United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EMB Report 85-FPE-09
October 1986
Air
Hazardous Waste
Treatment, Storage, and
Disposal Facilities
Field Sampling and
Analysis Protocol
For Collecting and Characterizing
Soil Samples from TSDF's
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EPA-450/3-86-014
ESED No. 85/12
EMB No. 85-EMB-09
FIELD SAMPLING AND ANALYSIS PROTOCOL FOR COLLECTING AND
CHARACTERIZING SOIL SAMPLES FROM HAZARDOUS WASTE TREATMENT, STORAGE,
AND DISPOSAL FACILITIES (TSDF)
By
William G. DeWees
Scott S. Steinsberger
Steven J. Plaisance
CEM/Engineering Division
Entropy Environmentalists, Inc.
Research Triangle Park, North Carolina 27709
Contract Nos. 68-02-3852 and 68-02-4336
Clyde E. Riley, Task Manager
Prepared for
United States Environmental Protection Agency
Office of Air Quality Planning and Standards
Emission Standards and Engineering Division
Emission Measurement Branch
Research Triangle Park, North Carolina 27711
October 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~35i Environmental Protection Agency, Research
Triangle Park, North Carolina 277H; or, for a nominal fee, from the National
Technical Information Service, 5285 Port Royal Road, Springfield, Virginia
22161.
Publication No. EPA-450/3-86-014
EMB Report No. 85-EMB-09
ii
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TABLE OF CONTENTS
Section . Page Number
1.0 INTRODUCTION 1-1
1.1 Establish Goals of Program 1-2
1.2 Develop Test Plan . 1-2
1.3 Conduct Field Sampling 1-3
1.4 Sample Analysis . 1-4
1.5 Emission Modeling 1-4
1.6 Update to Program 1-4
2.0 COMPOUNDS MEASURED AND DETECTION.LIMITS OF 2-1
ANALYTICAL METHODS
3.0 SAMPLING APPARATUS . 3-1
.4.0 . SAMPLING APPARATUS PREPARATION AND CLEANUP 4-1
5.0 FIELD SAMPLING PROCEDURES 5-1
5-1 Facility or Site Documentation 5"!
5.2 Process Identification 5-1
5-3 Grid Layout and Sample Location 5~3
5-4 Sample Collection Procedures . 5"H
5.4.1 Scooping . 5-13
5.4.2 Coring 5-14
5.4.3 Sweeping 5-l4
5.4.4 Vacuuming 5-15
5.5 Collection of Background Samples 5-16
6.0 SAMPLE HANDLING AND TRANSPORT 6-1
7.0 FIELD SAMPLING SAFETY CONSIDERATIONS 7-1
8.0 ANALYTICAL METHODS 8-1
8.1 Raw Sample Analyses and Physical
Characterization 8-1
8.1.1 Loss-on-Drying (LOD) Determination 8-4
8.1.2 Oil and Grease Content Determination 8-4
8.1.3 Sample Drying Procedure 8-4
8.1.4 Silt Screening Procedure 8-7
8.1.5 Sonic Sieving Procedure (Optional) 8-9
8.1.6 Sample Packaging 8-11
8.2 Chemical Analysis 8-12
8.2.1 Metals Analysis 8-12
8.2.2 Cyanide Analysis 8-12
8.2.3 Semivolatile Organic Analysis 8-12
8.2.4 Pesticides Analysis 8-14
iii
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TABLE OF CONTENTS (continued)
Section . Page Number
9.0 QUALITY ASSURANCE PROCEDURES 9-1
10.0 REPORT FORMAT 10-1
11.0 REFERENCES " 11-1
IV
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LIST OF TABLES
Table No. Page No.
2.1 Pesticide Detection Limits 2-2
2.2 Semivolatile Organic Detection Limits 2-3
2.3 Metals, Measurement Methods, and Quantifiable
Detection Limits . 2-4
3.1 Sampling Equipment Specifications 3~3
4.1 Sampling Equipment Preparation and Clean-Up 4-2
8.1 Metals and Measurement Methods 8-13
8.2 Semivolatile Organic Compounds for Analysis 8-15
8.3 Pesticides for Analysis 8-17
9.1 Spiking Compounds: Metals 9~2
9.2 Spiking Compounds: Acid Extractables II 9-4
9.3 Spiking Compounds: Neutral Extractables V 9-5
9.4 Spiking Compounds: Neutral Extractables VI . 9-6
9.5 Spiking Compounds: Pesticides II 9-7
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LIST OF FIGURES
Figure No. .. Page No.
5.1 Example site plot plan. 5-2
5.2 Example form for recording process information. 5-4
5-3 Process dimensions for three unpaved roadway samples
(Processes 01, 02, and 03). 5-5
5-4 Schematic showing dimensions of landfill and stabilization
areas and locations and dimensions of process areas
sampled. 5-6
5.5 Example sketch of process and grid showing suggested
- technique for location sampling points. 5-7
5.6 Example form for sketching process and grid
specifications and recording sampling information. 5~8
5.7 Example sketch showing optimal sampling grid location on
process and sampling locations resulting from process
configuration. 5-10
5.8 Example sketch showing optimal sampling grid location on
process and sampling locations resulting from process
configuration. 5-12
5.9 Example label for sample jars. 5-13
6.1 Example chain-of-custody form. 6-2
8.1 Flow diagram for samples taken from a process. 8-2
8.2 Soil sample processing instruction sheet. 8-3
8.3 Loss-on-drying (LOD) determination data sheet. 8-5
8.4 Sample drying weight loss data sheet. 8-6
8.5 Silt screening data sheet. 8-8
8.6 Percent PM-20 determination data sheet 8-10
8.7 Sample label. 8-11
vi
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1.0 INTRODUCTION
This sampling and analysis protocol presents the procedures for collecting
and characterizing soil samples (surface samples) from processes within
treatment, storage, and disposal facilities (TSDF's). The soil
characterization data, along with meteorological data and process operational
;
data, are used in emission factor equations and dispersion models to assess
the impact on ambient air of contaminated fugitive particulate emissions from
TSDF's. Several emission factor equations for fugitive particulate emissions
are presented in the U.S. Environmental Protection Agency's (EPA's)
Publication AP-42. ' Additional emission factor equations, discussion of
relevant meteorological and process operational data and the calculation of
total emissions are presented in the EPA report of a study conducted to
estimate the magnitude of contaminated fugitive particulate emissions from
TSDF's.3
This sampling and analysis protocol presents generic procedures. It does
not require detailed knowledge of the process (an area devoted to a particular
operation that is a potential source of contaminated fugitive particulate
emissions) or process operational conditions to successfully collect and
characterize process soil samples.
The soil samples (surface samples) are subjected to a series of' laboratory
analyses to determine three physical parameters necessary for the emission
factor equations and a number of chemical parameters needed to calculate the
degree of contamination. The first physical parameter, percent silt on a
weight/weight (w/w) basis (silt content), is determined by dry sieving the
samples. The silt content is defined as the portion of soil material passing
through a 200-mesh screen (<75 urn). Silt content is that fraction of the soil
that can become airborne and figures prominently in particulate emission
models of open dust sources.
The second physical parameter is the fraction (w/w) of silt having a
physical diameter less than 20 ym (PM-20).* This parameter, which is
presented as an optional determination in this protocol, is measured using a
sonic sieving device and is defined as the material passing through a 20-ym
screen. The primary rationale for PM-20 determinations is that some hazardous
*This should not be confused with airborne particulate (e.g., PM1fJ which
is defined in terms of aerodynamic diameter (unit density spheres).
1-1
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materials tend to adsorb preferentially on the surfaces of or exist in the
finer particles at TSDF's. If entrained, this material may remain airborne
for long periods of time and thus may be transported considerable distances
from the site.
The third physical parameter is percent moisture which is gravimetrically
determined as sample weight loss after oven-drying. It should be recognized
that the percent moisture value may represent not only moisture loss, but also
VOC losses. Percent moisture is a parameter that appears in several emission
factor models.
Following separation, the silt (and PM-20 sample fractions, if applicable)
are analyzed to determine the degree of contamination for the species of
interest. These generally include (a) metals, (b) semivolatile organics, and
(c) PCB's/pesticides. Total cyanide levels may also be analyzed. In the case
of land treatment samples, a portion of the original raw sample is analyzed
for oil and grease content.
In organizing and implementing the sampling and analysis program, it is
recommended that the tester use the phases described below.
1.1 ESTABLISH GOALS OF PROGRAM
Because of the complexity and potential effort involved in assessing the
impact of contaminated fugitive particulate from a facility, the individual or
group establishing the goals of the program should be familiar with- the
procedures involved and the facility to be assessed. Process operating
conditions, soil characteristics, and the degree of soil contamination affect
emissions, and therefore, require that each process be tested separately.
Emission factor models and dispersion models require considerable input data,
therefore, program goals must be based on (a) the number of processes to be
assessed and (b) the total effort involved in acquiring the necessary data.
1.2 DEVELOP TEST PLAN
A test plan is highly recommended to define the exact parameters required
by the emission factor calculations and dispersion models and to determine the
number and types of processes to be sampled.
In preparing a test plan:
Identify each process to be tested;
Identify and define meteorological data required for emission factor
calculation;
1-2
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Identify and define process operations data required for emission
factor calculation;
Determine sampling techniques;
Specify sample handling procedures;
Define sample sizing procedures;
Define analyses for degree of contamination;
Define quality assurance procedures;
.Define the safety requirements;
Identify sampling equipment;
Develop a schedule for each phase of program;
Assign responsibilities; and,
Outline coordination of test firm, facility, and responsible agency.
1.3 CONDUCT FIELD SAMPLING
The actual sampling procedures described in this protocol are not difficult
to execute. The two major obstacles to successful and/or representative
sampling are likely to be (1) weather and (2) unexpected process operations and
activities. Although the weather cannot be controlled, testing can be
scheduled to optimize the potential conditions. In the case of process
operations, it is possible that some processes could be active during
sampling. Trucks may be bringing in waste and/or earth moving equipment may be
adding soil cover, etc. The tester should coordinate with the facility before
hand, to avoid trying to grid and/or sample an area with moving equipment.
The sampling procedures are designed to obtain a representative sample of
soil including that which could become airborne. The collected samples are
analyzed for the concentration of likely soil contaminates including metals,
cyanide, semivolatile organics, oil and grease, and pesticides. The sample
collection techniques generally are as follows: (1) for undisturbed hard soil
surfaces, a sweeping technique is used to obtain surface samples; (2) for paved
surfaces, a vacuuming technique is used; (3) for moderately disturbed soil
surfaces, a scooping technique is used to obtain near surface samples; and (4)
for soil surfaces that are mechanically disturbed to a specific depth, coring
is used to sample to the depth of the disturbance.
Meteorological data for making long term emission estimates is obtained
from the nearest weather station. Process operational data is collected at the
time of testing. Plant records may be used to determine the relationship of
current operational data to the long term operations. Both the meteorological
1-3
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data and the process operational data should be representative of the time
period for which the impact of the emissions is to be determined.
1.4 SAMPLE ANALYSIS
The analytical phase of the program involves two major steps. The first
step is determining the physical characteristics of the soil (moisture
content, silt content, and PM-20 content, if applicable). The oil and grease
content is also measured in this first step, if applicable (land treatment
samples). The second major step involves physically separating the soil into
the desired size fractions and analyzing for degree of contamination. The
recommended quality assurance checks (audit samples, surrogate spikes, and
duplicate analyses) provide the precision and relative accuracy of the
analytical phase.
The analytical results for the soil's physical characteristics and the
degree of contamination should, along with the meteorological and process
operational data, provide the parameters necessary to calculate emissions
using the applicable emission factor equations.
1.5 EMISSION MODELING
The data collected during the sampling and analysis phase are used in
emission factor equations to estimate the magnitude of emissions on a process-
specific basis. Dispersion equations can then be used to calculate the impact
of the contaminated fugitive particulate on a site-specific basis. The
emission factor equations and procedures for utilizing the emission models are
not included in this document. The reader is referred to the previously
mentioned EPA study and other EPA documents ' to conduct this portion of the
program.
1.6 UPDATE TO PROGRAM
EPA is conducting on-going work in the area of modeling fugitive
particulate emissions. As a result, the reader is encouraged to check the
literature and with EPA to see if new models or protocols have been developed
as a result of these studies.
The sampling phase of the program uses a routine scientific approach to
obtain a representative sample. Therefore, it is not anticipated that any
major changes will be made in the sampling protocol. However, as the degree
of variation found in typical processes is better documented, then the number
1-4
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of samples to be taken at a particular process to obtain a desired variation
will be better defined. Also, conditions for determining when samples should
and should not be collected may be better defined with more testing experience.
The analytical procedures also are not anticipated to change greatly. The
only portion of the analytical phase that has, thus far, required substantial
modification is the sample extraction cleanup procedures. Many soil samples
contain a high concentration of organics that are not the compounds to be
measured. These organics (typically aliphatics) tend to interfere in the
sample analysis for the organics of interest and can cause a substantial
increase in the detection limits for these organics.
1-5
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2.0 COMPOUNDS MEASURED AND DETECTION LIMITS
OF ANALYTICAL METHODS
The compounds measured in assessing the degree of contamination of the soil
fractions are metals, cyanide, semivolatile organics, oil and grease (land
treatment samples), and pesticides/PCB's. The list of semivolatile organics
and pesticides for which analyses are conducted and their detection limits as
presented were developed from the Hazardous Substance List (HSL) in EPA's
4
Contract Laboratory Program (CLP) Statement of Work. The CLP was chosen
because the large number of samples that have currently been analyzed through
this EPA program provide the maximum opportunity for technology transfer
studies. The CLP also draws heavily from the procedures in EPA SW-846 which
allows other data to be utilized.
The detection limits for pesticides (Table 2.1) and semivolatile organics
(Table 2.2) are based on extracting 30 grams of material as specified by the
low-level extraction procedure in the CLP. If other organic material is
present in significant quantities, sample cleanup procedures will have to be
used. Ultimately, the laboratory may have to dilute the sample extract to
protect the analytical equipment, and these detection limits may not'be
achievable.
The quantifiable detection limits listed for the metals (Table 2.3) are
those that can be obtained for the compounds listed using the analytical
methods described in this protocol. In the case of chromium, samples are
initially analyzed for total chromium content. If the results for any sample
show a relatively significant concentration of chromium, then another aliquot
of that sample is analyzed for hexavalent chromium (the most toxic form) using
procedures in SW-846. Cyanide content is determined colorimetrically following
EPA Method 335.2 with a detection limit of 0.5Vg/g.
If the user of this protocol has knowledge of the compounds present or is
only interested in a few compounds, the quantifiable detection limits may be
improved through the use of more specific analytical techniques and more
sophisticated sample cleanup procedures.
2-1
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TABLE 2.1. PESTICIDE DETECTION LIMITS
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Compounds Detection Limit
( g/kg)
ALDRIN
Alpha - BHC
Beta - BHC
Delta - BHC
Gamma - BHC
CHLORDANE
4,4'-DDD
4, 4 '-DDE
4,4'-DDT
DIELDRIN
ENDOSULFAN I
ENDOSULFAN II
ENDOSULFAN SULFATE
ENDRIN
ENDRIN KETONE
HEPTACHLOR
HEPTACHLOR EPOXIDE
TOXAPHENE
AROCLOR 1016
'AROCLOR 1221
AROCLOR 1232
AROCLOR 1242
AROCLOR 1248
AROCLOR 1254
AROCLOR 1260
8
8
8
8
8
80
16
16
16
16
8'
16
16
16
16
8
8
160
80
80
80
80
80
160
160
2-2
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TABLE 2.2. SEMIVOLATILE ORGANIC DETECTION LIMITS
Number
1
2
3
4
5
6
7
8
9
10
11
12 '
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
Compounds
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-DINITHOPHENOL
2-METHYLNAPHTHALENE
2-METHYLPHENOL
4-METHYLPHENOL
NAPHTHALENE
2-NITROANILINE
3-NITROANILINE
4-NITROANILINE
NITROBENZENE
2-NITROPHENOL
4-NITROPHENOL
N-NITROSO- DI -N- PROPYLAMINE
N-NITROSODIPHENYLAMINE
PENTACHLOROPHENOL
PHENANTHRENE
PHENOL
PYRENE
1 , 2 . 4-THICHLOROBENZENE
2,4. 5-TRICHLOROPHENOL
2,4. 6-TRICHLOROPHENOL
Detection
(ug/kg)
330
330
330
330
1600
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
1600
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
1600
1600
1600
330
330
1600
330
330
1600
330
330
330
330
1600
330
2-3
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TABLE 2.3. METALS, MEASUREMENT METHODS, AND QUANTIFIABLE DETECTION LIMITS
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
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* (Eg)
Molybdenum (Mo)
Nickel (Ni)
Osmium (Os)
Selenium* (Se)
Silver* (Ag)
Thallium (Tl)
Vanadium (V)
Zinc (Zn)
Measurement Method**
ICAP
GFAA
GFAA
ICAP
ICAP
ICAP
ICAP
ICAP*
ICAP
ICAP
ICAP
ICAP
ICAP
Cold Vapor AA
ICAP
ICAP
ICAP
GFAA
ICAP
GFAA
ICAP
ICAP
Quantifiable
Detection Limi
(Vg/g)
40
1.0
1.0
0.7
0.1
10.0
0.4
0.7
0.7
7-3
100
10.0
5-9
0.25
9.0
2.2
4.0
1.0
10
1.0
3.9
0.2
**
Eight RCRA metals
»
ICAP = Inductively-Coupled Argon Plasmography
GFAA = Graphite Furnace Atomic Absorption
AA = Atomic Absorption
Other methods are used to measure hexavalent chromium (Cr IV), if appropriat
(see page 2-1).
2-4
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3-0 EQUIPMENT
The use and specifications of the sampling equipment are described in this
section. Recommended field safety equipment is discussed separately in Section
7.0. The following is an inventory and description of the function of the
equipment. Quantities and physical specifications for each item used in the
referenced EPA study are presented in Table 3-1- The tester may substitute
similar equipment that will accomplish the desired goals.
Surveyors Chain - For measuring process dimensions and laying out sampling
grids.
Surveyors Tape - For measuring and laying out sampling grid.
Wooden Survey Stakes, Gutter Spikes, Survey Flags - For marking process
boundaries, grid axes, and sampling points, as needed.
Plastic Flagging - For flagging gutter spikes and stakes, and marking process
boundaries.
40 Quart Cooler - For transporting sample jars and coolant.
Plastic Sheet Roll - Ground cloth on which to set coolers for sample marking
and storage.
Carboy (20 gallon) - Contains distilled water for rinsing and decontamination
of tools.
Disposable Scoops - For taking near sub-surface soil samples.
Glass Jars - Contain and transport soil samples, without contamination.
Cap Liners - Seal glass jars.
Plastic Core Tube - For collecting core samples for metals analysis.
Stainless Steel Core Tube - For collecting core samples for organics analysis.
Wooden Dowel - For pressing cored soil from the metal and plastic core tubes.
Surveyors Hammer - For driving core tubes into soil.
Wallpaper Paste Brushes - For sweeping and collecting road dust.
Vacuum Sweeper - For collecting road dust from paved surfaces.
Shovel - For general excavation.
3-1
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Pick-ax - For general excavation.
Stainless and/or Plastic Steel Bucket - For washing and decontamination of
sampling .tools.
Bottle Brush - For cleaning and decontaminating core tubes.
Plastic Bags - Contain contaminated equipment prior to decontamination and
materials for disposal.
Permanent Marking Pen - For marking sampling scoops/jars.
Bound Log Book - For recording field notes.
Compass - For orienting processes on site plan and laying out process sampling
grids.
Site Description Forms - For recording the layout and condition of each
process site at the time of sampling.
Chain-of-Custody Forms - For tracing the possession of the samples from origin
to analysis.
3-2
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TABLE 3.1. SAMPLING EQUIPMENT SPECIFICATIONS
Description
Dimension*
Material*
Quantity*
Surveyors Chain
Surveyors Tape
Plastic Flagging
Wooden Survey Stakes
Survey Flags
Gutter Spikes
40 Quart Cooler(s)
Plastic Sheet Roll
Carboy
Disposable Scoops
Glass Jars
Cap Liners
Plastic Core Tube
Steel Core Tube
Dowel
Surveyors Hammer
Wallpaper Paste
Brushes
Vacuum Sweeper
(continued)
200' long, 1/4" wide
100' long, 3/8" wide
1-3/10" x 50 yds
1" x 2" x 18"
4" x 5" x 30"
10" long
Adequate to hold
sample jars
12' x 100' roll
20 gallon
190 mm long x 118 ml
capacity
Nominal 475 ml capacity
with wide neck
To fit glass jars
30 cm long x 3-2 cm I.D.
30 cm long x 3.2 cm I.D.
40 cm long x 2.5 cm
diameter
5 Ib x 18" handle
7" handle, 3" bristles,
6" wide
N/A
Steel 1
Steel 2
Plastic 1 carton
Wood . 200
Plastic 100
Aluminum 50
Plastic 3
5 mil poly- 2
ethylene
Nalgene 1
or glass
Styrene 300
Glass with 300
phenolic cap
Teflon 300
PVC 24
Stainless steel 24
Wood 48
Steel/wood 1
Plastic with 25
nylon bristles
With nylon bristle 1
attachment and
utilizing disposable
paper dust bags
3-3
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TABLE 3.1. (continued)
Description
Shovel
Pick-ax
Bucket
Bottle Brush
Plastic Bags
Marking Pens
Log Book
Compass
Dimension
Standard long handle
Standard long handle
12 liter
12" long x 1-1/2"
diameter
Assorted: 2-quart and
20 gallon
Standard 8-1/2" x 11"
Liquid filled,
5 increments
Material Quantity
Steel/wood 1
Steel/wood 1
Stainless steel 1
Wire with plastic 2
bristles
Polyethylene 50 each
Permanent ink 20
Hard cover 1
Plastic/glass 1
*These are the dimensions, materials of construction, and quantity of equipment
used in the referenced EPA study; the tester may substitute similar equipment
that will accomplish the desired goals.
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4.0 SAMPLING APPARATUS PREPARATION AND CLEANUP
Certain sampling equipment items require special pre- and/or post-sampling
treatment. Pre-sampling activities involve preparation of the sampling equip-
ment to ensure that contaminants are not introduced into the samples.
Post-sampling activities, such as equipment clean-up, involve protecting the
samples from external contamination and loss of any constituents, as well as
decontamination of sampling equipment for later use and disposal of equipment
designed for use at only one site, process, or sampling grid cell. Equipment
preparation and cleanup procedures are outlined in Table 4.1. The operations
noted on the table are discussed below.
A. Soap and water wash - A solution of laboratory soap and water is used
to wash surface contaminants from items which are subsequently rinsed_
in water which conforms to the specifications for ASTM, Type 3 water.
B. Methylene chloride rinse - Items are rinsed in methylene chloride in
order to remove surface organic contaminants.
C. Nitric acid rinse - Items are rinsed in a dilute (50/50) nitric acid
solution in order to remove surface traces of metals.
D. Oven dry - Items are dried in a 120°C oven for one hour to evaporate
moisture and volatiles.
E. Disposal of - Items are disposed of in a proper manner after use,
thereby requiring no additional clean-up.
4-1
-------
TABLE 4.1. SAMPLING EQUIPMENT PREPARATION AND CLEAN-UP
Pre-Sampling
Description Preparation
Surveyors Chain
Surveyors Stakes
Surveyors Tape
Plastic Flagging
Survey Flags
Gutter Spikes
40 Quart Cooler
Plastic Sheet Roll
Carboy
Disposable Scoop
Glass Jar
Cap Liners
Core Tube (plastic)
Core Tube (steel)
Dowel
Surveyors Hammer
Wallpaper Paste Brush
Vacuum Cleaner
Bottle Brush
Shovel
Pick-ax
Bucket
Plastic Bags
Marking Pens
Log Book
Compass
A
A
A
A
A
A
A
A'
A.B.C
A.B.C.D
A.B.C, D
A.B.C
A.B.C.D
A
A
.A.B.C .
A.B.C
A
A
A
A
A
Sampling Post Sampling
Site Process Cell Clean-up
A"
-E . .
A ..__ -
E
E
E
A A
E
A
E
A.B.C
A.B.C
A
A
E
A A A
A.B.C
A
A
A
E
E
A
A
A
A
A
A
E
E
E
A
E
A
E
A
A
A
A
A
A = Soap and water wash, ASTM Type 3 water rinse
B = Methylene chloride rinse
C = Nitric acid rinse
D = Oven dry
E = Disposal of
4-2
-------
5.0 FIELD SAMPLING PROCEDURES
The field sampling procedures are comprised of four phases: (1) facility or
site documentation, (2) process identification, (3) grid layout and sample
location, and (4) sampling procedure selection. The purpose of this phased
approach is to systematically locate the likely sources (processes) of fugitive
particulate emissions, to locate representative sampling locations, and to
select sampling techniques for these processes according to their land
utilization and surface characteristics. The following sections discuss each
of these phases.
5.1 FACILITY OR SITE DOCUMENTATION
A plot plan should be obtained or drawn for each facility or site selected
for sampling. If possible, the plot plan submitted as part of the RCRA Part B
permit application should be used. This plot plan should be drawn to an
applicable topographical scale (such as 1:24,000) and should show the
orientation of true north and the site's major topographical features, both
natural and man-made (see example shown in Figure 5-1. ) It should also be of
sufficient detail and scale to show the exact location and size of processes
sampled.
5.2 PROCESS IDENTIFICATION
This phase involves identifying and marking the relevant "processes" at the
candidate site (i.e., areas devoted to a particular operation that are
potential sources of contaminated fugitive particulate emissions). Typical
processes include: (1) active faces of landfills, (2) surfaces or pits in
which liquid waste streams are mixed with solidifying agents, (3) temporary
soil covers, (4) equipment access and operation areas, (5) surface
impoundments, (6) waste piles, (7) land treatment facilities, and (8) access
roads.
In general, processes can be classified into two broad categories:
disturbed and undisturbed surfaces. Disturbed surfaces are those areas in
which the soil is agitated or overturned to some depth on a routine basis
(i.e., daily or biweekly) exposing non-surface material. Examples are storage
piles, land treatment facilities, and temporary soil covers. Undisturbed
surfaces are areas not routinely agitated or overturned by mechanical
activity; examples are equipment access areas and roads. For roads and
5-1
-------
VJl
i
E. NORTON LAND
DISPOSAL SITE
CRAM DON, MS.
CRIPPLE
CREEK
SOLIDIFICATION
PIT (PROCESS B)
CHAIN
LINK
FENCE
^ACCESS ROAD
(PROCESS C)
ASTE PILE
(PROCESS A
OFFICE
TRAILER
SCALE: 1:24.000
BACKGROUND
SAMPLES
XX
HIGHWAY 61
N
Figure 5.1. Examp^^^te plot plan.
-------
equipment access areas, 'vehicular traffic alters the surface by pulverizing the
surface material; however, this effect typically does not restore full erosion
potential like exposing non-surface material would.
With the help of facility operators, define the approximate boundaries of
the process(es) to be sampled, record the location and dimensions of these
process(es) on the site plot plan, and record pertinent process and operating
characteristics that are expected to affect the generation of fugitive
particulate. Figure 5-2 may be used to record process information. Then, mark
the boundaries (usually four corners) of the first process to be sampled with
surveyor's flags or wooden stakes. Measure and record the process boundaries
and calculate the measured area.
If a process (such as a road or large land treatment area) is too large to
sample as a whole, select a representative area of the process and mark the
boundaries of this area for sampling. See Figures 5-3 and 5-^ for example
schematics of the areas sampled for such processes.
5.3 GRID LAYOUT AND SAMPLE LOCATION
Once the process is identified and the boundaries determined, a decision
8
must be made whether systematic grid sampling or sampling of a representative
area of the process is to be used. As a general rule, systematic grid sampling
is used for all process except roadways and equipment access areas; for these,
samples are collected from representative areas of the process.
For the systematic grid sampling, a 5 by 5 rectangular grid matrix is
used. This grid is superimposed over the process area. Sample .aliquots are
then collected from the process by sampling the center of each of the
twenty-five grid cells.
To locate the sampling grid on the process, a rough sketch of the process
can be made (see example in Figure 5-5). A form such as that shown in Figure
5-.6 may be used to sketch the process and sampling grid in the field.
Considering the shape and dimensions of the process, the grid should be
superimposed over the process so that:
The maximum area of the process (at least 8>5% by visual approximation)
is inside the grid, and
No more than 25% (by visual approximation) of the grid area is outside
the process boundaries.
Once they're determined, Figure 5«6 may be used to record the grid dimensions
and orientation.
5-3
-------
Site Name
Site Location
Team Leader Date
Team Members
Process Name
Process Designation Date Sampled
Process Description
Process Operations
Site Name
Site Location
Team Leader Date
Team Members
Process Name
Process Designation Date Sampled
Process Description
Process Operations
Figure 5-2. Example form for recording process information.
5-4
-------
DIRT ROADWAY (PROCESS 0 I)
24"
16'
16'
ui
i
ui
LIFT ACCESS AREA (PROCESS 02)
68'
IMPOUNDMENT ACCESS ROAD (PROCESS 03)
34'
Figure 5-3- Process dimensions for three unpaved roadway samples
("Processes 01, 02, and 03).
-------
Ul
I
PROCESS 04
(105' x 30')
PROCESS Ob
(2001 x 60')
Figure 5.4. Schematic showing dimension
locations and dimensions o
landfill and stabilization areas and
less areas sampled.
-------
PERCENT
OF GRID
WIDTH
PERCENT
Of C
LEN
108-
50??-
90%-
'RID
3TH
1
30S
-70S
1
JOOS j
30?? 70% '00?5
ii ! !
10?? 50?? 90??
V
^^^^^^^^^^^^^
^^^^^^^^^^^^^^^^
o
o
o
o
o
O
_
O
o
o
o
^"
r. ................. .
O
o
o
o
o
o
o
o
o
o
~-
y
,-.....-....-.......,
o
0
.
"
o
o
o
^/
x - ..~yr~
X X GLITTER SPIKE OR STAKES AND PLASTIC FLAGGING
^^
!
r
ROW i
.
ROW 2
L
ROW 4
i
Xaow 5
N
-«- PROCESS BOUNDARY AND FLAGS OR STAKES y^
O SAMPLING LOCATION
Figure 5.5. Example sketch of process and grid showing suggested technique for
locating sampling points.
5-7
-------
DATE
PROCESS DESIGNATION.
! GRID ! GRID
SITE NAME
LENGTH
PROCESS NAME
SAMPLING TECHNIQUE
SAMPLING TEAM
10%
502
90S
WIDTH J
PROCESS AND GRID LAYOUT
(Indicate Process Boundaries & Dimensions, Grid Dimension & Orientation, and Sampling Locations.)
Total Area Inside Grid (LxW)
Total Area of Processes Inside Grid (Include Names)
Total Area Covered Inside Grid (Note Covering)
Total Effective Process Area inside Grid
Figure 5.6. Example form for sketching process and grid specifications and
recording sampling information.
-------
The following technique is recommended for marking the sampling grid on the
process itself. First, drive wooden stakes or gutter spikes into the ground at
three of the grid corners. Then, run lengths of plastic flagging between the
stakes or spikes to define two perpendicular sides of the grid (see Figure
5.5). The table in Figure 5.6 may be used to calculate the distances along the
grid length and width used to locate the sampling points.
For example, to locate the points on the first row of the grid, mark a
point along the flagging at 10% of the grid length. A test team member located
at that point can then feed the appropriate length of surveyor's tape or chain
to another test team member as he moves across the grid parallel to the grid
J!»,
width which has been marked with plastic flagging. The sampling points will be
at 10, 30, 50, 70, and 90 percent of the grid width. As these points are
located they should be staked or flagged.
Carefully document the relationship of the grid to process boundaries and
other landscape features. This includes estimating the square area of those
areas within the grid that are permanently covered preventing wind erosion.
These areas include standing water, rock piles, gravel, drums, etc. The sum of
these areas must be subtracted from the total area of the grid (length x width)
which will be used in modeling the fugitive particulate emissions. Areas of
other processes not being examined may fall within the grid area such as the
active face of a landfill in a landfill area, or an access road or equipment
access area; these areas must also be subtracted from the grid area.'
In some cases, there may be some obstacle to sampling at the center of a
grid cell. These obstacles may include: (1) standing water, (2) waste drums or
other waste containers, (3) parked equipment, (4) rocks, and (5) significant
holes at the location. Under these circumstances, the sample should be taken
at another suitable point in the cell as close to the center as possible. If
an entire cell is covered by one or more of these obstacles, then that cell is
not sampled and as previously stated, all the area covered is subtracted from
the total area of the grid.
Some process configurations and/or relationships to other processes may
increase the difficulty in choosing a rational grid location. One such
situation is illustrated in Figure 5-7. In this case, the grid is located to
maximize process coverage. It covers a portion of another process (the access
road) and a portion of a pond. Two of the grid cells are not sampled at all
since their entire area covers a separate process and/or an area of permanent
coverage (the standing water in the pond). As previously discussed, the
5-9
-------
Ul
I
y/
POND
ACCESS
ROAD AND
LtVY
O
STAKED
PROCESS
BOUNDARY
SAMPLING
LOCATION
Figure 5.7. Example sketch showing optimal sampling grid location on process and
sampling locations resulting from process configuration.
-------
permantly covered area within the grid (the pond) must be subtracted from the
total area of the grid and the area of the access road (a separate process)
within the grid must also be subtracted. If these grid cells instead covered
non-process related land that was not permanently covered, then it would be
appropriate to sample them (see the next example).
In another case illustrated in Figure 5-8, (1) a separate process (active
face of a landfill) falls in the middle of the process being sampled (the
landfill) and (2) one entire grid cell falls outside the process. In this
case, all the grid cells are sampled (see Figure 5-8 for locations). The grid
is superimposed over the process so that^the active face will not completely
cover any grid cells while still maximizing process coverage. For the cells
where the active face covers the center of the cells, the samples are taken as
close to the center as possible. For the one cell totally outside the process,
the sample is taken at the middle since it is non-process related and its area
will be included in. that used for the emission models. In situations such as
the preceding two examples, the grid should be situated to optimize the process
coverage while introducing the least bias possible.
5.4 SAMPLE COLLECTION PROCEDURES
One soil aliquot is taken from the center (exceptions previously addressed)
of each grid cell sampled. The five aliquots from each of the five rows (see
Figure 5-5) are composited in a sample jar. And later, during sample analysis,
the silt screened from each sample jar is composited into a single sample for
the process.
The type of collection procedure used to take the aliquots from a given
process is primarily a function of the process and its surface characteristics
(i.e., disturbed or undisturbed surfaces). Four sample collection methods are
used to account for these variations: scooping, coring, sweeping, and
vacuuming. Each is described in detail later in this section.
Since scooping is the method most routinely used, the general activities
common to the use of all sample collection methods are described with reference
to this method. First, establish a sample-handling area near the process to be
sampled. Spread a plastic groundcloth over a 3~ to 4-m square area to prevent
contamination by local dust. Move containers of prepared sampling jars and the
other needed sampling equipment to this groundcloth.
During sampling, disposable scoops are used to fill one 475 ml sample jar
per grid row. Jars should be completely filled when possible, leaving little
or no head space. Thus, each aliquot should be approximately 90-100 ml in
5-11
-------
VJ1
I
o
STAKED
PROCESS
BOUNDARY
SAMPLING
LOCATION
Figure 5.8. Example sketch showing optimal sampling grid location on process and
sampling locations resulti^^fcpom process configuration.
-------
volume. Manually remove rocks greater than approximately one-quarter inch in
diameter and other non-soil debris from the sample. Precleaned plastic putty
knives can be used to aid in filling the scoops (particularly during road sampling
when a "backstop" is necessary to push material into the plastic scoop). On windy
days, a windbreak device may be used to prevent any fine dust particles from being
blown from the scoop.
Immediately after each sample jar is filled, label it with the site, date,
process, and the sample number including the jar number (see Figure 5-9)- A
' recommended sample numbering scheme employs one or two letters to identify the
site, a two-digit number to identify the process and a one digit number to identify
the jar. For example, the first jar taken from the first process sampled at Acme
Waste is labeled AW-01-1.
After sampling all the candidate cells in a process and before the lids are
placed tightly on the sampling jars for shipment, clean the jar threads with a
brush to remove any soil particles. Screw the lid onto the jar, wrap the lid with
electrical tape to prevent any loss of soil, and place the jar back into the box.
At the completion of sampling at a site, dispose of the brushes, putty knives, and
scoops. Label, seal,, and inventory the boxes of sample jars and place them into
chilled coolers for transport.
SITE: .
DATE:
PROCESS:
SAMPLE NO.:
Figure 5-9- Example label for sample jars.
5.4.1 Scooping
Near sub-surface samples of moderately disturbed surfaces (i.e., stabili-
zation areas and active landfills) are taken at depths from 0 to 3 cm by digging
out the desired sample thickness with disposable plastic scoops. Scooping can be
conducted on a wet or muddy surface (i.e. after a rain); however, sampling should
not be conducted when water is standing on the surface to be sampled.
5-13
-------
As previously stated, one scoop (aliquot) is taken from each grid cell. The
five aliquots from one row of the grid are deposited into a single sample jar.
Rocks greater than approximately one-quarter inch in diameter and other non-soil
debris should be manually removed from the soil. Label the jars with the
appropriate sample number and sampling information.
5.4.2 Coring
If possible, disturbed surface areas should be sampled using a coring
technique to extract samples to depths up to 15 cm (6 in.). For this protocol,
two types of coring tubes are employed: one made of stainless steel (to collect
soil for organics analysis) and one made of PVC plastic (to collect soil for
metals analysis). Like scooping, coring can be conducted on a wet or muddy
surface (i.e., after a rain); however, sampling should not be conducted when water
is standing on the surface to be sampled. .
To collect the two core samples at each sampling location, drive each core-
tube into the soil to the nominal depth of disturbance for the particular
process. Extract the core tube from the soil, and force the soil core out into
the sample jar by pushing a wooden dowel through the tube. Rocks and non-soil
debris should be removed manually from this material prior to sealing the glass
jar.
When using the coring technique, the soil taken from the grid cells should
consist of two samples (segregated into separate sets of 5 sample jars): one
taken for metals analysis using the plastic core tube and one taken for organics
analysis using the stainless steel core tube. Label the sample jars as previously
discussed, with the addition of an "M" to the sample number on the jars of soil
taken for metals analysis and an "0" to the sample number on the jars taken for
organics analysis.
In cases where it is impossible to drive the core tube to the desired depth or
where it is difficult or impossible to extract the soil from the core tube once
sampled, a modified coring technique may have to be used. In this case, drive the
core tube to the greatest depth which will still facilitate sampling. Then, to
collect enough sample volume to fill 1/5 of the jar, take additional cores from
the same area, as needed.
5.4.3 Sweeping
Hard-crusted, undisturbed soil surfaces, such as unpaved roads and equipment
access areas are sampled using a "sweeping" or "brushing" technique.
-------
Road samples are obtained either (1) from a single strip spanning all the
travel lanes, usually 0.5 m (1 to 2 ft) in Width depending upon the amount of
road dust (see Figures 5.1 and 5.2) or (2) from four incremental strips, each
approximately 8 in. wide, spanning half the road and spread out evenly along
the roadway segment of interest. The selected site should have a dust loading
and traffic characteristics typical of the entire roadway segment of interest.
It should be at least several road widths away from corners, bends, drives, and
changes in grade. For other areas sampled with the sweeping technique, a
reasonably sized rectangular area is chosen to be representative of the whole
area. . ,,
Sweeping cannot be conducted on a wet or muddy surface. If the surface is
generally wet, sample at the time of the least wetness. If continuous wetting
is used for dust suppression, then there is no need to sample. Sweep or brush
loose particulate matter within the area to be sampled into piles or a ridge
using a disposable brush. Brush or otherwise move material into one of the
disposable scoops and deposit into the sample jar. Care should be taken to
brush all the loose particulate from the sampling area, but not to loosen and
dislodge any other material from the surface which is not already loose.
Remove rocks and non-soil debris. Label and seal the jars as previously
discussed.
5.4.4 Vacuuming
The vacuuming technique is used for paved roads. Loose particulate matter
is vacuumed from within the aliquot area. Paved roads are sampled using the
"Procedures for Sampling Surface/Bulk Materials" developed by Midwest Research
Q
Institute which specify collection of one sample per 8 km (5 miles) of paved
road. This sample should consist of at least two separate increments per
travel lane. Thus, the gross .sample collected from a two-lane roadway would
consist of four sample aliquots. Each aliquot should consist of a lateral
strip 0.3 to 3 m (1 to 10 ft) in width across a travel lane. The exact width
is dependent on the amount of loose surface material on the roadway. For a
visually dirty road, a width of 0.3 m (1 ft) is generally sufficient; however,
for a visually clean road, a width of 3 m (10 ft) is typically needed to obtain
an adequate sample.
This sampling procedure is considered the preferred method of collecting
surface dust from paved roadways. In many instances, however, the collection
of a number of sample aliquots,may not be feasible because of manpower,
equipment, and traffic/hazard limitations. As an alternative method, samples
5-15
-------
can be obtained from a single strip across all the travel lanes. When it is
necessary to use this sampling strategy, care must be taken to select sites
that have dust loadings and traffic characteristics typical of the entire
roadway segment of interest. In this situation, sampling from a strip 3 m to 9
m (10 to 30 ft) in width is suggested. In cases where samples are removed from
the road surface by vacuuming and large aggregate is present, sampling must be
preceded by broom sweeping to collect the larger material.
After sampling, check the contents of each vacuum sweeper .bag and remove
rocks and non-soil debris prior to transfer of the sample to the sample jars.
Mark the sample jars as previously described. Paper sweeper bags are used so
they can be discarded after a single use. Vacuuming cannot be conducted on a
wet or muddy surface. If the surface is generally wetted, sample at the time
of the least wetness. If continuous wetting is used for dust suppression,
then there is no need to sample.
5.5 COLLECTION OF BACKGROUND SAMPLES
At least one background sample should be collected at each facility.
Background samples are used to determine the nominal value for the elements
and/or compounds in the soil in the area of the site that are naturally
occurring or are non-process related. Background samples should be taken in an
area (1) that is off-site or away from any process operations and is upwind of
the TSDF to ensure a low degree of contamination from site activities and (2)
that has soil characteristics and vegetation as similar as possible to the
site. Thus, the ideal background sample would come from a site that only
differs from the study area by the lack of the contaminates under
investigation. Background samples are generally collected using the scooping
technique and are handled in the same manner as the process samples and thus,
the same guidelines apply with respect to sampling under wet or muddy
conditions.
5-16
-------
6.0 SAMPLE HANDLING AND TRANSPORT
This section describes the specific techniques used to maintain sample
integrity.
To avoid contamination, field equipment that will be exposed to sample
material should be transported on-site in sealed bags or coolers. Collect
scooped samples using disposable, individually wrapped, sterile, nonreactive
plastic scoops. Deposit the contents 0^, the scoops directly into sample jars.
In the case of cored samples, clean the core tubes before sampling and pack
them in sealed plastic bags. Deposit core sample aliquots directly into the
sample jars from the core tube. Collect swept samples using a new disposable
brush (transported to the site in sealed plastic bags); disposable scoops are
used to deposit the swept samples into the glass sample jars. Collect vacuumed
samples using a new vacuum sweeper bag transported on-site in a sealed plastic
bag. Transfer the contents of the sweeper bag directly into the sample jars.
In all cases, fill sample jars completely, leaving no head space. Label
each sample jar (see Figure 5-9) with the facility sampled, date, process
description, and sample number, seal with electric tape, and store it in a
cooler at a temperature less than 20 C to minimize loss of volatile
components. Use a chain-of-custody form for each process. The form should
identify each sample and all personnel having custody of the samples at all
phases of sample handling. Many agencies will have their own chain-of-custody
forms and procedures which should be used by their staff and contractors. An
example chain-of-custody form is shown in Figure 6.1.
When all samples have been collected for a particular site, move the
sample storage cooler to an uncontaminated area and decontaminate it prior to
transport. This decontamination procedure should include washing with soap and
water and a final rinse with distilled water.
Samples should be transported from the field in sealed coolers. Surface
transportation or air freight can be used to transport the samples for long
distances; however, during transport, sample jars must be maintained at
temperatures less than 20 C to prevent the evaporation of any volatile
components. Pack samples to be shipped by air freight in insulated, impact
resistant coolers and cool with "blue-ice," an airline-approved coolant. Make
6-1
-------
DATE:
COOLER NO.
SITE NAME:
LOCATION:
CHAIN OF CUSTODY FORM
CASE A
CASEB
LABELS CHECKED:
SAMPLES COOLED:
JAR LIDS CHECKED AND SEALED:
SAMPLES INVENTORIED:
COOLER CH&J.ED:
SAMPLE TRANSPORT:
SAMPLE RECEIVED:
SAMPLE ANALYSIS:
CASES SEALED:
COOLER SEALED:
Figure 6.1. Example chain-of-custody form.
6-2
-------
arrangements with laboratory personnel so that samples can be picked up and
transferred to the laboratory as quickly as possible.
Federal regulations governing the shipment of hazardous wastes are found in
Title 40 of the Code of Federal Regulations, Part 26l. However, Section 261.4
exempts samples of "water, soil, or air collected for the sole purpose of
testing to determine characteristics or composition" when the samples are being
shipped to a laboratory for analysis. When shipping samples to the laboratory,
the tester should comply with shipper requirements and provide, as a minimum:
Tester's name, mailing address and telephone number;
Laboratory's name, mailing address and telephone number;
Date of shipment;
Quantity of sample;
i
Description of sample;"and
Suitable packaging as previously discussed.
Prior to the initial analyses (moisture, silt, and PM-20 determinations),
keep all field samples in a locked refrigerator or cool area at a. temperature
less than 20°C. During the drying, screening, and sieving operations, samples
must be handled using techniques to prevent contamination (e.g., using clean
gloves). To prevent dispersal of contaminated soil in sample handling areas,
conduct screening and sieving operations within a closed system such as a glove
box. All equipment that comes into contact with soil samples must be
decontaminated initially and then decontaminated after each use, or disposed of
in the appropriate manner.
If the chemical analyses are to be performed by another laboratory, the
resulting silt and PM-20 samples should be placed in small amber sample vials
for transport or shipment for further analysis. Use 10-ml vials for metals
samples and 40-ml vials for organic samples. In cases where they are not
shipped or analyzed immediately, store samples at or below 20°C. For shipping,
pack samples carefully (in bubble pack in a styrofoam cooler) and use
"blue-ice" as the coolant to keep sample temperatures at or below 20°C.
All samples should be extracted for metals and organics analysis within 14
days of collection. If, for some reason they must be kept for a longer period,
they should be stored at 4 C. All samples should be completely analyzed within
40 days of extraction.
6-3
-------
7.0 FIELD SAMPLING SAFETY CONSIDERATIONS
This section addresses field sampling safety considerations only.
Laboratory safety should be considered by each laboratory performing the
particle size distribution and/or chemical analyses involved in the sampling
program.
Many of the safety considerations involved in sampling a TSDF using this
protocol depend on the specific facility being sampled. Therefore, the initial
step in developing a set of safety procedures to accompany the field sampling
portion of the program is to check with the company management and safety
professionals concerning facility safety requirements, and, in addition, their
recommended safety procedures to be applied to the sampling program. This
section of the protocol presents a number of suggested safety considerations
for sampling contaminated particulate emissions from TSDF's; however, because
the precise safety precautions must be tailored to the specific facility and
situation, this protocol clearly cannot address every possible circumstance.
Based on the objectives of this type of sampling program, which involve
sampling soils for contamination in and around hazardous and toxic materials
TSDF sites, it is anticipated that the personnel conducting the sampling will
be encountering relatively low levels of toxic materials, and these materials
will be bound up in the soil particles. Thus, the hazards of exposure are
simplified to an extent, and principally involve direct dermal contact with the
soil and inhalation of soil particulate. Based on these assumptions, the
minimum level of personal safety equipment suggested is that which will protect
sampling personnel from contact with the soil to be sampled, will provide some
protection against liquid materials, and will protect against inhalation of the
low levels of organics and dusts which might reasonably be expected to be
present at these sites. This equipment consists of Saran-coated Tyvek
coveralls (with attached hoods and boots), nitrile rubber gloves, chemical
splash goggles, and air-purifying respirators with organic vapor cartridges and
particulate filters. To provide a proper and protective respirator fit, men
must not have facial hair (i.e., beards, mustaches, and long side burns).
Personnel wearing this equipment, in particular the respirators, must be
thoroughly fit tested and instructed in its proper use.
7-1
-------
Due to the significant labor costs inherent in frequent decontamination, it
is recommended that personal protection equipment be selected so as to be A
completely disposable. In this way, when sampling is completed at a particular!
site, each member of the sampling team can remove his protective outfit, stow
it in a plastic bag (which should be disposed of in the appropriate manner),
and wash his/her hands, face, and any other areas of potentially exposed skin.
As an additional protective- measure, members of the sampling team should
have immediately available to them a 15-minute (or greater) portable oxygen
unit to be used for escape purposes in the unlikely event of exposure to toxic
gases or particulate. This unit should be transported to the site in a plastic
bag which can remain on the unit during sampling and then be disposed of when
leaving the site.
7-2
-------
8.0 ANALYTICAL METHODS
The methods for the analysis of soil samples collected at TSDF's involve
physical characterization by drying and sieving followed by chemical
determinations of the degree of contamination of the different soil size
fractions. The scheme for analysis of the five jars of soil sample collected
from the same process is depicted in Figure 8.1. It is advisable to note the
processing instructions for all samples (and sample jars) on a form similar to
ja,
the one shown in Figure 8.2. Ten (10) g aliquots of the "raw" sample in each
jar (i.e., not dried) are taken for each loss-on-drying (LOD) determination and,
for land treatment samples, 10 g for each the oil and grease determination. The
LOD value is used to determine the proper drying method for the remainder of the
sample in the jars. After drying, the soil portions are screened individually,
by jar, to determine percent silt content; the non-silt material is discarded.
The individual silt fractions from each jar collected at a single process
are combined to make a homogeneous composite silt sample. This composite sample
is then used to determine the organic and metal contents. Organics analysis
requires 30 S of silt and metals analysis requires 10 g of silt. The remaining
composite silt sample is kept as an archive sample and can be used for quality
assurance and quality control purposes. Background samples are handled in the
same manner.
As explained in the introduction, a further option is to determine the PM-20
content of the soil and the degree of contamination in this fraction. Sonic
sieving of a 200 to 300 g portion of the composite silt sample is used for the
PM-20 determination. If enough composite silt sample is available, a PM-20
fraction and a "greater than PM-20" (>PM-20) fraction may be produced for the
analysis of chemical contamination in each fraction. These analyses also
require 30 g and 10 g of material for organics and metals analysis,
respectively. Typically, if this done, an excess of >PM-20 material is produced
and should be kept in case of accidental loss of the >PM-20 sample.
8.1 RAW SAMPLE ANALYSES AND PHYSICAL CHARACTERIZATION
As previously stated, the LOD determination, sample drying, and the
screening for silt determinations are conducted on the samples which are still
divided by sample jar into five portions. Following screening, the silt
fractions from each of the jars are combined into the composite silt sample
which is used for the remainder of the analyses. For the purposes of the
8-1
-------
5 SAMPLE JARS OF SOIL
ONE
475 ML
SAMPLE JAR
ONE
475 ML
SAMPLE JAR
ONE
475 ML
SAMPLE JAR
^H
CONTENTS
OF JAR
1
|
ONE
475 ML
SAMPLE JAR
ONE
475 ML
SAMPLE JAR
i i
DESICCATION OR OVEN DRYIN6
CONTENTS
OF JAR
CONTENTS
OF JAR
CONTENTS
OF JAR
CONTENTS
OF JAR
1 1 1 II
SCREEN FOR SILT CONTENT,
CONTENTS
OF JAR
CONTENTS
OF JAR
I ,
COMBINE
NEED 40 g
FOR ANALYSIS
,
CONTENTS
OF JAR
1
<75 jwn
CONTENTS
OF JAR
CONTENTS
OF JAR
I
ALL SAMPLES AND MAKE HOMOGENEOUS
REMAINDER OF SILT
1 ill 1
DIVIDE SAMPLE
30 g VIAL
10 g VIAL
SONIC SIEVIN6
>40g
75 TO 10 Jim
OPTIONAL
ARCHIVE SAMPLES
MOg
LESS THAN 10 jim
SEAL
PORTION
IN JAR
OPTIONAL FOR QA/QC PURPOSES
,,
MAKE HOMOGENEOUS AND DIVIDE
DIVIDE SAMPLE
30 g VIAL
10 g VIAL
75 to 10 jim
OPTIONAL
1
1
1 r
SAMPLE
DIVIDE SAMPLE
30 g VIAL
10 g VIAL
Less Than 10 jim
OPTIONAL
1
ANALYZE SAMPLES FOR
METALS, PESTICIDES. SEMIVOLATILE CRGANICS, CYANIDE
LOO DETERMINATION
AND OIL & GREASE^^
~~^ DETERMINATION ^^)|
10 g FROM EACH JA^T
DISCARD
^^ NON-SILT
MATERIAL
Figure 8.1. Flow diagram for samples taken from a process.
8-2.
-------
SOIL SAMPLE PROCESSING SHEET
Site Identification
Process Description __
Sample Jar Numbers '
Unprocessed Samples to be Taken for Special Analysis
Analysis ^ __ Amount
Sample Jar Numbers " *_
Samples taken by Date
Analysis Amount
Sample Jar Numbers
Samples taken by Date
Loss on Drying Determination 105 degrees C for hours
Sample Jar Numbers
Analyst Date Comments
Silt Screening.Instructions
Sample Jar Numbers
Analyst Date Comments
Sonic Sieving Instructions (Optional)
Sample Jar Numbers
Analyst Date Comments
Figure 8.2. Soil sample processing instruction sheet.
8-3
-------
discussion of these raw sample analyses, these portions by jar are referred to
as samples also.
8.1.1 Loss-pn-Drying (LOP) Determination
ASTM Method 02216-yi ("Laboratory Determination of Moisture Content of ,
Soils") is used to provide an indirect measure of the moisture content of each
soil sample. A data sheet similar to the one shown in Figure 8.3 is used to
record the LOD data.
For the LOD determination, analytically weigh approximately 10 g of the
"raw." soil sample from each sample jar into a tared, 5~cm diameter glass jar
with a tight fitting lid. If there is standing water in the jar, it should not
be sampled for the LOD determination. Remove the jar lids and dry the samples
overnight (12 to 16 hours) in an oven at 105 C. Remove the LOD samples from
the oven and place them in a desiccator to cool; remove the cooled samples
from the desiccator and replace the jar lids.. Reweigh each dried LOD sample
and determine the percent LOD using the following formula:
a . rtn Jar and Sample Wet Wt. - Jar and Sample Dry Wt. inr,./
ft LUU s ^______ jj IvJU/i
Sample Wet Wt.
8.1.2 Oil and Grease Content Determination
Analyze any land treatment samples for oil and grease content according to
Method 503 D in "Standard Methods for the Examination of Water and Wastewater."
The method involves extraction of a 10 g of "raw" sample with
l,l,2-trichloro-l,2,2-trifluoroethane (Freon 113) followed by gravimetric
determination of the dried extract.
8.1.3 Sample Drying Procedure
Dry the contents of each sample jar taken from a process using one of the two
procedures described below, depending on the average percent LOD measured for that
process. If the LOD is less than 10 percent, desiccate the five sample portions
over anhydrous calcium sulfate until they show no more than on.e percent weight loss
upon further drying. If the measured LOD is greater than 10 percent, dry the fivev
sample portions in an oven at 105 C until they show no more than one percent
weight loss upon further drying. A data sheet similar to the one shown in Figure
8.4 is used to record and calculate the actual sample weight loss during
desiccation or drying.
8-4
-------
LOSS-ON-DRYING (LOD) DETERMINATION DATA SHEET
Site
Process
Analyst \ ] Date
Reviewed by Date
Sample Jar Number ' -**
Jar Tare Wt. (g)
Jar and Sample Wet Wt. (g)
Sample Wet Wt. (g) '
Sample Wet Wt. = Jar and Sample Wet Wt. - Jar Tare Wt.
Oven Temperature(°C)
Time In Oven
Time Out Oven
Total Drying Time
Jar and Sample Dry Wt. (g)
% LOD
T nn = Jar and Sample Wet Wt. - Jar and Sample Dry Wt. nnt/
LOD Sample Wet Wt. x 100%
Figure 8.3- Loss-on-drying (LOD) determination data sheet.
8-5
-------
SAMPLE DRYING WEIGHT LOSS DATA SHEET Oven
Desiccation
Site Analyst Date
Process Reviewer Date
Sample Jar Number Pan Tare Weights
Time Sample Pan Weights Sample Weight
» =' -' Pan Tare Wts. =
+ = - Pan Tare Wts. =
+ = - Pan Tare Wts. =
+ = Pan Tare Wts. =
Sample Jar Number Pan Tare Weights
Time Sample Pan Weights Sample Weight
+ = - Pan Tare Wts. =
+ = - Pan Tare Wts. =
+ = - Pan Tare Wts. =
+ = Pan Tare Wts. =
Sample Jar Number Pan Tare Weights
Time Sample Pan Weights SampJ.e Weight
+ = - 'Pan Tare Wts. =
+ = - Pan Tare Wts. =
+ = - Pan Tare Wts. =
+ = - Pan Tare Wts. =
Percent Sample Wet Wt. - Sample Dry Wt.
Weight = Sample Wet Wt. x
Loss
% WEIGHT LOSS AT TIME INTERVAL
Sample Jar Number
Time _______
Time
Time
Time
Figure 8.4. Sample drying weight loss data sheet.
8-6
-------
In the desiccation procedure, clean the desiccator by washing the interior
with water which conforms to the specifications for ASTM, Type 3 water (referred
to herein as D.I. water). Followed this with an acetone rinse and a final
methylene chloride rinse. Spread a one-inch layer of anhydrous calcium sulfate
over the bottom of the desiccator. Split the contents of each sample jar
(approximately one kg) between two tared, 9-inch Pyrex pie plates that have
been previously cleaned with D.I. water, acetone, and methylene chloride.
Determine each pie plate tare weight and the weight of each pie plate with its
wet sample contents. Place sample in the desiccator and desiccate until it
shows no more than one percent weight Iqs^s on further desiccation. Determine
the weight of each pie plate with the sample portion when dry and calculate the
percent loss-on-desiccation using the following formula:
% Weight Loss * Sample Wet Wt. - Sample Dry Wt. x IQQ%
Sample Wet Wt.
For oven-drying, first wipe the oven interior clean with D.I. water,
followed by acetone and methylene chloride. Split the contents of each sample
jar between two clean, tared pie plates. Determine each pie plate tare weight
and the weight of each pie plate with its wet sample contents. Set the oven
temperature at 105 C. Place sample in the oven and dry until it shows no more
than one percent weight loss on further drying (dry enough to be sieved);
remove to a clean desiccator to cool. Determine the dry weight of the sample
and calculate the percent loss-on-drying using the formula above.
Return the .desiccated or oven-dried samples to clean, dry sample jars and
e at <
same day.
store at or below 20 C;* or keep the samples in the desiccator and sieve the
8.1.4 Silt Screening Procedure
The dried soil from each separate sample jar is sieved through a 40-mesh
screen (425-micrometer) stacked on top of a 200-mesh screen (75-micrometer)
using a sieve shaker. The silt fraction of the soil is collected in a
tare-weighed receiver pan below the 200-mesh screen. Record the screening data
using a silt screening data sheet such as the one shown in Figure 8.5.
First, clean the sieve stack with D.I. water, acetone, and methylene
chloride before processing each set of sample jars. Determine the weight of
the sample portion in each jar and screen each portion separately. Run the
*If not extracted within 14 days after collection, the samples must be stored
at 4°C.
. 8-7
-------
SCREENING DATA SHEET
Site
Sample Jar No.
Method of Drying
Screens Used
Process
Date
Desiccator Oven (Check One)
Sieve Stack Top Bottom (Check One)
WEIGHT OF ORIGINAL SAMPLE
Sample Jar
Empty Jar w/Lid
TOTAL'
g *
3 +
g
g
Original SAMPLE WEIGHT (Sample Jar Wt. - Empty Jar Wt.)
WEIGHT OF SILT
Silt and Pan w/Lid after
Pan w/Lid (Empty)
min. of screening
FIRST SILT WEIGHT (Silt and Pan Wt. - Empty Pan Wt.)
First Silt Weight
FIRST PERCENT SILT
Sample Weight
Silt and Pan w/Lid after
Pan w/Lid (Empty)
x 100%
min. of screening
SECOND SILT WEIGHT (Silt and Pan Wt. - Empty Pan Wt.)
Second Silt Weight
SECOND PERCENT SILT
x 100%
Sample Weight
DIFFERENCE in Percent Silt » Second % Silt - First % Silt
If difference is greater than 1% reacreen the sample for
redetermine % Silt. Check difference in % Silt again. Repeat until difference is
less than 1%.
minutes and
FINAL PERCENT SILT
Final Silt Weight
Final Silt Weight
x 100%
Sample Weight
JAR MARKED
ANALYST
Weight of Silt in Jar w/Lid
Weight of Jar w/Lid (Empty)
SILT SAMPLE WEIGHT (Silt in Jar - Jar Wt.)
JAR STORED IN REFRIGERATOR
REVIEWED BY
g-
g-
(Check Off)
Figure 8.5- Silt, screening data sheet.
8-8
-------
screen in increments of 10 to 15 minutes until less than 1 percent difference
is seen in the cumulative silt yields between successive weighings. Calculate
the percent silt yield for each portion using the following formula:
j. 0-1.. Final Silt Wt. inn»
.'
After the silt from a single sample jar is screened, transfer it to a clean
dry jar and store at or below 20 C.* After the silt is screened from all five
jars of sample from a single process, roadway or background area, combine the
five portions to form a single composite silt sample. Homogenize the silt
composite by sieving through~a stack of two 40-mesh screens. Store the
homogenized silt composite in a clean, dry jar at or below 20 C.*
8.1.5 Sonic Sieving Procedure (Optional)
Sonic sieving is used, at the test coordinator's option, to determine the
percent PM-20 content of the composite silt sample (approximately 200 to 300 g)
from one process. Sonic sieving of the composite silt sample is also used to
produce sufficient amounts of PM-20 and >PM-20 material to perform organic and
metal analyses, if appropriate.
Set up a sonic sieve system consisting of a sonic sifter with variable
amplitude and vertical pulsing, a sieve stack with a 270-mesh (53-micrometer)
sieve over a 625-mesh (20-micrometer) sieve, and a horizontal pulse
attachment. Collect the PM-20 material in a fines collector located under the
20-micrometer sieve. Use a data sheet such as the one shown in Figure 8.6 to
record the PM-20 determination data.
For the determination of percent PM-20 content, tare the fines collector on
an analytical balance before assembling the sieve stack. Add a 1-g sample
(analytically weighed to the nearest 0.1 mg) of the composite silt sample to
the sieve stack. Run the sonic sieve in increments of 10- to 15-minutes using
both horizontal and vertical pulsing. Weigh the fines collector after each
run. Repeat the sieving runs on the 1-g sample until less than one percent
*If not extracted within 14 days after collection, the samples must be stored
at 4°C.
8-9
-------
PERCENT PM-20 DETERMINATION DATA SHEET
Site
Silt Sample No.
Process
Analyst
Date
Fines Collector Tare Wt. (WO)
Weigh Boat with Sample (Wl)
Weigh Boat without Sample (W2)
Silt Sample Wt. (Wl - W2)
grams
grams
grams
grams
After
minutes of sonic sieving
Fines Collector Wt. (W10)
grams
Percent PM-20 =
W10 - WO
x 100# =
Silt Sample Wt. (Wl - W2)
After
minutes of sonic sieving
Fines Collector Wt. (W20)
grams
Percent PM-20 =
W20 - WO
x 100% =
Silt Sample Wt. (Wl - W2)
After
minutes of sonic sieving
Fines Collector Weight (W30)
grams
Percent PM-20 =
W30 - WO
Silt Sample Wt. (Wl - W2)
x 100% =
Percent Difference between Second and Third Sieving
% Difference .
rd * ~2° ' Second * PM-20
Silt Sample Wt. (Wl - W2)
percent
percent
percent
The percent difference should be less than 1%. If not, continue sieving until
the percent difference between the last sieving and the next to last sieving is
less than 1%. Begin a new data sheet when needed.
Figure 8.6. Percent PM-20 determination data sheet
8-10
-------
difference is seen in the cumulative PM-20 yield. Calculate the percent PM-20
using the following formula:
._ n.« Wt. of Collector with Cumulative PM-20 - Collector Tare Wt. inn
Percent PM-20 = x 100
Silt Sample Wt.
Calculate the percent difference in PM-20 yield on successive runs using the
following formula:
Percent Cumulative PM-20 Wt. - Previous Cumulative PM-20 Wt.
* Deference = Silt Sample Wt. .
For the production of PM-20 for chemical analysis, sonic sieve 1 to 5 g of
composite silt sample (depending on sieving characteristics) for 5 to 15
minutes (again depending on sieving characteristics). Remove the material
retained on the sieves and store in a jar labeled >PM-20. Add a fresh charge
(1 to 5 g) of the composite silt sample to the sieve. Since 10 g and 30 g are
required for metals and semivolatile organics analyses, respectively, repeat
the sieving until about 40 grams of PM-20 material are produced.
Before the PM-20 production run for each process, clean the sonic sieve stack
with D.I. water and l,l,2-trichloro-l,2,2-trifluoroethane (Freon 113). Also, for
each production run, use a new fines collector and a new diaphragm cleaned with
soap and tap water and D.I. water. During PM-20 production runs, the sieves may
blind and can be cleaned by sonication in a beaker with l,l,2-trichloro-l,2,
2-trifluorethane. Allow the sieves to air dry before using.
8.1.6 Sample Packaging
If any of the samples are sent to another laboratory for chemical analysis,
pack in amber vials. (40-ml with Teflon-lined septums and phenolic caps). Before
use, clean and rinse the vials sequentially with dilute nitric acid, D.I. water,
acetone, and pesticide-grade methylene chloride. Package into the vials 30 g of a
sample for organic analysis and 10 g of a sample for metals analysis. Label the
vials as shown in Figure 8.7.
Sample No. AW-10-2 Date: 03/18/86
Description: 30 g Silt Composite
Process: Landfill Cell 10
Site: Acme Waste Disposal Co.
Figure 8.7. Sample label.
8-11
-------
8.2 CHEMICAL ANALYSES
8.2.1 Metals Analysis
For analysis of the metals of interest listed in Table 8.1, the methods
used are from the EPA publication, "Testing Methods for Evaluating Solid
Waste," SW-846. Prepare samples for analysis of all metals except mercury (Hg)
by acid digestion using EPA Method 3050 (SW-846). Prepare and analyze the
mercury sample by the cold-vapor atomic absorption procedure following EPA
Method 7471 (SW-846). Use the following two modifications in.the final
dilutions of the digested samples. Dilute the samples for ICAP determination
by EPA Method 6010 (SW-846) and furnace atomic absorption determination of
antimony (Sb) by EPA Method 7041 (SW-846J to achieve a final concentration of
5% hydrochloric acid. Dilute the digested samples for arsenic (As)
determination by EPA Method 7060 (SW-846), for selenium (Se) determination by
EPA Method 7740 (SW-846), and for thallium (Tl) determination by EPA Method
7841 (SW-846) to achieve a final concentration of 0-5# nitric acid.
For chromium, the analysis described above, using EPA Method 6010 and
ICAP, should serve as a screening technique. If the results for any sample
show a relatively significant concentration of chromium, then another aliquot
of that sample should be analyzed for hexavalent chromium (Cr VI) which is muc
more toxic than the other forms. This further analysis is conducted using EPA*
Method 3060 (alkaline extraction) in combination with EPA Method 7195
(co-precipitation/AA), 7196 (colorimetric), or 7197 (chelation/AA).
8.2.2 Cyanide Analysis
Cyanide determinations are performed by colorimetric measurement following
EPA Method 335.2 found in "Methods for the Evaluation of Water and Wastewater."
The method involves distillation of the cyanide, as hydrocyanic acid, into a sodium
hydroxide absorbing solution. The cyanide ion in the absorbing solution is
determined colorimetrically.
8.2.3 Semivolatile Organic Analysis
For the semivolatile organic analysis, prepare the samples by sonication
extraction (Method 3550, SW-846) using the procedures specified in the CLP
Statement of Work for Organic Analysis. Prepare the extracts at the low
concentration level using 30 g of sample and subject them to adsorption
chromatography on Sephadex LH-20. Concentrate the extracts and determine their
weight. Take approximately 200 mg of each concentrated extract, weigh accurat
8-12
-------
TABLE 8.1. METALS AND MEASUREMENT METHODS
Element
Measurement Method*
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)
ICAP
GFAA
GFAA
ICAP
ICAP
ICAP
ICAP
ICAP*
ICAP
ICAP
ICAP
ICAP
ICAP
Cold Vapor AA
ICAP
ICAP
ICAP
GFAA
ICAP
. GFAA
ICAP
ICAP
*Eight RCRA metals
**ICAP = Inductively-Coupled Argon Plasmography
GFAA = Graphite Furnace Atomic Absorption
AA = Atomic Absorption
Other methods are used to measure hexavalent chromium (Cr IV), if appropriate
(see page 8-12 for discussion).
8-13
-------
and redissolve in 2 ml of a 1:1 mixture of methylene chloride and methanol.
Calculate the dilution factor for the LH-20 procedure using the following
formula:
LH-20 Dilution Factor = Weight of Concentrated Extract (mg)
Exact Weight of 200 mg Portion
Calibrate and monitor the LH-20 system according to the procedure in the
CLP for the gel permeation chromatography system.. For the LH-20 procedure, use
an eluent solvent system consisting of a 1:1 mixture of methylene chloride and
methanol. Load the 200 mg redissolved sample extract directly onto the
column. Adjust the eluent flow rate to 100 ml per hour. Collect the proper
fraction containing the aromatic compounds, .and' concentrate the fraction to
one ml.
Analyze the extract according to the CLP procedure: screen them by gas
chromatography with a flame ionization detector (GC/FID) to determine the
proper dilution level. Minimize the amount of dilution to maintain the
detection level at as low a level as possible. Use a capillary-column gas
chromatograph/mass spectrometer (GC/MS) to analyze for the organic compounds
listed in Table 8.2 which were derived from the Hazardous Substances List (HSL)
in the CLP. Use the internal standard calibration method in the CLP to
quantify the HSL compounds found in the extracts.
Samples particularly high in oil and grease (such as those obtained from
land treatment processes) may require additional cleanup or other treatment for
analysis. Additional cleanup can be achieved by repeating the LH-20
procedure. Each time the cleanup procedure is repeated, the sample(s) should
be rescreened by GC/FID to determine if the additional cleanup is continuing to
make progress. Following each cleanup, use the quality control guidelines
described in the CLP for surrogate recovery to ensure that excessive loss of
aromatic compounds does not occur. In some instances, even repeated cleanup
will not yield samples which can be analyzed at the low concentration level.
In these instances the analyst may analyze them at the medium concentration
level and/or may consider alternative analytical techniques. These techniques
may include the methods from EPA SW-846 which utilize other cleanup procedures
with GC techniques and which are only specific for certain groups of compounds.
8.2.4 Pesticides Analysis
For samples selected for pesticides analysis, follow the CLP procedures for
8-14
-------
TABLE 8.2. SEMIVOLATILE ORGANIC COMPOUNDS FOR ANALYSIS
ACENAPHTHENE
ACENAPHTHYLENE
ANTHRACENE
BENZO (a) ANTHRACENE
BENZOIC ACID
BENZO (a) PYRENE
BENZO (ghi) PERYLENE
BENZO (b) FLUORANTHENE
BENZO (It) 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 PHTHALOTE
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(1.2.3-cd) PYRENE
ISOPHORONE
2-METHYL-4.6-DINITROPHENOL
2-METHYLNAPHTHALENE
2-METHYLPHENOL
4-METHYLPHENOL
NAPHTHALENE
2-NITROANILINE
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
8-15
-------
pesticides and PCB's. For this analysis, use a portion of the sample's
semivolatile organic extract and subject the extract to solvent exchange.
Analyze the solvent-exchanged extract for the pesticides and PCB's (AROCLOR's)
listed in Table 8.3 using gas chromatography/electron capture detection
(GC/ECD).
8-16
-------
TABLE 8.3. PESTICIDES FOR ANALYSIS
ALDRIN
-Alpha - BHC'
Beta - BHC
Delta - BHC
Gamma - BHC
CHLORDANE
4,4'-ODD
4,4'-DDE
4,4'-DDT
DIELDRIN
ENDOSULFAN I.
ENDOSULFAN II
ENDOSULFAN SULFATE
ENDRIN
ENDRIN KETONE
HEPTACHLOR
HEPTACHLOR EPOXIDE
TOXAPHENE
AROCLOR 1016
AROCLOR 1221
AROCLOR 1232
AROCLOR 1242
AROCLOR 1248
AROCLOR 1254
AROCLOR 1260
8-17
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9.0 QUALITY ASSURANCE PROCEDURES
The quality assurance (QA)/quality control (QC) procedures described in
this section provide a performance audit, quality control, duplicate analyses,
and independent analyses. The quality control procedures for providing
corrective action are the internal quality control procedures instituted by
each individual laboratory.
The internal QC procedures, instituted by each laboratory should involve
the use of known QC samples, spiked samples, duplicate samples, matrix spiked
samples, duplicate matrix spiked samples, surrogate spiked samples, and method
blanks.
For the metals analysis, use National Bureau of Standards (NBS) water
(16^3 B) as check samples for the accuracy of the instrumentation. Use a
marine sediment reference material (MESS-1)* and an NBS fly ash sample
(1633 A)** as QC samples to check the overall accuracy of the digestion and
analysis procedures. Spike one process sample with the eight elements listed
in Table 9-1, and calculate their percent recoveries to assess matrix effects.
Prepare and analyze another sample in duplicate to demonstrate analytical
precision.
For the QC on the analysis of the semiVolatile organics and pesticides,
follow the procedures in the Contract Laboratory Program (CLP) protocol. Use
an extra 60 g of a sample for a matrix spike (MS) and a matrix spike duplicate
(MSD). Determine the percent recoveries and calculate the relative percent
difference (RPD) for the duplicates. Compare the results for the MS and MSD
with the acceptable percent recovery range and the RPD specified in the CLP
protocol. Spike all samples prior to extraction with surrogate compounds and
determine the percent recoveries of these compounds. Recovery of less than 10%
of any one surrogate or recovery of two or more surrogates outside the recovery
limits stated in the CLP require that the sample extract be reanalyzed. If the
recovery is outside the limits upon reanalysis, then the sample must be
reextracted and reanalyzed.
^Available from Marine Analytical Chemistry Standards Program of the Canadian
National Research Division of Chemistry, Montreal Road, Ottawa, Canada,
K1A OR9.
**Available from the National Bureau of Standards, Office of Standard Reference
Materials, Rm B-311, Chemistry Building, Washington, DC 20234.
9-1
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TABLE 9.1. SPIKING COMPOUNDS: METALS
Solvent: 0.5% Nitric Acid
Compound
Concentration
(yg/ml)
Arsenic (As)
Barium (Ba)
Beryllium (Be)
Cadmium (Cd)
Calcium (Ca)
Copper (Cu)
Lead (Pb)
Magnesium (Mg)
Manganese (Mn)
Selenium (Se)
Silver (Ag)
Zinc (Zn)
100
100
100
100
100
100
100
100
100
100
100
100
9-2
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Analyze two blank samples consisting of a purified solid matrix spiked
with surrogate compounds and carried through extraction and concentration. One
blank is for the samples and the other blank is for the MS and MSD. Compare
the results with both the CLP specified surrogate recovery limits for the
blanks and with the CLP limits on the levels of common phthalate esters and
Hazardous Substances List (HSL) compounds.
Conduct a performance audit to assess "the precision and accuracy of the
laboratory analyses. This audit should be conducted only once during the
entire testing program at a TSDF. From a homogeneous composite sample, remove
three 30-g aliquots for an organics analysis audit and three 4-g aliquots for a
metals analysis audit. Spike one of the 30-g aliquots with the EPA reference
materials whose contents are listed in Tables 9.2, 9-3. 9-4, and, if
applicable, 9-5- The amount of spiking material should be at least ten times
the anticipated detection limit in a 30-g sample. Spike one of the 4-g
aliquots with the elements listed in Table 9-1- Use a multi-element atomic
absorption standard. The amount of material to be added to a 4-g sample should
yield a concentration ten times the anticipated detection limit for the metals
analysis.
Have the laboratory analyze the spiked sample and two of the unspiked
samples. Replicate analysis of the spiked sample is recommended. The
duplicate unspiked samples analyzed by the laboratories give a measure of
precision. Use the mean of the duplicate analysis to correct the spiked sample
results for corresponding compounds present in the unspiked sample. Compare
the corrected results of the spiked sample to the true value to determine the
accuracy of the analysis.
9-3
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TABLE 9.2. SPIKING COMPOUNDS: ACID EXTRACTABLES II
Standard Code: C-090-01
Solvent:
Compound
Concentration
Benzole acid
p-Chloro-m-cresol
2-Chlorophenol
o-Cresol
p-Cresol
2,4-Dichlorophenol
2,4-Dimethylphenol
4,6-Dinitro-o-cresol
2,4-Dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
Concentration corrected for purity.
9-4
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TABLE 9.3. SPIKING COMPOUNDS: NEUTRAL EXTRACTABLES V
Standard Code: C-040
Solvent: CH-C1
Compound
Purity
Concentration
Acenaphthene
Anthracene
Benzo (k) f luoranthene
Dibenz (a, h) anthracene
Dibenzofuran
1 ,2-Dichlorobenzene
1 , 4-Dichlorobenzene
bis (2-Ethylhexyl ) phthalate
Fluorene
Hexachlorobenzene
Hexachlorocyclopentadiene
Isophorone
Nitrobenzene
N-Nitrosodi-n-propylamine
Pyrene
98+
99+
99+
99+
99+
99+
99+
99+
99+
99+
99+
99+
99+
99+
99+
. 2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
9-5
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TABLE 9.4. SPIKING COMPOUNDS: NEUTRAL EXTRACTABLES VI
Standard Code: C-041
Solvent:
Purity
Compound
Concentration
(yg/ml). .
Benzo ( a) pyrene
Benzo { g , h , i ) perylene
Benzyl alcohol
4-Bromophenyl phenyl ether
bis ( 2-Chloroethyl ) ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
Diethyl phthalate
Dimethyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Hexachlorobutadiene
Hexachloroe thane
Naphthalene
98+
99+
99+
99+
99+
99+
99+
99+
99+
99+
99+
99+
99+
99+
99+
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
9-6
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TABLE 9-5. SPIKING COMPOUNDS: PESTICIDES II
Standard Code: C-093-01 Solvent: Toluene/Hexane (1:1)
Concentration
Compound (yg/ml)
Aldrin 2000
Alpha-BHC 2000
Beta-BHC 2000
Delta-BHC 2000
Gamma-BHC 2000
4,4'-ODD 2000
4,4'-DDE 2000
4,4'-DDT 2000
Dieldrin 2000
Endosulfan II 2000
Endosulfan II 2000
Endosulfan sulfate 2000
Endrin 2000
Endrin aldehyde 2000
Heptachlor 2000
Heptachlor epoxide 2000
Endrin ketone 1000
p,p'-Methoxychlor 2000
Concentration corrected for purity.
9-7
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10.0 REPORT FORMAT
Data generated during this type of sampling program are generally presented
in a site-specific report for the particular facility visited. This type of
report includes data applicable to processes at the site and quality assurance
data generated by the sampling program. A brief description of the report
format follows.
I. Introduction - Discuss intent of the study and contents of
the report. Specific items should include:
Overall goals of the test
Specific goals of the test
Names and location of all businesses, contractors,
or agencies involved
Inclusive dates and duration of test period
Statement identifying each sampling location
Statement identifying the kinds of samples taken
and analyses conducted
Deviations from or modifications of sampling and
analysis protocol
II. Summary and Discussion of Results - Present results in
tabular form and discuss. Discussion of the results should
explain the data presentation and address any modification
or changes to the testing protocol and their effect on
sample collection and/or analysis. Conclusions may be drawn
concerning the degree of contamination and how the measured
results may have been affected by sampling and/or analysis.
Specific results presented should include:
Summary of total emissions from facility
Summary of meteorological data
Summary of emissions from each process
Process operational data for each process
Silt content for each sample collected
PM-20 content for each sample collected
Other soil characteristics (i.e., moisture
content, oil and grease content) for each sample
collected, if applicable
Degree of contamination for each sample collected
Performance audit and other quality control
results
10-1
-------
III. Process Descriptions and Operations - Present process
descriptions and the process operating data gathered.
IV. Sampling - Present the plot plan and sampling grid
layouts. Discuss the methods for selecting the sampling
grids and the sample collection procedures. Discuss any
deviations from the sampling protocol and any problems
encountered including time and date and/or associated
sample runs, steps taken to modify the protocol, and
possible effects on sample collection.
This section should also discuss the procedures, locations
and techniques used in collecting and analyzing the
meteorological data.
V. Analyses - Present the analytical procedures used including
any deviations from the analytical protocol.
VI. Appendices - Include results and calculations, raw field
data, analytical data, program participants, sampling logs,
and additional information as necessary.
10-2
-------
11.0 REFERENCES
1. "Compilation of Air Pollutant Emission Factors, Fourth Edition." AP-42,
U.S. Environmental Protection Agency, Research Triangle Park, North
Carolina. September
2. Cowherd, C., B. Petermann, and P. Englehart. "Fugitive Dust Emission
Factor Update for AP-42." Midwest Research Institute Final Report, EPA
Contract No. 68-02-3177, Assignment No. 25, prepared for Industrial
Environmental Research Laboratory, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, September 1983.
3. "Assessment of Hazardous Waste TSDF Particulate Emissions." Draft final
report by MRI prepared for the U.S. Environmental Protection Agency under
Contract No. 68-02-3891, Work Assignment No. 5, May 5, 1986.
4. U.S. Environmental Protection Agency Contract Laboratory Program,
Statement of Work for Organic Analysis, 7/85 Revision.
i
5. "Test Methods for Evaluating Solid Waste, Physical/Chemical Methods,"
Second Edition. U.S. Environmental Protection Agency, Office of Solid
Waste and Emergency Response, Publication No. SW-846, July 1982.
6. "Methods for Evaluation of Water and Waste Water." EPA Publication No.
600/4-79-020.
7. "ASTM D 1193-74, Standard Specifications for Reagent Water."
8. Mason, B.J. "Preparation of Soil Sampling' Protcol: Techniques 'and
Strategies." .EPA Publication No. 600/4-83-020, May 1983.
9. "Appendix A: Procedures for Sampling of Surface/Bulk Materials." From the
report "Handbook for Eva!
prepared by MRI for the 1
Contract No. 68-02-3891.
report "Handbook for Evaluating Control Technology for Sources of PMin"
prepared by MRI for the U.S. Environmental Protection Agency under
11-1
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-450/3-86-014
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
"Field Sampling and Analysis Protocol for Collecting
Soil Samples from Hazardous Waste Treatment, Storage,
and Disposal Facilities"
5. REPORT DATE
Issued October 1986
6. PERFORMING ORGANIZATION CODE
AUTHOR(S)
William G. DeWees, Scott S. Steinsberger, Ph.D,
Steven J. Plaisance
8. PERFORMING ORGANIZATION REPORT NO.
PERFORMING ORGANIZATION NAME AND ADDRESS
Entropy Environmentalists, Inc.
CEM/Engineering Division
P. 0. Box 12291
Research Triangle Park, NC 27709-2291
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME ANO ADDRESS
U. S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Emission Standards and Engineering Division
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
U. S. EPA Task Manager - Clyde E. Riley, Emission Measurement Branch, ESED, OAQPS
16. ABSTRACT
This document is a sampling and analysis protocol to be used in designing
programs to collect and characterize soil samples (surface samples) from
processes within hazardous waste transfer, storage, and disposal facilities
(TSDF's). The soil characterization data, along with meteorological data and
process operation data are used in emission factor equations and dispersion
models to assess the impact on ambient air of contaminated fugitive particulate
emissions from TSDF's. The sampling procedures are designed to collect
representative soil samples from the TSDF processes. The analytical procedures
are designed for physical characterization (weight-loss-on-drying, silt
content, and PM-20 content) and chemical characterization (metals, cyanide,
semivolatile organics, oil and grease, PCB's, and pesticides). Procedures are
described for analysis of separate soil fractions (silt, and if desired, PM-20)
to determine the degree of contamination in that size fraction of the species
of interest.
17.
KEY WORDS ANO DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATi Field/Group
Air Pollution
Sampling
Analysis
Soil Surveys
Fugitive Emissions
TSDF' s
Particulate.Emissions
Silt
PM-20
Hazardous Waste
Sampling & Analysis
Protocol
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (Tills Report)
Unclassified
21. NO. OF PAGES
68
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
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