounds Measured B-9
B.3 Pesticides Analyzed For and Their Quantifiable Detection B-ll
Limits
B.4 Spiking Compounds: Acid Extractables II B-15
B.5 Spiking Compounds: Neutral Extractables V B-16
B.6 Spiking Compounds: Neutral Extractables VI B-17
B.7 Spiking Compounds: Pesticides II B-18
B.8 Spiking Compounds: Metals B-19
v
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1.0 INTRODUCTION
On September 21, 1985. Midwest Research Institute (MRI) observed process
operations at Burlington Northern's facilities at Paradise and Somers,
Montana. While on site, MRI took grab samples of the soil from two
treatment, storage, and disposal related processes. It was originally
intended that this site would be sampled in a manner similar to that of the
seven other sites sampled as part of this study. However, due to (1) limited
funds and (2) the availability of soil contamination data already obtained
for this site, only limited grab sampling was conducted by MRI.
The purpose of visiting this site and the others in the sampling program
was to provide preliminary data on the magnitude of fugitive particulate
emissions from various processes at treatment, storage, and disposal
facilities (TSDF's) and the degree to which these emissions are
contaminated. The U. S. Environmental Protection Agency (EPA) anticipates
utilizing the analytical data from this program with emission models to
estimate contaminated fugitive particulate emissions from TSDF's. The
information generated by this study may ultimately be used by the Office of
Air Quality Planning and Standards (OAQPS) of EPA to assess the adequacy of
regulations governing contaminated fugitive particulate emissions from
TSDF's.
The grab samples of soil collected by MRI at this facility were analyzed
to determine the following:
1-1
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• The percent by weight of silt in the soil (i.e., material that
passes through a 200 mesh screen and has a nominal diameter
less than 75 urn) and the percent by weight of moisture in the
soil.
• The degree of contamination of the soil silt fraction with
metals, cyanide, and semivolatile organics.
• The percent by weight of soil silt that is less than 20 urn in
diameter based on a sonic sieving technique.
At the Burlington Northern facilities, the two processes sampled were a
soil storage pile at Somers, MT and a surface impoundment at Paradise, MT. No
background samples were taken.
Samples taken were analyzed for silt content, PMin content, metals,
cyanide, and semivolatile organics as described in Chapter 4. Research
Triangle Institute (RTI) conducted the analyses for metals and cyanide and PEI
and Associates performed the analyses for the semivolatile organics.
Additional cleanup of semivolatile organic extracts was performed by Triangle
Laboratories, Inc.
Field sampling was performed by Mr. Phillip Englehart of Midwest Research
Institute (MRI). Mr. Lee Beck (EPA Lead Engineer) of the Industrial Studies
Branch (ISB) observed the sampling program.
This report is organized into several chapters addressing various aspects
of the sampling and analysis program. Immediately following this chapter is
the "Summary and Discussion of Results" chapter which presents table summaries
of data on silt and PMlf. content and degree of contamination for each sample
fraction analyzed.
Following the "Summary and Discussion of Results" chapter is the "Process
Description" chapter (supplied by MRI) which includes descriptions of the
processes sampled. The next chapter, "Sampling and Analysis," discusses the
sample collection procedures, sample preparation, and sample analysis. The
1-2
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appendices present the Analytical Data (Appendix A); detailed Analytical
Procedures (Appendix B); Sampling Program Participants and Obserers (Appendix
C); and Processs Operations Data (Appendix D).
1-3
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2.0 SUMMARY AND DISCUSSION OF RESULTS
This chapter presents a summary of the analysis results and a brief
discussion of the sampling and analysis procedures used. Since the detailed
sampling and analytical procedures are not addressed in this chapter, it is
recommended that the reader review Chapter 4, "Sampling and Analysis," prior to
reading this chapter.
Soil samples were collected from two processes at Burlington Northern
facilities. The processes included: (1) a soil storage pile at Somers, Montana
and (2) a dry surface impoundment at Paradise, Montana. The analytical
procedures used were those described in the Sampling and Analysis Protocol
written specifically for this sampling program. These are briefly described in
Chapter 4 and detailed in Appendix C. The sampling procedures deviated from
the Sampling and Analysis Protocol in that the samples were collected using
grab sampling techniques and therefore should not be considered random nor
representative of the process from which they were taken.
This site-specific report is intended to present the data relevant to the
samples obtained at one facility in this study and the procedures used to
obtain these samples. Some statistical analyses may be performed on the data
concerning this site; however, the majority of statistical analyses may involve
the data collected over the entire study and will be included in a summary
report to be completed at the conclusion of the program.
The sampling plan for the Burlington Northern facilities is shown in
Table 2.1. In this case, the sample collection techniques involved using a
scooping technique to obtain near surface samples. The analyses of the
collected samples were conducted to measure the concentration of the most
2-1
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TABLE 2.1. SAMPLING PLAN FOR BURLINGTON NORTHERN
Process Process Number of Collection Analyses
Sampled Designation Samples Method
Soil Storage Pile — 4 Grab Loss on drying
Silt and PM1Q .
Metals and cyai
Semivolatile organics
Somers, MT , Sample Silt and PM content
Metals and cyanide
Surface Impoundment —'• 2 Grab Loss on drying
Paradise, MT Sample Silt and PM1f) content
Metals and cyanide
Semivolatile organics
2-2
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likely compounds or elements that could be soil contaminates (metals, cyanide,
semivolatile organics, and pesticides).
According to the Sampling and Analysis Protocol, the collected samples were
to be analyzed for the metals, cyanide, semivolatile organics, and pesticides.
If significant quantities of cyanide, semivolatile organics, or pesticides were
not expected to be present in samples from a particular process, the analysis
of those corresponding compounds was not performed. MRI decided that at this
particular site, pesticides were not likely to be present in significant
quantities and therefore, pesticides analyses were deleted. All. samples were
analyzed for metals, cyanide and semivolatile organics. Complete lists of
compounds or elements for which analyses were conducted and their detection
limits are presented in Chapter 4 (see Tables 4.2 and 4.3). Organic compounds
in some samples caused the detection limits to be higher than desired for the
semivolatile organic analyses. An alternative cleanup method was developed to
minimize this problem, and the samples were analyzed at a lower detection
limit.
The analytical results are discussed in the following subsections.
Complete analytical data sheets are presented in Appendix B.
2.1 SOIL STORAGE PILE (SOMERS, MONTANA)
Four grab samples were collected from the soil storage pile. The storage
pile precluded the use of a sampling grid. The percent weight loss on drying
(LOD) determined on a ten-gram aliquot of each sample averaged 11.7 percent.
The storage pile samples were oven dried at 105 C for 1.5 hours and then stored
in a desiccator for 67-5 hours prior to being screened for silt content. The
silt content of the four jars constituting the storage pile samples (sample
identification numbers 11 through 14) averaged 10.2 percent silt by
2-3
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weight (see Table 2.2). The composite silt material (sample identification by
number 52) separated from the soil samples was sonic sieved. Material passing
through a 20 urn sieve constituted the PM content. The PM _ content averaged
10.84 percent by weight of the silt material. The silt screening did not
produce a sufficient quantity of silt to allow the production of PM1(-. or
greater than PM.- material (silt not passing through a 20 urn sieve, refered to
as >PM,0) for the chemical analyses.
Results of the analyses for metals, cyanide, and semivolatile organic
compounds are shown in Table 2.3. The analytical results for the metals and
cyanide in the storage pile silt sample (sample ID 51) are in terms of
micrograms of the metal or cyanide per gram of silt sample (dry basis). The
storage pile silt sample (sample ID 50) was also analyzed for semivolatile
organic compounds. The analysis was on the storage pile silt composite sample
extract prepared by following the low-level procedures in the U. S. EPA
Contract Laboratory Program, Statement of Work for Organic Analysis, 7/85
Revision (referred to as the CLP in this report). The extract was screened by
gas chromatography/flame ionization detection (GC/FID) as specified in the CLP
and found to be at the medium level concentration (organic compound content
greater than 19.8 ug/g) and cleaned by adsorption chromatography on Sephadex
LH-20. The cleaned extract was analyzed after a 9-1-fold dilution resulting
from the cleanup procedure and a second 10-fold dilution necessary to protect
the gas chromatograph/mass spectrometer (GC/MS). At a detection limit of 29-7
ug/g, sixteen semivolatile compounds found on the CLP hazardous substance list
(HSL) were detected in the soil storage sample (see Table 2.3). Four
compounds (acenapthylene, benzo(k)fluoranthene, indeno(l,2,3-cd)pyrene, and
benzo(g,h,i)perylene) were found in the sample at concentrations below the
quantifiable detection limit; they met the mass spectral criteria, however, and
are reported as estimated values.
2-4
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TABLE 2.2.
ANALYTICAL RESULTS OF SILT SCREENING, WEIGHT LOSS ON DRYING, AND PM
FUGITIVE PARTICULATE FROM TSDF (85/12)
10
SIEVING
Site and
Process
Somers, MT
Soil Storage Pile
Paradise, MT
Surface Impoundment
Sample I
ID
11
12
13
14
Average
Std. Dev,
21
22
Average
Std. Dev.
3ercent
Silt*
7-7
8.8
14.8
9-3
10.2
1.6
0.4
1.0
Percent
Loss on
Drying
16.65
8.40
9-53
12.21
11.7
3.2
9-26
11.98
10.62
0.9
Sample
ID
52
52
3-7
62
62
1.92
Percent
PM10
11.26
10.41
10.84
0.60
0.81
1.05
0-93
0.17
*A11 silt values determined using a full stack of sieves.
2-5
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TABLE 2.3. ANALYTICAL RESULTS FOR METALS, CYANIDE, AND SEMIVOLATILE ORGANIC
HSL COMPOUNDS, FUGITIVE PARTICULATE FROM TSDF (85/12)
Metals Analysis
Sample Identity
Element
Aluminum (Al)
Antimony (Sb)
Arsenic (As)
Barium (Ba)
Beryllium (Be)
Cadmium (Cd)
Chromium (Cr)
Cobalt (Co)
Copper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Molybdenum (Mo)
Nickel (Ni)
Osmium (Os)
Selenium (Se)
Silver (Ag)
Thallium (Tl)
Vanadium (V)
Zinc (Zn)
cyanide
Organic Analysis
Sample Identity
Compound
Napthalene
2 -Methy Inapthal ene
Acenapthylene
Acenapthene
Dibenzofuran
Fluorene
Phenanthrene
Anthracene
Fluor anthene
Pyrene
Benzo( a) anthracene
Chrysene
Benzo(k) f luoranthene
Benzo( a)pyrene
Indeno( 1, 2, 3-cd)pyrene
Dibenz (a, h) anthracene
Benzo(g,h, i)perylene
Sample Detection Limit
Soil Storage, RCRA Pond
51
Silt
(ug/g)
23,736
<0. 5
7.4
222
1.00
16.3
31.5
6.2
132
18,405
95.7
219
<0.03
<6
12.8
<2
<0. 5
<9
0.6
39.4
4, 157
<0.5
Soil Storage, RCRA Pond
50
Silt
(ug/g)
120
300
8. 4 J
680
420
650
710
480
370
290
170
160
6. 1 J
59.0
21.0 J
N.D.
15.0 J
(ug/g) 29.7
Pond Bottoms
61
Silt
(ug/g)
16, 461
<0.5
2. 1
176
0. 40
<5
21. 5
4.4
362
12, 412
41.8
126
0. 12
<6
12. 1
<2
<0.5
<9
<0.5
26.7
298
<0.5
Pond Bottoms
60
Silt
(ug/g)
240
670
38. 0 J
2,800
1, 500
2,600
4,800
2,300
2, 600
2, 100
790
850
480
280
120
30 J
89 J
94. 0
N.D. = less than the samples detection limit.
J = Estimated value where the compound meets the mass spectral
criteria but the result is less than the quantifiable limit.
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With the exception of (1) the sampling procedures, (2) diluting the
semivolatile organic sample extract prior to the GC/MS analysis, and (3) the
use of the LH-20 cleanup method for the second analysis, all procedures for the
soil storage pile samples followed the Sampling and Analysis Protocol.
2.2 SURFACE IMPOUNDMENT (PARADISE, MT)
The surface impoundment at Paradise, MT was also not sampled using a grid
layout; instead two grab samples were collected from this process. The scoop
sampling technique was employed to obtain the near-surface samples . The LOD
for the samples (ID numbers 21 and 22) averaged 10.62 percent by weight. The
samples were oven dried at 105 C for 1.5 hours followed by desiccation for 18.5
hours prior to silt screening. The two samples were screened for silt content
which averaged 1.0 percent silt by weight (see Table 2.2). The silt composite
(sample identification number 62), resulting from screening samples 21 and 22,
was then sonic sieved for PM..,-, content which averaged 0.93 percent by weight.
The screening did not produce a sufficient quantity of silt to allow the
production of PM-,n and >PM1_ fractions for chemical analyses. The results for
the metals and cyanide are expressed in micrograms (ug) of the metal per gram
of sample on a dry basis.
The silt fraction from the surface impoundment samples was also analyzed
for semivolatile organic HSL compounds at two different detection limits. The
analysis was conducted on the sample extract prepared by the low-level
procedure. The sample extracts were screened by GC/FID and found to be at the
medium concentration level. The extracts were cleaned by adsorption
chromatography on Sephadex LH-20. The cleaned extracts were analyzed after a
20-fold dilution, in addition to the 14. 3-fold dilution resulting from the
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cleanup procedure. In the silt sample, seventeen semivolatile HSL compounds
were detected. Three compounds (acenapthylene, dibenz(a,h)anthracene, and
benzo(g,h,i)perylene) were found at concentrations below the sample's
quantifiable detection limit of 9^.0 ug/g (see Table 2.3).
With the exception of (1) the grab sampling, (2) diluting the semivolatile
organic sample extracts prior to the GC/MS analysis, and (3) the use of the
LH-20 cleanup method, all procedures used for the surface impoundment samples
followed the Sampling and Analysis Protocol.
2.3 CONCLUSIONS
No major problems were encountered collecting the grab samples; for
sampling, the Sampling and Analysis Protocol was not followed and the samples
should therefore not be considered representative of their respective processes
as specified by this protocol.
The LOD measurement was intended to measure the moisture content of the
soil samples. However, the LOD procedure is an indirect measure of moisture
along with volatile components. A high bias can occur when volatile compounds
are lost from the sample during the procedure. The LOD values were used to
select the drying procedures for the samples (e.g., desiccation or oven
drying). In the analyses of the samples, no problems were encountered in
obtaining silt content or determining PM10 content. The results of the metals
analyses are also believed to be accurate.
The only significant problem encountered during the organic analyses was
the fact that the samples contained a significant amount of non-HSL organic
compounds. This prevented the semivolatile organics analyses from being
conducted at the level described in the analytical protocol. Because of the
high concentrations of organics, the samples had to be diluted to protect the
2-8
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analytical equipment. An alternative sample clean-up procedure was used on the
sample extracts in an attempt to remove these organics. The clean-up procedure
used on the semivolatile organic sample extracts allowed the samples to be
analyzed at lower quantifiable detection limits.
2-9
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3.0 PROCESS DESCRIPTION
The primary rationale for conducting a site survey at this facility,
was different than that for the remaining sites visited as part of the TSDF
particulate emissions study. Whereas the other facilities were chosen to
represent more or less "permanent" TSDFs that might be expected to continue
operations indefinately, this facility was chosen for a site visit in order
to observe a set of activities with finite duration. Specifically, this
facility was visited in order to observe the excavation of residual hazar-
dous material from a surface impoundment (SI), and subsequent transfer of
this material to an acceptable storage unit. Based on conversations with
regional EPA personnel it appears that this sequence of operations--
excavation and transfer—is an option that many facilities will pursue in
response to the November 1984 Hazardous and Solid Waste Amendments to
RCRA.1 These amendments require that operating Sis have a double liner
system; as a result residual material must be removed in order to install
the liner system or alternatively to "close" the SI.
Because construction was not completed on the storage unit, no actual
excavation and transfer operations were observed during the site visit.
The following description represents the anticipated excavation and trans-
fer procedures as supplied by facility personnel.
Figure 3.1 provides a schematic of the expected operations. The ex-
isting surface impoundment (A) contains approximately 14,500 yards3 of
residual creosote-contaminated material (EPA hazardous waste No. K001).
The existing storage pile (B) contains approximately 4,000 yards3 of K001
material. Note that B is located at a separate facility about 80 miles
from A and C. After completion, the new storage pile (C) will contain
about 18,500 yards3 of K001 material. C will have a double lined system
with a bottom liner of 40 mil HOPE and an upper liner of 100 mil HOPE. The
pile surface will be covered with plastic to prevent moisture infiltration
and to control wind erosion.
According to facility personnel it is anticipated that the material in
storage will eventually be used in a land treatment operation (D). At the
time of survey, two pilot plots (200 ft2 each) had been established and ex-
periments were underway to determine environmentally acceptable loading
rates, application frequencies, etc. About 20 acres are available for de-
velopment of a full-scale land treatment unit. It is anticipated that the
unit will consist of four, equal area (~ 5 acre) plots.
Resource Conservation and Recovery Act (RCRA) Section 3004 Part (o)(l)(A)
RCRA Section 3005 Part (j)(l) and (9).
3-1
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PtLE
B
DISPOSAL
,
I
Figure 3.1. Schematic of expected operations for management of K001
wastes at the Paradise and Somers, MT facilities.
3-2
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The principal equipment types, functions, and approximate level of
activity expected for the excavation and transfer operations, are sum-
marized below.
Equipment (commercial
designation if available)
Function
Activity units
Excavator (JD-690A)
Front-end loader
(CAT 645-E or
CAT 745-HB)
5 or 6 dump trucks—
3 axle, 10 wheel;
3 tag-along trailers.
Excavation of material re-
maining in slough at
Paradise, MT (A). Will
be transferred to dump
trucks and move to
storage pile (C).
Anticipated function will
be removal of material
from existing waste pile
(C) and transfer to dump
trucks/trailers.
Transfer of waste pile ma-
terial from C to A.
Bucket capacity-1 yd3;
short duration project
with activity exceeding
8 hr/day.
Short duration project.
Activity will probably
exceed 8 hr/day.
Dump truck capacity—12 yd3;
taa-along trailer capacity--
10 yd3.
In removal of material from the existing waste pile, the front-end
loader will be the only equipment operating in the waste pile area. An
HOPE liner will be located adjacent to the pile and will be used as the
load-in area. This represents an operational/control measure to prevent
spreading of the contaminated material. After completion of the operation,
the liner will be steam-cleaned.
3-3
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4.0 SAMPLING AND ANALYSIS
This section outlines the procedures used for the sampling and analysis of
the samples collected at the Burlington Northern facilities. Sample
collection procedures did not follow those presented in the Sampling and
Analysis Protocol developed for this sampling program. Rather, they consisted
only of grab sampling the soil in specific areas and piles selected by the
tester. The analytical procedures used to analyze these soil grab samples did
follow the Sampling and Analysis Protocol. Analyses specific to this site are
described in this chapter; any deviations from the standard analysis procedures
(see Appendix C) are discussed.
Two processes were sampled: a soil storage pile and a surface
impoundment. The samples from each of these processes were analyzed for silt
and PM1f) content, metals, cyanide, and semivolatile organics. A tabular
presentation of the sampling plan for the Burlington Northern facilities which
specifies the number and types of samples and the locations at which they were
collected can be found in Chapter 2 (see Table 2.1). The subsections that
follow further describe the applicable analytical procedures.
4.1 SOIL STORAGE PILE (SOMERS, MT)
The soil storage pile was located at Somers, Montana. MRI determined that
four samples would be collected from this pile. A simple grab sampling
technique with no procedures to ensure representativeness was used to collect
the samples. The four samples collected were numbered 11 through 14.
A ten-gram aliquot of each sample from this site was first analyzed for
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weight loss on drying (LOD) by drying for 12 to 16 hours in a 105 C oven.
Because the LOD value was greater than ten percent, all samples were oven dried
at 105 C for 1.5 hours and stored for 67-5 hours in a desiccator (see Table
4.1). Following drying, the samples were screened to determine percent silt
content and were sonic sieved to determine percent PM-.^ content (see Appendix C
for specifics of sample handling during each of these analyses). The part of
the silt sample that did not pass through the 20 urn sonic sieve was referred to
as the "greater than PM " (>PM10) fraction.
TABLE 4.1. SAMPLE DRYING PROCEDURE SUMMARY
Sample ID
Process Description
Drying Procedure
11
21
Soil Storage Pile
Somers, MT
Surface Impoundment
Paradise, MT
Oven dried at 105 C for 1.5 hours
and stored for 67-5 hours in a
desiccator
Oven dried at 105 C for 1.5 hours
followed by 18.5 hours of
desiccation
Using the screening techniques described in Appendix C, all the samples
from this process were utilized to make composite samples of the silt. A
portion of this fraction was then sent to RTI for metals and cyanide analysis.
The silt screening did not produce a sufficient quantity of silt to allow for
the production of PM1f) and >PMin material for chemical analysis.
The procedures used for analysis of the metals followed the methods
outlined in the EPA publication "Testing Methods for Evaluating Solid Waste,"
SW-846. The metals measured and the detection limit of the analytical methods
used are shown in Table 4.2. Samples for analysis of all metals except mercury
(Hg) were prepared by acid digestion using EPA Method 3050 (SW-846). Mercury
4-2
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TABLE 4.2. METALS, MEASUREMENT METHODS, AND DETECTION LIMITS*
Element
Aluminum (Al)
Antimony (Sb)
Arsenic** (As)
Barium** (Ba)
Beryllium (Be)
Bismuth (Bi)
Cadmium** (Cd)
Chromium** (Cr)
Cobalt (Co)
Copper (Cu)
Iron (Fe)
Lead** (Pb)
Manganese (Mn)
Mercury** (Hg)
Molybdenum ( Mo )
Nickel (Ni)
Osmium (Os)
Selenium** (Se)
Silver** (Ag)
Thallium (Tl)
Vanadium (V)
Zinc (Zn)
Detection Limits (ug/g)*
ICAP*** GFAA*** Cold Vapor AA***
40
1.0
1 r>
— — — — — J. . U
0.7
0.1
10.0
0.4
0.7
0.7
7.3
100
10.0
5.9
0*5C
• o
9.0
2? _____
.£. — — — — —
4.0
In
. u
10
1.0
3.9
0.2
Detection limits were calculated as three times the standard deviation of
the values measured for compounds at or near the suspected detection limit
in the background sample. For compounds not detected in the background
sample, the detection limits were calculated as three times the standard
deviation of the background noise. Fe, Mg, and Al detection limits were
determined using low level standards as three times the standard deviation
of the values measured.
**
Eight RCRA metals
***
ICAP = Inductively-Coupled Argon Plasmography
GFAA = Graphite Furnace Atomic Absorption
AA = Atomic Absorption
4-3
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(Hg) samples were prepared and analyzed by the cold-vapor atomic absorption
procedure following EPA Method 7^71• Two modifications were used in the final
dilutions of the digestates. The samples for inductively-coupled argon
plasmography (ICAP) determination by EPA Method 6010 and furnace atomic
absorption determination of antimony (Sb) by EPA Method 7041 were diluted to
achieve a final concentration of 5# HC1. The sample digestates for arsenic
(As) determination by EPA Method 7060, for selenium (Se) determination by EPA
Method 7740, and for thallium (Tl) determination by EPA Method 7841 were
diluted to achieve a final concentration of 0.5$ nitric acid.
Cyanide determinations were done by colormetric measurement following EPA
Method 335-3 found in "Methods for the Evaluation of Water and Wastewater,"
EPA-600/4-79-020. The analyses for metals and cyanide were performed without
any problems.
A portion of the composite sample of the silt was also sent to PEI; this
was analyzed for the semivolatile organic compounds listed in Table 4.3- The
silt from the soil storage pile was prepared for analysis of semivolatile
organics following the low concentration level extraction method detailed in
EPA Contract Laboratory Program, Statement of Work for Organic Analysis, 7/85
Revision (referred to as the CLP in this report). The sample extracts were
screened by gas chromatography/flame ionization detection (GC/FID) to determine
the concentration level of the organic compounds in the sample extract. The
extracts were found to be at the medium level (i.e., containing any organic
compound over 19.8 ug/g). An alternative cleanup procedure for the sample
extracts using adsorption chromatography was developed to reduce the amount of
sample dilution necessary to protect the GC/MS, which correspondingly allowed
the GC/MS analyses to be conducted at a lower detection limit. The
4-4
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TABLE 4.3. SEMIVOLATILE ORGANIC COMPOUNDS FOR ANALYSIS
ACENAPHTHENE
ACENAPHTHYLENE
ANTHRACENE
BENZO (a) ANTHRACENE
BENZOIC ACID
BENZO (a) PYRENE
BENZO (ghi) PERYLENE
BENZO (b) FLUORANTHENE
BENZO (k) FLUORANTHENE
BENZYL ALCOHOL
BIS (2-CHLOROETHOXY) METHANE
BIS (2-CHLOROETHYL) ETHER
BIS (2-CHLOROISOPROPYL) ETHER
BIS (2-ETHYHEXYL) PHTHALATE
4-BROMOPHENYL PHENYL ETHER
BUTYL BENZYL PHTHALATE
4-CHLOROANILINE
4-CHLORO-3-METHYLPHENOL
2-CHLORONAPHTHALENE
2-CHLOROPHENOL
4-CHLOROPHENYL PHENYL ETHER
CHRYSENE
DIBENZO (a,h) ANTHRACENE
DIBENZOFURAN
1,2 DICHLOROBENZENE
1,3 DICHLOROBENZENE
1,4 DICHLOROBENZENE
3,3'-DICHLOROBENZIDINE
2,4-DICHLOROPHENOL
DIETHYLPHTHALATE
2,4-DIMETHYLPHENOL
DIMETHYL PHTHALATE
DI-N-BUTYLPHTHALATE
2,4-DINITROPHENOL
2,4-DINITROTOLUENE
2,6-DINITROTOLUENE
DI-N-OCTYL PHTHALATE
FLUORANTHENE
FLUORENE
HEXACHLOROBENZENE
HEXACHLOROBUTADIENE
HEXACHLOROCYCLOPENTADIENE
HEXACHLOROETHANE
INDENO(l,2,3-cd) PYRENE
ISOPHORONE
2-METHYL-4,6-DINITROPHENOL
2-METHYLNAPHTHALENE
2-METHYLPHENOL
4-METHYLPHENOL
NAPHTHALENE
2-NITROANILINE
(Continued)
4-5
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TABLE 4.3. (continued)
3-NITROANILINE
4-NITROANILINE
NITROBENZENE
2-NITROPHENOL
4-NITROPHENOL
N-NITROSO-DI-N-PROPYLAMINE
N-NITROSODIPHENYLAMINE
PENTACHLOROPHENOL
PHENANTHRENE
PHENOL
PYRENE
1,2,4-TRICHLOROBENZENE
2,4,5-TRICHLOROPHENOL
2,4,6-TRICHLOROPHENOL
extract from the soil storage pile sample was concentrated and subjected to an
adsorption chromatography cleanup procedure using Sephadex LH-20 (described in
Appendix C). The clean up procedure resulted in a 9-1-fold dilution of the
sample extract. The extracts were diluted another 10-fold prior to analysis on
a capillary-column gas chromatograph/mass spectrometer (GC/MS). The dilutions
resulted in a detection limit of 29-7 ug/g for the semivolatile organic HSL
compounds. The dilutions resulted in a higher detection limit than the
originally intended level of 0.330 ug/g, but the dilutions were necessary to
protect the GC/MS.
4.2 SURFACE IMPOUNDMENT (PARADISE, MT)
The surface impoundment was located at Paradise, MT. MRI determined that
two samples would be collected by the simple grab sampling technique described
earlier. The two samples taken from the surface impoundment were numbered 21
and 22.
Because the LOD determination on a 10-gram portion of sample yielded a
value greater than 10 percent, the samples from this process were oven-dried at
4-6
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105°C for 1.5 hours followed by desiccation for 18.5 hours prior to screening
(see Table 4.1). They were then screened to determine percent silt
content and sonic sieved to determine PMin content (see Appendix C for a
complete explanation of sample handling during these analyses).
The same screening and sieving techniques used for the soil storage pile
samples were used to make a composite sample of the silt from the surface
impoundment. Portions of the silt composite were sent to RTI for metals and
cyanide analyses and to PEI for semivolatile organics analysis. All samples
were analyzed for metals, cyanide, and semivolatile organic compounds as
described previously for the composite sample from the soil storage pile.
Like the soil storage pile sample, the semivolatile organic extract from
the surface impoundment sample was prepared by the low-level procedure,
concentrated, and subjected to the LH-20 cleanup procedure. The cleaned
extracts were analyzed by GC/MS after an additional 20-fold dilution following
a 14.3-fold dilution resulting from the LH-20 cleanup procedure. The detection
limit for the surface impoundment silt sample was 94.0 ug/g (see Table 2.4)
after a total of a 285-fold dilution.
4-7
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5.0 QUALITY ASSURANCE
The quality assurance (QA) measures for the chemical analyses were
conducted internally by each laboratory. For the metals analysis, RTI used
National Bureau of Standrads (NBS) water (1643 B) as check samples for the
accuracy of the instrumentation. An NBS fly ash sample (1633 A) was used as a
QA sample to check the overall accuracy of the digestion and analysis
procedures. One sample was spiked with eight elements and their percent
recoveries calculated to assess matrix effects. Another sample was analyzed in
duplicate to demonstrate analytical precision. Quality assurance results for
the metals analysis are presented in Table 5-1-
For the QA on the analysis of the semivolatile organics and pesticides
(Table 5-2), PEI used a sample (ID number 50) for a matrix spike (MS) and a
matrix spike duplicate (MSD). The percent recoveries were determined and the
relative percent difference (RPD) for the duplicates were calculated. The
percent recoveries of the matrix spike compounds were outside the QA limits for
all compounds except 2-chlorophenol in the MS and MSD samples and phenol in the
MS sample. For acenaphthene and pyrene, the concentration of these compounds
originally in the unspiked sample were 205 and 86.7 times higher than their
matrix spike concentrations. For all the spike compounds, the spike concen-
trations were 5-to-10 fold less than the sample's quantifiable detection limit
due to the sample dilutions necessary to protect the GC/MS. Six semivolatile
compounds were detected in the MS and/or MSD samples, but not in the unspiked
sample (see Table 5-2). The dilutions of the samples may also have been the
reason that the compounds were found in the MS and/or MSD but not the unspiked
sample.
5-1
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TABLE 5.1. QUALITY ASSURANCE RESULTS FOR METALS ANALYSIS
Sasiple Identity
Eleaents (ug/g)
AluainuB (Al)
Antisony (Sb)
Arsenic (As)
Ban us (Ba)
Beryllium (Be)
Cadoiua (Cd)
Chromium (Cr)
Cobalt (Co)
Copper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Nn)
Mercury (Hg)
Molybdenui (Mo)
Nickel (Nil
Osiiui (Os)
Selenium (Se)
Silver (Ag)
ThalliuB (Tl)
Vanadiua (V)
Zinc (Zn)
cyanide
EPA Check
Expected
(ug/g)
-
8.2
43.0
-
29.0
9.1
7.1
43.0
8.9
-
43.0
13.0
-
-
-
-
7.6
-
25.2
130
10.0
-
Saople
Found
(ug/g)
-
9.0
43.6
-
30.5
7.7
6.8
40.1
12.3
-
43.0
12.9
-
-
-
-
6.9
-
26.7
123
10.0
-
NBS Fly Ash 1633 A
Expected
(ug/g)
140,000
7.0
145
1500
12.0
1.0
196
46.0
118
94,000
72.4
190
0.17
29
127
-
10.3
-
5.7
300
200
-
Found
(ug/g)
18,000
3.5
136
743
3.9
3.0
41.4
15.9
43.3
35,000
64.5
78.0
0.18
66
40.0
-
7.6
-
2.7
121
94.2
-
NRC Sedisent MESS-1
Expected
(ug/g)
58,000
0.73
10.6
-
1.9
0.6
71.0
10.8
25.1
36,500
34.0
513
-
-
29.5
-
0.4
-
0.7
72.4
191
-
Found
(ug/g)
14,000
0.73
10.3
46.0
0.9
0.1
31.3
10.5
23.3
23,000
53.2
322
-
25.4
22.8
-
0.4
-
0.3
42.9
247
-
Matrix Spike Recovery
Expected
(ug/g)
30,859
-
25.50
1,713
482
481
173
10.1
594
15,285
521
619
0.45
109
136
-
20.0
494
19.9
158
703
-
Found
(ug/g)
31,436
-
28.30
1,300
422
412
142
11.5
541
14,718
446
550
0.46
84
119
-
19.7
437
17.8
147
599
-
Percent
-
-
nn
76*
B8X
867.
827.
-
91X
-
861
89X
103X
77Z
881
-
99Z
88*
B9Z
93?
B5X
-
Duplicates
Silt
(ug/g)
89,102
1.5
12.0
94.4
3.7
<5
4,278
250
248
173,248
97.3
192
<0.03
89.3
528
<2
<0.5
52.3
0.5
694
963
<0.5
Silt
(ug/g)
83,695
1.3
5.7
88.6
3.6
<5
4,103
240
239
172,113
94.5
187
<0.03
92.0
483
<2
<0.5
116
<0.5
663
912
<0.5
5-2
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TABLE 5.2. QUftLITY ASSURANCE RESULTS FOR SEMIVOLftTILE ORGANICS ANALYSIS
SOIL SURR06ATE PERCENT RECOVERY SUMMARY
Sample Identity
Surrogate Cotpounds
Nitrobenzene-dS
2-Fluorobiphenyl
Terphenyl-dl4
Phenol -d5
2-Fluorophenol
2,4,6-Tribronophenol
Silt
50
72X
108X
171X
01
OX
721
Silt
60
OX
2561
456X
114!
OX
OX
Sample
Blank
OX
IX
120X
OX
OX
72X
Matrix
Spike
637.
144X
180X
68X
23X
54X
Matrix Spike
Duplicate
72X
126X
154X
63X
OX
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All samples received were also spiked with surrogate compounds and then the
percent recoveries of these compounds were determined. For nitrobenzene-dp.,
the recoveries were within the QC limits for samples 50, 50 MS, and 50 MSD and
the compound was not detected in the method blank or sample 60. For
2-fluorobiphenyl, the recoveries were within the QA limits for sample 50, above
the limit for samples 60, 50 MS, and 50 MSD, and below the limit for the method
blank. For terphenyl-d^, the recovery for the method blank was within the QA
limits and for samples 50, 60, 50 MS and 50 MSD the recoveries were above the
QA limit. For phenol-dn, the recoveries for samples 50 MS and 50 MSD were
5
within the QA limits and for sample 60 the recovery was above the QA limit.
The compound was not detected in the method blank or sample 50. For
2-fluorophenol, the recoveries were below the QA limit for all five samples
with the compound only being detected in sample 50 MS. For 2,4,6-tribromophenol,
the recoveries were within the QA limits except for sample 60 where the
compound was not detected. Because the sample extracts were diluted, the
surrogate compounds were present only in trace quantities. Surrogate compound
recovery data are less accurate when the surrogates are at trace levels.
An analysis was conducted on a method blank sample consisting of a purified
solid matrix spiked with surrogate compounds and carried through extraction,
clean up, and concentration. The CLP specifies surrogate recovery limits for
the blanks as well as limits on the levels of common phthalate esters and
Hazardous Substances List (HSL) compounds. The blank results for di-n-
butylphthalate were below the specified limit.
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