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SAMPLE COLLECTION GUIDANCE DOCUMENT
Hazardous Waste Section
Waste Management Branch
February 1991
Revised May 1991
Revised October 1991
Revised July 1993
Table of Contents
I. INTRODUCTION
II. SAMPLE PROCEDURES
m.
TableofC
A. ? Questions ?
B. Safety
C. Office Review
D. Arrival at the Facility
E. Sample Collection
1 . Collecting representative samples
2. Split vs Duplicate samples
3. Sampling equipment
4. Sampling methods
5. Sample handling and preservation
6. Decontamination procedures
7. Quality assurance/ quality control
8. Notes and photographs
F. Forms
1. Sample labels
2. Sample Analysis Request fonns
3. Chain of Custody fonns
4. Receipt for Samples fonns
ATTACHMENTS
Sample Request Instruction Sheets
Example of Sludge and Surface Water
Sampling Scenerios
Sample Containers and Preservation Procedures
for Ground Water Monitoring
Analytical Methods for Organic
and Inorganic Compounds
Practical Quantitation Limits
for Organic Compounds
Instruction Manual for pH/Temperature/
Conductivity Meter
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2
2
3
3
4
4
7
10
11
12
13
14
14
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Attachment A
Attachment B
Attachment C
Attachment D
Attachment E
Attachment F
I. INTRODUCTION
This document is intended to provide general guidance on collecting samples that could be
introduced as evidence in legal proceedings. The guidance is general in nature because each
site is different and has its own set of unique circumstances. The techniques and procedures
outlined in the following pages are standard sampling methods used by the Ground Water
Unit of the Hazardous Waste Section during Site Investigations, Comprehensive Ground
Water Monitoring Evaluations (CMEs), and Operation and Maintenance Evaluations
(O&Ms).
It is vital that samples be collected in a manner which will not jeopardize sample integrity.
Court cases or hearings involving hazardous waste contamination can be won or lost based
on the integrity of the sample data. This book contains procedures that will assist Hazardous
Waste Section (HWS) field personnel in obtaining samples and maintaining sample integrity.
This includes methods for collecting various types of samples, using the appropriate sample
containers, completing the associated paperwork, and decontaminating non-disposable field
equipment.
II. SAMPLE PROCEDURES
A. ? Questions ?
If questions arise regarding sampling techniques, sample handling or preservation
protocol, completion of paperwork, or decontamination of equipment, please feel free
to contact a member of the Ground Water Unit (GWU) at [phone].
Questions regarding the specific sampling procedures for constituents not listed on the
sample analysis request forms (such as cyanide) should be directed to the Ground
Water Unit.
Questions regarding analytical/laboratory procedures should be directed to John Neal
for organic analysis and Bill Walker or Paul Childers for inorganic analysis. Samples
sent to the State laboratory should be directed to Arnold Hall. State laboratory
personnel can be reached at [phone].
B. Safety
It is HWS policy that personnel safety is of ultimate importance. In many cases,
HWS personnel must determine in the field whether or not sampling can be conducted
in a controlled, safe environment. If HWS personnel consider the situation unsafe,
the first priority is to leave the scene. If questions regarding safety arise, HWS
personnel may refer to the Hazardous Waste Section's Health and Safety Manual or
contact Lafayette Atkinson, Safety Officer, at [phone].
For most sampling inspections, level D protective clothing is appropriate. This
generally includes the use of steel-toed safety boots, hard hat, and safety glasses.
Occasionally, increased levels of protection are necessary to safely proceed with
sampling. All health and safety considerations should be described in the Site Safety
Plan and discussed with Lafayette Atkinson prior to sample collection. In the
following discussion on sample collection, it is assumed that all the necessary safety
precautions have been taken.
C. Office Review
Prior to conducting a sampling event, it is highly recommended that HWS personnel
gather and review as much information as possible about the area to be sampled and
the material to be sampled. If the data are available, the inspector should be familiar
with the following items, including but not limited to:
1. facility layout and contacts,
2. waste generation processes,
3. waste streams,
4. historical sampling/analytical data, and
5. safety/contingency plans.
With this knowledge, one can gather all necessary equipment, minimize the number
of samples that must be collected, and minimize exposure to any hazard at the site. If
you have any questions on sample collection procedures, you are encouraged to call a
member of the GWU prior to collecting the sample if at all possible.
D. Arrival at the Facility
When arriving at a facility to collect a sample, HWS personnel should inform the
facility owner/operator that split/duplicate samples will be offered in State provided
containers. The owner/operator should also be informed that upon completion of the
sampling, he/she will be asked to sign a form acknowledging acceptance or rejection
of split/duplicate samples.
Remember that the priorities when collecting samples are to act professional, maintain
your integrity, and maintain the samples' integrity. Any appearance of impropriety
will be used to question the validity of your work and the data you collect.
2
E. Sample Collection
1. Collecting representative samples
A representative sample is a sample that represents the actual conditions at the
site. It is important to obtain a representative sample in order to characterize
the contamination, if evident, at the facility.
When determining where to collect a representative sample, it is advantageous
to be familiar with the facility's waste stream or waste handling procedures.
For environmental media samples (i.e. soil or water) one needs to be
especially careful not to introduce contamination to the area to be sampled.
This includes, but is not limited to, using decontaminated equipment for all
sampling and avoiding contact with the media before, during, and after
sampling.
For concentrated media (i.e. sludge or liquid), it is important to (a) avoid
introducing contamination to the sample, and to (b) determine if the material
being sampled is representative of the majority of the waste generated at the
site. It is very important to note if the sample represents a small unique type
of waste or if the sample represents the typical waste generated at the site. To
avoid incorrectly characterizing a facility's waste, the sampler needs to
determine if the sample is typical or atypical of the waste generated at the site.
2. Split vs Duplicate samples
The purpose of collecting split/duplicate samples is to allow the facility the
opportunity to analyze the "same" substance the State will analyze.
Prior to initiating sampling, HWS personnel should always notify the facility
representatives that split/duplicate samples will be offered in containers
provided by the State. When gathering field equipment and sample containers
prior to the sampling event, sampling personnel should bring enough
containers to provide the facility with split/duplicate samples.
The collection of split samples consists of: (A) placing the media in properly
decontaminated container, (B) mixing thoroughly, and (C) filling the individual
sample containers with the composited material.
Split samples may be collected for soil or other solid samples that are to be
analyzed for inorganic parameters or semi-volatile organic compounds. Split
Soil or other solid samples to be analyzed for volatile organic compounds
should not be collected as split samples because thorough mixing will likely
3
cause excessive volatilization.
The collection of duplicate samples is accomplished by filling containers with
material from a similar location at approximately the same time. Most
samples collected by the HWS, are obtained as duplicate samples because the
additional equipment and sample handling required for split samples increases
the potential for compromising a sample's integrity. For example, obtaining
split ground water samples is not recommended because it would require
compositing the water, mixing the water thoroughly, and then transferring the
water to the appropriate sample bottles.
3. Sampling equipment
When collecting samples it is vital to use equipment constructed of material
that will not compromise the sample integrity. The equipment should also be
cleaned so that contamination will not be introduced into the sample. These
conditions limit us to using primarily teflon, glass, stainless steel, or teflon
coated stainless steel equipment. If the sample container can not be used to
gather the sample substance directly, properly decontaminated equipment
should be used to transfer the substance to the container (e.g. teflon hailers for
ground water sampling, clean glass sample bottle for shallow surface water
samples, or stainless steel scoops for soil sampling). If a piece of equipment
is used to transfer the substance to the sample container, a "better" duplicate
sample can be obtained by transferring a portion of the material on the scoop
or in the bailer into one container and the remaining portion into the
"duplicate" container. For example, when using a teflon bailer to collect a
ground water sample, it's advisable to pour part of the water in the bailer into
one container and part of the water into the "duplicate" container.
4. Sampling methods
The sampling methods listed below describe gathering the sample material and
supporting data. Sampling personnel should be aware of the appropriate
sample handling procedures (such as donning a new, clean pair of
protective/nonreactive gloves at each sampling point) to avoid introducing
contaminants to the sample. The sample handling procedures are provided in
section 11.E.5 .
Ground Water Sampling
Most ground water samples will likely be collected from one of two sources; a
ground water monitoring well or a tap at a private residence with a well. If an
equivalent ground water sample is desired, HWS personnel will collect the
4
samples as duplicates because it is not technicall y feasible to mix ground water
prior to sampling.
The sampling procedure for a ground water monitoring well includes:
measuring the water level; purging the well; and obtaining the ground water
sample. In order to determine the ground water flow direction, water levels in
the wells should be measured. Well depth measurements should also be made
to ensure the integrity of the well bottom. All water levels and well depths are
to be measured to the nearest 0.01 ft below the surveyed measuring point
(e.g., top of casing). Prior to measuring the water levels, non-vented or
sealable well caps should be removed to allow the water level to equilibrate.
The measuring device should be decontaminated between each well by washing
with phosphate free soap and rinsing thoroughly with organic-free water.
Note : Ac id or isopropanol rinses should not be used as they may damage the probe.
Measurements should proceed from the least to the most contaminated wells to
minimize potential cross-contamination via the water level measuring device.
After measuring water levels in all wells, HWS personnel should purge the
wells to remove stagnant water. The volume of water in the well should be
calculated from the water level and well depth measurements. Monitoring
wells should be purged with a bailer or a pump. Purging equipment should be
constructed of material that will not compromise sample integrity. During
purging, water should be withdrawn from the top of the water column.
Purging should proceed from the least to the most contaminated well. Wells
are purged when one of the following tasks is completed:
a minimum of one volume of water is removed from the well, and 3
consecutive readings of pH, temperature, and conductivity (measured
after each well volume) show no more than a 10 % variation,
the well is purged to dryness, or
3-5 volumes of water are removed from the well.
Note: If a well has historically been contaminated, the purge water should be
managed properly.
When purging is completed, sample collection should be conducted as soon as
technically feasible and within 24 hours. The sampling should be done with a
decontaminated bailer or an appropriate pump that will allow for the collection
of representative samples. When sampling with a bailer, an equal portion
from each bailer should be poured into "duplicate" sample containers. This
5
procedure is continued until all sample containers from each set are full. Once
all of the sample containers to be submitted to the laboratory have been filled ,
an additional cubitainer is filled for measurement of field parameters (see
section II.E.5.d below regarding field parameters).
If the well, such as one at a residence, is not accessible with the HWS's
equipment, sampling personnel should collect a sample from the tap closest to
the wellhead and prior to the pressure tank. If there is not a tap prior to the
pressure tank, then a water sample should be collected from the tap closest to
the well. When collecting a sample from a residential well , it is important to
allow the water from the tap to run until the pump cuts on and any stagnant
water in the lines has been flushed . Collecting samples from a tap involves
alternately filling duplicate containers from each set until all sample containers
are full. Once all of the sample containers to be submitted to the laboratory
have been filled, an additional cubitainer is filled to measure the field
parameters pH, temperature, and specific conductance.
Surface Water Sampling
If necessary, HWS personnel should collect surface water samples as
duplicates because compositing is not feasible for water samples. Surface
water sampling includes filling sample containers with water from a stream or
pond. Surface water samples are obtained by standing downstream of the
water to be sampled, turning the container sideways, partially submerging the
container allowing water to fill the container with minimal agitation. Sampling
personnel should minimize the amount of floating debris entering the
container. This procedure is followed until all sample containers from each set
are filled. Once all of the sample containers to be submitted to the laboratory
have been filled, an additional cubitainer is filled. This sample is used to
measure field parameters.
If several sampling points (for surface water or soil) are established in the
same stream, begin sampling at the farthest downstream station, and proceed
in an upstream direction so that flowing water will not carry soil and possible
contamination to the next sampling station.
Soil/Sludge Sampling
When an equivalent set of samples is necessary, it is recommended that HWS
personnel collect soil or sludge samples as duplicates. If it is technically
feasible, soil/sludge samples to be analyzed for inorganic parameters and semi-
volatile organic compounds may be collected as split samples. Soil or sludge
samples for organic parameters should be collected as duplicates because
compositing might volatilize the organic parameters. A description of split vs
6
duplicate sampling is provided in section II.E.2 above.
When collecting duplicate samples, fill one sample container with the
soil/sludge, then fill the "duplicate" container, and fill the remaining
containers similarly. If split samples are necessary, the media should be
composited in a compatible container such as a decontaminated glass bowl.
The composited soil/sludge should then be transferred to the appropriate
containers for inorganic parameters.
Soil sample containers for volatile organic analysis should be filled with
minimal headspace) to reduce volatilization of voes.
Pond/Lagoon Sampling
When an equivalent set of samples from a pond or lagoon is necessary, HWS
personnel should collect duplicate samples. The sampling is conducted by
attaching an appropriate sample container to a rod that is long enough to
collect samples away from the edge of the pond/lagoon. The container
attached to the end of the rod is dipped into the sample material and filled.
Equal portions of the sample material are then poured into each set of the
similarly prepared sample containers. Sample containers from each set are
filled alternately until all like containers are filled.
Note: Samples for metals or SVOes are collected in a similarly prepared container,
and samples for voes are collected in a container prepared especially for
voes. Whenever a sample container is used to transfer media from the
source to a sample container destined for the lab, HWS personnel must be sure
to use a compatible "transfer" container.
5. Sample handling and preservation
The tasks listed below are general guidelines for HWS personnel to follow
when initiating the actual sample collection:
a. When collecting ground water samples, the containers for
analysis of voes should be preserved prior to filling (see S.f of
this section).
b. Put on new, clean, protective/nonreactive disposable gloves for
collecting samples, handling samples or equipment, and
decontaminating sampling equipment. A new pair of gloves
should also be donned at each sampling point.
7
• C. Obtain the appropriate containers and equipment to be used at
the sampling location.
d. Fill the containers as described in section Il.E.3 above. Keep
in mind that precautions should be taken to avoid introducing
contaminants to the sample. This includes, but is not limited to
procedures such as: keeping the top of the container closed at all
times except when transferring substance into the container, and
avoiding, where possible, contact between your gloves and the
substance entering the sample container.
e . When collecting water samples, the next step after the sample
containers have been filled is to obtain pH, temperature, and
specific conductivity readings (field measurements are not made
on soil, sludge, or liquid samples). Instructions for proper use
of the pH meters provided by the State are found in Attachment
F of this document. When collecting field measurements, the
probes the probes should be thoroughly rinsed with de-ionized
water before and after the probes are in the sample water. The
sample for field measurements is not sent to the laboratory, and
should be disposed of properly. Additionally, all rinse water
from rinsing the probes or other decontamination procedures
should be collected and disposed of properly.
f. Water samples that have a "no headspace" requirement should
be preserved prior to filling. Water samples that are allowed to
have headspace in the container may be preserved after the
container is filled. Attachment C is a table showing the types
and amounts of preservatives recommended for the listed
parameters for ground water samples. Sampling personnel who
do not have access to chemical preservatives, but anticipate
sampling for compounds requiring field preservation other than
ice, should contact the Ground Water Unit prior to sample
collection. For example, a water sample collected for cyanide
analysis would require field preservation by adding NaOH so
the pH is greater than 12. Subsequently, sending an
unpreserved water sample for cyanide analysis to the laboratory
will provide no useful data.
CAUTION: If the potential for a reaction between the
preservative and the water is unknown, DO NOT
USE CHEMICAL PRESERVATIVES. Always
wear protective/non-reactive gloves and eyewear
when using chemicals.
8
Of the frequently collected water samples, the following should
be preserved in the field, when technically feasible:
-Water samples for VOC analysis should be preserved by
putting 3 drops of concentrated HCl in the vials prior to filling
the vials with sample water.
-Water samples for metals analysis should be preserved with
1:1 HNO3 (1 part de-ionized water, 1 part HNO3) until the pH
of the sample is < 2 (usu. 5 ml will sufficiently lower the pH).
After adding the acid, the pH should be checked by pouring a
small amount of the sample over litmus paper to ensure that the
pH is less than 2.
g. Once the sample containers have been filled, and the necessary
field measurements and preservation procedures have been
completed, the containers should be placed into plastic zip-lock
bags. Each sample should be placed into a separate zip-lock bag
in order to minimize the potential for cross contamination.
h. Environmental samples (surface water, ground water, or soil)
should be placed in a cooler with ice or ice packs. It is
important to place environmental samples and ice or ice packs
into the coolers as soon as possible after sample collection in
order to observe the proper preservation procedures. It is
recommended that waste or concentrate samples (sludge or
liquid) also be kept on ice.
1. The associated paperwork should then be completed as described
in section 11.F of this document. Labels should be placed on
the containers, containers placed back in coolers, and ice packs
replaced on top of samples. The Receipt for Samples and Chain
of Custody forms should be signed by appropriate personnel. If
the samples are to be sent to the State lab via a lock box, the
completed forms should be placed in a zip-lock bag and taped to
the top of the cooler or the underside of the lock box cover.
The lock box should be locked and sent to the lab as soon as
possible to avoid exceeding the sample holding times.
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6. Decontamination procedures
Field equipment should be clean prior to coming into contact with the sample
material to avoid introducing contaminants to the sample. Non-dedicated
sampling equipment (i.e., sample equipment used at more than one sampling
point) should be decontaminated between each sampling point. Generally, this
includes, but is not limited to equipment such as auger buckets, scoops, pails,
and hailers, constructed of stainless steel, glass, or teflon. Glass coliwasas
and drum thieves are disposable, but should be decontaminated prior to use
because they are usually not pre-cleaned.
The decontamination procedures for stainless steel equipment are as follows:
a. Remove excess soil/sludge with tap water rinse.
b. Wash with de-ionized or organic-free water and phosphate-free
soap.
c. Rinse with de-ionized or organic-free water.
d. Rinse with isopropyl alcohol.
e. Rinse with organic-free water.
f. Let air dry.
The decontamination procedures for teflon or glass equipment are as follows:
a. Remove excess soil/sludge with tap water rinse.
b. Wash with de-ionized or organic-free water and phosphate-free
soap.
c. Rinse with de-ionized or organic-free water.
d. Rinse with 10% nitric acid.
e. Rinse with de-ionized or organic-free water.
f. Rinse with isopropyl alcohol.
g. Rinse with organic-free water.
h. Let air dry.
Rinsate from the decontamination procedures should be collected in a
nonreactive container and disposed of properly. Because of the supplies
needed to decontaminate field equipment, decontamination is more easily
conducted in a laboratory environment. However, if multiple samples must be
taken at the facility, and only one set of decontaminated sampling equipment is
available, Section personnel should be prepared to decontaminate equipment in
the field.
Other equipment that comes into contact with the sample material such as rope
and disposable protective/nonreactive gloves should be disposed of after
sample collection at each sampling location.
7. Quality assurance/quality control
Quality assurance/quality control procedures are employed to help ensure the
integrity of field samples and the validity of analytical data. Field and
equipment blanks are types of blanks used to detect contaminants that are
attributed to items such as a) contaminated sample containers, b) a
contaminated supply of de-ionized or organic-free rinse water, c) sample
handling techniques that introduce contaminants to the sample, or d)
contaminated sampling equipment.
Section personnel should prepare the following field blanks:
Field blanks -organic-free water should be collected in one of each
type of sample container used in the field. Organic-free water is
transported into the field and poured into the appropriate sample
containers during the sampling event. The blank should be handled like
a sample, and returned to the laboratory for analysis. Sampling
personnel should collect one field blank per sampling event.
Equipment blanks -when non-dedicated equipment is used for sample
collection, HWS personnel should collect an equipment blank to ensure
that the equipment has been properly decontaminated. After
decontamination, the equipment should be rinsed with organic-free
water and the rinsate collected in each type of container used in the
field. Sampling personnel should obtain at least one equipment blank
for each day of sampling.
All blanks should be collected, preserved, and handled according to the sample
collecting procedures described in this document.
Similar to other samples, all the paperwork involved with labelling, requesting
analysis, and recording chain of custody must be completed for the field
blanks. The field blanks will not be recorded on the Receipt for Samples form
unless splits or duplicates of the field blanks are collected and provided to the
facility representative. Field blanks should be analyzed for the same
parameters as the samples.
11
8. Notes and photographs
Detailed notes should be taken at the facility describing the sampling event.
The inspector/sampler should record all aspects of the event, including, but not
limited to:
a. facility name and location
b. type and purpose of sampling inspection
c. participants
d. environmental conditions
e. descriptions of sampling locations
f. date and time of collection of each sample
g. types of containers
1. preservatives used
J. analysis requested
k. unusual sampling procedures
1. sampling equipment
m. decontamination procedures
n. quality assurance/quality control measures
When sampling ground water, the following information should also be
recorded in the field book:
o. water level and well depth measuring equipment
p. location and elevation of measuring point
q. depth of water level below measuring point
r. depth of well bottom below measuring point
s. time and date of well purging
t. equipment used for purging
u. volume of purged water
v. field measurements (pH, temperature, conductivity)
At each sample location, two (2) sets of photographs should be taken, and each
photo should be labeled with: 1) time, 2) date, 3) facility, 4) description, and
5) signature (generally, photographs of permanent monitoring wells are not
necessary). Try to include a large permanent structure (building, etc.) in each
photo to provide scale and sampling location if additional samples are needed.
A map should also be drawn showing the sample locations and approximate
distances to permanent structures.
12
F. Fonns
In some cases, the most difficult part of sample collection is the paperwork involved.
Attachment A of this document describes completing the paperwork for each type of
media that you may encounter and be requested to sample. The first part of the
Attachment A describes different scenarios that you may encounter, specifies the type
of container(s) to be used, and demonstrates how the Sample Analysis Request sheet
should be completed. The following paragraphs describe the various forms that you
will be required to complete.
1. Sample Labels
Sample labels are necessary to identify the contents of each sample container
for all personnel that may handle the samples, including samplers, transporters
(if necessary), and lab personnel. The Hazardous Waste Section currently uses
the following two types of sample labels to identify samples: (1) primary
labels, which are divided into organic and inorganic labels; and (2) secondary
labels.
Each primary label has a unique, pre-printed sample identification number.
Two types of primary labels are necessary because the State Laboratory has an
organic lab separate from the inorganic lab. The organic labels are used to
identify samples analyzed for organic constituents (volatiles, semi-volatiles,
herbicides, pesticides, etc.), and the inorganic labels are used to identify
samples analyzed for inorganic constituents (metals, chloride, sulfate, etc.).
It is recommended that each sample container be labeled. The secondary
labels are used to identify additional sample containers that have the same
sample identification number. For example, a set of ground water samples for
organic parameters may consist of two I-liter containers and two 40 ml vials,
for a total of four containers that can be identified by the same unique
identification number. Since each primary organic label has a unique number,
secondary labels are needed to identify the remaining three containers.
The primary and secondary sample labels are shown below:
13
The use of sample labels in specific sampling situations is described in the
following pages and examples of completed sample labels are found in
Attachment B. The pre-printed unique identification number should be
recorded in the field notebook along with the sample location description.
2. Sample Analysis Request forms
Sample Analysis Request forms are necessary to inform the laboratories which
specific analyses are to be run on each sample. The latest version of the
Sample Analysis Request form is DHS 3191 (Revised 2/91) and instructions
for completing the form are printed on the back of each sheet. The following
pages describe how to complete the form for specific sampling situations.
Examples of completed Sample Analysis Request forms are found in
Attachment B.
3. Chain of Custody forms
Chain of Custody forms are used to track the samples from the field to the
laboratory. Each person who has possession of the samples signs the Chain of
Custody form starting with the sampler and ending with the laboratory
personnel. Organic and inorganic samples must be listed on separate Chain of
Custody forms because the organic and inorganic samples go to two separate
laboratories. Samples should be listed on the Chain of Custody forms by the
unique pre-printed sample number on the label. Completing the remainder of
the Chain of Custody form is self-explanatory. Examples of completed Chain
of Custody forms are found in Attachment B.
4. Receipt of Samples form
The Receipt for Samples form is used to acknowledge a facility owner/
operator's acceptance or rejection of split/duplicate samples. As part of each
sampling event, HWS personnel should offer split/duplicate samples to the
facility owner/operator in containers provided by the Section. The
owner/operator (or site representative) should also be informed that he will be
asked to sign a form acknowledging acceptance or rejection of the samples.
[Note: If HWS personnel can find out, prior to sampling, whether or not the
site representative wants split/duplicate samples, they may be able to avoid
filling too many (or too few) containers. It may be advisable in certain
situations to automatically collect split/duplicate samples to give the site
representative every opportunity to accept the samples.]
14
scgd.txt
A Receipt for Samples form should be completed and signed by a HWS
representative and signed by the owner/operator to acknowledge acceptance or
rejection of the split/duplicate samples. The Receipt for Samples form is
located on the back of the Chain of Custody form and similarly, organic and
inorganic samples should be listed on separate forms. Samples should be
listed on the Receipt for Samples form by the unique pre-printed sample
number on the primary label. Completing the remainder of the Receipt of
Samples form is self-explanatory. Examples of completed Receipt of Sample
forms are found in Attachment B.
15
Attachments
Attachment -A
SAMPLE REQUEST INSTRUCTION SHEETS
voes-WATER
Sample Condition: Well/Stream/Pond/etc.
Substance: Ground Water/Surface Water
Analysis Requested: Volatile organic compounds
Containers:
Preservative:
Sample Labels:
Analysis Forms:
Two (2) 40 ml glass vials with septum top
Fill with no headspace; Cool to 4 ° C
If samplers have access to chemical preservatives, ground water
samples for VOCs should be preserved with 3 drops of concentrated
HCl prior to filling the vials.
Attach an organic sample label with a unique identification number to
one of the glass vials and write the sample ID # on the glass portion of
the other vial with a permanent marker.
Note: If a semi-volatile water sample is collected at the same
sample point, the same organic sample ID # can be used
to identify the two VOC vials and the two semi-volatile
bottles.
Check ( ./) the appropriate spaces for sample type and requested
analyses as shown on the attached form(s).
Note: If a semi-volatile water sample is collected at the same
sampling point, one analysis request sheet can be used
for analyses of both volatile and semi-volatile
compounds.
Chain-of-Custody: List all organic sample(s) (by sample ID# printed on the label) on the
Chain-of-Custody form(s) that go to the organic chemistry laboratory.
use [z_) 4c ml 6 la-:;s \J 1tlls v,., rWl ~ph.Hn ~p~
N.C. Ocpartmcnt or Environment, SAMPLE ANALYSIS REQUEST
I kahh, & Natural Resources
Solid Waste Management Division
State Laboratory or Public llealth
P.O. Box 28047, 306 N. Wilming1on St~et
Raleigh, North Carolina 27611
.,le Number ----------------Field Sample Number ________________ _
Name of Sile Sile Location ------------------------------------
Collected By -----------ID# ____ Date Collected __________ Time ______ _
Agency: Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Checl 'th e1 e ►~ (1)~,,-(2-) Inorganic Compounds Results(mg/1)
Environmental Concentrate Comments Arsenic --Barium
✓ Ground water (1) --_ Solid (5) Cadmium --Chromium
V Surface water (2) --_ Liquid (6) Lead --Mercury
_Soil (3) Sludge (7) --Selenium --Silver --_ Other (4) Other (8) ------Organic Chemistry Inorganic Chemistry --
Parameter Results (mg/I) Parameter Results (mg/I) (mg/kg) Organic Compounds Results (mg/I)
~ P&T:GC/MS Arsenic benzene ----_ Acid:B/N Ext. Barium carbon tetrachloride ----MTBE Cadmium chlordane ------Chloride chlorobenzene ------Chromium chloroform ------
--__ Copper o-cresol --Fluoride m-cresol ------
--Iron __ p-cresol --Lead cresol ------
--__ Manganese --1,4-dichlorobenzene
--__ Mercury 1,2-dichloroethane
--Nitrate = 1,1-dichloroethylene --Selenium 2,4-dinitrotoluene --= heptachlor Silver --Radiochemistry Sulfates hexachlorobenzene ----······-··--·-Zinc hexachlorobutadiene ----Parameter Results (PCl/1) _pH hexachloroethane
__ Gross Alpha __ Conductivity = methyl ethyl ketone
Gross Beta TDS nitrobenzcne ----= pentachlorophenol TOC ----__ pyridine
Microbiology --__ tetrachlorocthylenc
--__ trichloroethylene
Parameter Results (Col/lOOml) --__ 2,4,5-trichlorophenol
----2,4,6-trichlorophenol
---= vinyl chloride
cndrin --lindane --Date Received Reported by __ methoxychlor
__ toxaphene
Date Extracted Date Reported 2,4-D --_ 2,4,5-TP (Silvex)
Oa1c Analy1.cd Lab Number --1\1 IC.: 1:ltJI (l).,.,..;,. .... ..1-, /U1\
I-CHEM CERTIFICATE OF ANALYSIS
CONTROL NO.001080
is is your Certificate of Analysis f or I-CHEM SUPERFUND-ANALYZED™ Product which has hcen prepared in accordance
.. 1th I-CHEM Performace-Based Specifications. This product meets or exceeds all analyte specifications established in the U.S.
EPA "Specifications and Guidance forOhtaining Contaminant-Free Sample Containers" for use in S1q1c1fund and other ha:ardm1s
waste p1-o,~rams. Please refer to the case label for information about the recommended application of this product.
Compound
Acetone
2,2-Dichloropropane
Bromodichloromethane
Ouantitation Limit(ug/L)
<5
< I
< I
cis-1,3-Dichloropropene
2-Butanone
< I
<5
< I Hexachlorobutadiene
n-Butylbenzene < I
p-Isopropyltoluene < I
Chlorobenzene < I
Naphthalene < I
Chloromethane < I
I, 1,2,2-Tetrachloroethane < 1
Dibromochloromethane < 1
1,2,3-Trichlorobenzene < I
1,4-Dichlorobenzene < I
I, I, I-Trichloroethane < I
Dichlorodinuoromethane < I
I ,2,3-Trichloropropane < I
trans-1,2-Dichloroethene < I
Vinyl Acetate < 5
Xylene (total) < I
Vinyl Chloride < I
Glass Sample Containers
for use in the analysis of Volatile Organics
Compound Ouantitation Limit(ug/L)
1,3-Dichloropropane <I
Bromohcnzene < I
trans-1 ,3-Dichloropropene < I
Bromomethane < I
Ethyl benzene <I
sec-Butylhenzene < I
lsopropylbenzene < I
Carbon Tetrachloride < I
Methylene Chloride <5
Chloroform < I
Styrene < I
1,2-Dibromo-3-chloropropane < I
Toluene < I
Dibromomethane < I
1.1 ,2-Trichloroethane <I
1,2-Dichlorobenzene <I
Trichlorofluoromethane <I
1, 1-Dichloroethane < I
1.3,5-Trimethylbenzene < I
I, 1-Dichloroethene <I
1,2,4-Trimethylbenzene < I
cis-1,2-Dichloroethene < I
Please keep this certificate for your records and to facilitate any necessary correspondence.
If additional information is required, contact our Technical Service Department at
(800) 443-/689 or [phone] inside California.
R 1
Corporate Quality Assurance Manager ~ nrintrerf on rrer:vcled oaoer
Compound Ouantitation Limit(ug/L)
Benzene < I
1.2-Dichloropropane <I
Bromoform <I
I, 1-Dichloropropene < I
tert-Butylbenzene < I
2-Hexanone <5
Carbon Disulfide <I
4-Methyl-2-pentanone <5
Chloroethanc < I
n-Propylbenzene < I
2 & 4 Chlorotoluene < I
Tetrachloroethene < I
1.2-Dibromoethane (EDB) <I
1.2,4-Trichlorohenzene < I
1,3-Dichlorobenzene < I
Trichloroethene < I
1,2-Dichloroethane < I
I ,
SVOCs -WATER
· 1 :
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Sample Condition: Well/Stream/Pond/etc.
Substance: Ground Water/Surface Water
Analysis Requested: Semi-volatile organic compounds
Containers:
Preservative:
Sample Labels:
Analysis Forms:
Two (2) I-liter amber glass bottles
Cool to 4° C
Attach an organic sample label with a unique identification number to
one of the amber bottles and write (with a permanent marker) the
sample ID # on the other bottle (the cap is a good place).
Note: If a VOC water sample is collected at the same sample
point, the same organic sample ID # can be used to
identify the two semi-volatile bottles and the two VOC
vials.
Check (.I) the appropriate spaces for sample type and requested
analyses as shown on the attached form(s).
Note: If a VOC sample is collected at the same sampling point,
one analysis request sheet can be used for analyses of
both volatile and semi-volatile compounds.
Chain-of-Custody: List all organic sample(s) (by sample ID # printed on the label) on the
Chain-of-Custody form(s) that go to the organic chemistry laboratory.
USf (z.) l ~ L.i+£( Amber c~ll\SS ~e+t\e5.
I
i'!.C. Department or Environment,
I kalth, & Natural Resources
Solid Waste Management Division
SAMPLE ANALYSIS REQUEST State uibonitory or Public Health
P.O. Box 28047, 306 N. Wilmington St~ct
Raleigh, Nonh Carolina 27611
itc Number ---------------Field Sample Number _______________ _
Name of Site ---------------Site Location ·-------------------
Collected By _________ _ ID# Dale Collected Time --------------------
Agency: Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Cnec\<... ~'t+hec (/) or (7-) Inorganic Compounds Results(mg/1)
Environmental Concentrate Comments Arsenic --Barium ✓ Ground water (1) --_ Solid (5) Cadmium --Chromium
~/ Surface water (2) --_ Liquid (6) Lead --Mercury
_ Soil (3) _ Sludge (7) --Selenium --Silver --_ Other (4) _ Other (8) --
----Organic Chemistry Inorganic Chemistry --
Parameter Results(mg/1) Parameter Results(mg/1) (mg/kg) Organic Compounds Results(mg/1)
P&T:G<::/MS Arsenic benzene -Z Acid:B/N Ext. ----Barium carbon tetrachloride ----MTBE Cadmium chlordane ------Chloride chlorobenzene ------Chromium chloroform --------__ Copper o-cresol --Fluoride m-cresol ----= p-cresol --Iron --Lead cresol ------
--__ Manganese --1,4-dichlorobenzene
--__ Mercury 1,2-dichloroethane
--Nitrate = 1,1-dichloroethylene --Selenium 2,4-dinitrotoluene --= heptachlor Silver --Radiochemistry Sulfates hexachlorobenzenc ----······-··--· Zinc hexachlorobutadienc ----Parameter Results (PCl/1) _pH hexachloroethane
__ Gross Alpha __ Conductivity = methyl ethyl ketone
Gross Beta TDS nitrobenzenc ----= pentachlorophenol TOC ----__ pyridine
Microbiology --__ tetrachlorocthylcnc
--__ trichloroethylenc
Parameter Results (Col/100ml) __ 2,4,5-trichlorophcnol --
----__ 2,4,6-trichlorophcnol
---__ vinyl chloride
cndrin --lindane --Date Received Reported by __ methoxychlor
__ toxaphene
Date Extracted Date Reported 2,4-D --2,4,5-TP (Silvex) --Date Analy,.ed Lab Number --l>I IS 3191 (Revised 2/91)
I-CHEM CERTIFICATE OF ANALYSIS
CONTROL NO. 0 0 1O80
This is your Certificate of Analysis for I-Cl-I EM SUPERFUND-ANALYZED™ Product which has hee n prepared in accordance
ith /-CI-IEM Pe,formace-Based Specifications. This product meets or exceeds all analyte specifications estahlished in rhe U.S.
cPA "Specifications and Guidance for Obtaining Contaminant-Free Sample Containers" for use in S11f1e1f11nd and other ha:ardous
waste programs. Please refer to the case label/or information about the recommended application of this product.
Glass Sample Containers
for use in the analysis of Semi-Volatiles, Pesticides, and PCBs
Compound Quantitation Limit(ug/L) Compound Quantitation Limit(ug/L)
Acenaphthene <5 Acenaphthylene <5
Bcnzo(a)anthracene <5 Benzo(a)pyrene <5
Benzo(k)fluoranthene <5 Benzo(g.h,i)perylene <5
Benzyl Alcohol <5 4-Bromophenyl-phenylether <5
4-Chloroaniline <5 4-Chloro-3-methylphenol <5
bis-( 2-Ch loroethy I )ether <5 bis-(2-Chloroisopropyl)ether <5
2-Chlorophenol <5 4-Chlorophenyl-phenylether <5
Di-n-butylphthalate <5 Di-n-octylphthalate <5
Dibenzofuran <5 1,2-Dichlorobenzene <5
1,3-Dichlorobenzene <5 3,3'-Dichlorobenzidine <5
Diethylphthalate <5 Dimethylphthalate <5
4.6-Dinitro-2-methylphenol < 20 2.4-Dinitrophenol < 20
2,6-Dinitrotoluene <5 bis-(2-Ethylhexyl)phthalate <5
Fluorene <5 Hexachlorobenzene <5
Hexachlorocyclopentadiene <5 Hexachloroethane <5
Isophorone <5 2-Methy !naphthalene <5
4-Methylphenol <5 2-Nitroaniline < 20
4-Nitroaniline <20 N-Nitroso-di-n-propylamine <5
N-Nitrosodiphenylamine <5 Naphthalene <5
2-Nitrophenol <5 4-Nitrophenol < 20
Phenanthrene <5 Phenol <5
1.2.4-Trichlorobenzene <5 2.4 .5-Trichlorophenol < 20
1.2-Diphenylhycirazine <5 Benzidine < 40
4'-DDD <0.02 Endosulfan II < 0.02
,,4'-DDE <0.02 Endosulfan Sulfate <0.02
4.4'-DDT <0.02 Endrin <0.02
Dieldrin <0.02 Endrin Aldehyde <0.02
Endosulfan I <0.01 Heptachlor <0.01
Methoxychlor <0.10 Endrin Ketone <0.02
Gamma-Chlordane <0.01 Toxaphene < 1.0
Aroclor-1221 <0.02 Aroclor-1232 <0.40
Aroclor-1248 <0.20 Aroclor-1254 < 0.20
Aroclor-1262 <0.20 Aroclor-1268 < 0.20
Pf eas~ ~eep t~1is certifi:cat~ for y~ur records and to facilitate any necessary correspondence.
add1t1onal 111formaflon 1s required, contact our Technical Service Department at
1800) 443-1689 or [phone] inside California.
Ra
Corporate Quality Assurance Manager @ printed on recycled paper
Compound Quantitation Limit(ug/L)
Anthracene <5
Benzo(b )fluoranthene <5
Benzoic Acid < 20
Butylbenzylphthalate <5
bis-(2-Chloroethoxy)methane < 5
2-Chloronaphthalene <5
Chrysene <5
Dibenzo(a.h)anthracene <5
1.4-Dichlorobenzene <5
2,4-dichlorophenol <5
2.4-Dimethylphenol <5
2,4-Dinilroroluenc <5
Fluoranthene <5
Hexachlorobutadiene <5
lndeno( 1,2.3-cd)pyrene <5
2-Methylphenol <5
3-Nitroaniline < 20
N-Nitrosodimethylamine <5
Nitrobenzene <5
Pentachlorophenol < 20
Pyrene <5
2.4.6-Trichlorophenol <5
Aldrin < 0.01
Alpha-BHC <0.01
Beta-BHC <0.01
Delta-BIIC <0.01
Gamma-BHC < 0.01
Heptachlor Epoxide <0.01
Alpha-Chlordane <0.01
Aroclor-101 6 < 0.20
Aroclor-1242 <0.20
Aroclor-1260 < 0.20
:METALS -WATER
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Sample Condition: Well/Stream/Pond/etc.
Substance: Ground Water/Surface Water
Analysis Requested: Metals
Containers:
Preservative:
Sample Labels:
Analysis Forms:
One (1) I -liter plastic jar
Cool to 4° C
If samplers have access to chemical preservatives, ground water
samples for metals should be preserved with 1: 1 HN03, so the pH< 2.
Procedure: Add 5 ml of 1: 1 HN03 to the sample; replace sample
container top snugly; shake container to mix the water and acid;
remove sample container lid and pour a small amount of sample over
litmus paper; if pH> 2, add HN03 in 2 ml increments while checking
pH; if pH< 2, close container, and prepare the sample for transport to
the lab.
Attach an inorganic sample label with a unique identification number to
the plastic jar.
Note: If a sample for non-hazardous inorganic constituents
(i.e., sulfate, chloride, etc.) is collected at the same
sample point, the same inorganic sample ID # can be
used to identify the plastic jar for metals and the plastic
cubitainer for the non-hazardous inorganics. The
inorganic sample ID # from the printed label should be
written on the seam side of the cubitainer with a
permanent marker.
Check (.I) the appropriate spaces for sample type and requested
analyses as shown on the attached form(s).
Note: If a sample for non-hazardous inorganics is collected at
the same sampling point, one analysis request sheet can
be used for analyses of metals and non-hazardous
inorganic constituents.
Chain-of-Custody: List all inorganic sample(s) (by sample ID# printed on the label) on
the Chain-of-Custody form(s) that go to the inorganic chemistry
laboratory.
N.C. Ocpartment or Environment,
I kahh, & Natural Resources
Solid Waste Management Division
SAMPLE ANALYSIS REQUEST State Laboratory or Public Health
P.O . Box 28047, 306 N. Wilmington Street
Raleigh, North Carolina 27611
G ile Number ---------------Field Sample Number _______________ _
Name of Sile ---------------Site Location -------------------
Collected By ----------ID# Date Collected Time --------------------
Agency: Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Gheck. e;-l-her c, Jo~ ('2-') Inorganic Compounds Results (mg/I)
Environmental Concentrate Comments Arsenic --
✓ Ground water (1)
Barium --Solid (5) Cadmium --
✓ Surface water (2)
Chromium --_ Liquid (6) Lead --Mercury
_ Soil (3) Sludge (7) --Selenium --Silver --_ Other (4) Other (8) ------Organic Chemistry Inorganic Chemistry --
Parameter Results (mg/I) Parameter Results (mg/I) (mg/kg) Organic Compounds Results(mg/1)
_P&T:GC/MS f Arsenic benzene --
(~ _ Acid:B/N Ext. Barium carbon tetrachloride --MTBE _L Cadmium chlordane ----Chloride chlorobenzene --l Chromium --
--chloroform --
--v Copper o-cresol --Fluoride m-cresol ----"?""Iron --p-cresol
--{ Lead cresol --
--4 Manganese --1,4-dichlorobenzene
--...i.:_ Mercury 1,2-dichloroethane
--Nitrate = 1,1-dichloroethylene
✓ Selenium 2,4-dinitrotoluene
JZ:silver = heptachlor
Radiochemistry Sulfates hexachlorobenzene ----······-··--·-£Zinc hexachlorobutadiene --Parameter Results (PCl/1) _pH hexachloroethane
__ Gross Alpha __ Conductivity = methyl ethyl ketone
Gross Beta TDS nitrobenzcne ----= pentachlorophenol TOC ----__ pyridine
M~crobiology --__ tetrachloroethylcnc
--__ trichlorocthylenc
Parameter Results (Col/lOOml) __ 2,4,5-trichlorophcnol ------2,4,6-trichlorophenol
----= vinyl chloride
cndrin --lindane --Dale Received Reported by __ methoxychlor
__ toxaphene
Date Exlradc<l Date Reported 2,4-0 = 2,4,5-TP (Silvex)
0J1c An aly,cd Lab Number --l>IIS 31'JI <Hevised 2/91)
I-CHEM CERTIFICATE OF ANALYSIS
CONTROL NO.001080
This is your Certificate of Analysis for I-CHEM SUPERFUND-ANALYZED1M Product which has been prepared in accordance
8,11 I-CHEM Pe,formace-Based Specificarions. This product meets or exceeds all analyte specifications established in the U.S.
~ A "Specifications and Guidance for Obtaining Co11ta111inant-Free Sample Contai11ers" for use in Supe,fund and other ha:ardous
waste programs. Please refer to the case label for information about the recommended application of this product.
Glass and Plastic Sample Containers
for use in the analysis of Metals and Cyanides
Analy1e Detection Limil(ug/L) Analyte Qetection Limit(ug/L)
Aluminum < 80 Coball < JO
Anrimony <5 Copper <10
Arse nic <2 Iron < 50
Barium < 20 Lead <2
Barium (Amber HOPE) < 50 Magnesium < 100
Beryllium < 0.5 Manganese <10
Cadmium <I Mercury <0.2
Calcium < 500 Nickel < 20
Calcium (HOPE) < 100 Potas~ium < 750
Chromium <10 Potassium (HOPE) < 100
0 /ease keep rhis certificate for your records and 10 facilitate any necessary correspondence.
·additional information is required, contact our Technical Sen ·ice Department at
[phone] or [phone] inside Califomiu.
R I
Co,porate Quality Assurance Manager @ printed on recycled paper
Analytc Retec1ion Limil(ug/L)
Selenium <2
Silver <5
Sodium <5000
Sodium (HOPE) < 100
Thallium <5
Vanadium <10
Zinc <10
Zinc (Amber HOPE) < 500
Cyanide < 10
NON-HAZARDOUS INORGANICS -WATER
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Sample Condition: Well/Stream/Pond/etc.
Substance: Ground Water/Surface Water
Analysis Requested: Non-hazardous Inorganic Constituents
Containers:
Preservative:
Sample Labels:
Analysis Forms:
One (I) I -liter plastic cubitainer
Cool to 4° C
Attach an inorganic sample label with a unique identification number to
the plastic cubitainer.
If a water sample for metals is collected at the same
sample point, the same inorganic sample ID # can be
used to identify the plastic jar for metals and the plastic
cubitainer for the non-hazardous inorganics; attach the
label to either container and write (with permanent
marker) the inorganic sample ID # from the printed label
on other container.
Check (.I) the appropriate spaces for sample type and requested
analyses as shown on the attached form(s).
Note: If a water sample for metals is collected at the same
sampling point, one analysis request sheet can be used
for analyses of metals and non-hazardous inorganic
constituents.
Chain-of-Custody: List all inorganic sample(s) (by sample ID # printed on the label) on
the Chain-of-Custody form(s) that go to the inorganic chemistry
laboratory.
N.C Dcpanmcnt or Environment,
I kallh, & Natural Resources
Solid Waste Management Division
u.se (1J l -L.ikr 'Pia.she. c.LA.bH·-o.iri e"
SAMPLE ANALYSIS REQUEST State Laboratory or Public Health
P.O. Box 28047, 306 N. Wilming1on Street
Raleigh, North Carolina 27611
ile Number ---------------Field Sample Number ----------------
Name of Sile ---------------Sile Location -------------------
Collected By _________ _ ID# Date Collected Time --------------------
Agency: Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type tt1 at i rPvte, Cr ) er (i.) Inorganic Compounds Results (mg/I)
Environmental Concentrate Comments Arsenic --
✓ Ground water (1)
Barium --Cadmium _ Solid (5) --
✓ Surface water (2)
Chromium --_ Liquid (6) Lead --Mercury
_ Soil (3) Sludge (7) --Selenium --Silver --_ Other (4) _ Other (8) ------Organic Chemistry Inorganic Chemistry --
Parameter Results (mg/I) Parameter Results(mg/1) (mg/kg) Organic Compounds Results (mg/I)
_P&T:GC/MS Arsenic benzene ----
-Acid:B/N Ext. Barium carbon tetrachloride ----MTBE Cadmium chlordane ---V Chloride ----chlorobenzene --Chromium chloroform ------
--Copper o-cresol
7 Fluoride --m-cresol ----= p-cresol --Iron --Lead cresol --------__ Manganese --1,4-dichlorobenzene
--Mercury 1,2-dichloroethane --,I-. = 1,1-dichloroethylene --y Nitrate
Selenium 2,4-dinitrotoluene --= heptachlor Silver --Radiochemistry L Sulfates hexachlorobenzene --······-··--· Zinc hexachlorobutadiene --Parameter Results (PCl/1) "; pH hexachloroethane
__ Gross Alpha V Conductivity = methyl ethyl ketone
Gross Beta ' TDS nitrobenzene --_x_ = pentachlorophenol TOC ----__ pyridine
Microbiology --__ tetrachlorocthylene
--__ trichloroethylene
Parameter Results (Col/100ml) --__ 2,4,5-trichlorophenol
----__ 2,4,6-trichlorophenol
---__ vinyl chloride
cndrin --lindane --Date Received Reported by __ methoxychlor
__ toxaphenc
Date Exlradc<l Date Reported 2,4-D --
--2,4,5-TP (Silvex)
Oatc Analyzed Lab Number --llll'-11'11 (llrv;<r<i ,tun
I•
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voes -LIQUID
.\
Sample Condition: Spills/Residues/Concentrates/etc.
Substance: Liquid
Analysis Requested: Volatile organic compounds (VOCs)
Containers:
Preservative:
Sample Labels:
Analysis Forms:
One (1) 125 ml glass jar for use in the analysis of voes
Cool to 4° C
Attach an organic sample label with a unique identification number to
the glass jar.
Note: If a semi-volatile liquid sample is collected at the same
sample point, the same organic sample ID # can be used
to identify the VOC jar and the semi-volatile jar. Attach
the label to one of the jars and write the ID # printed on
the label on the other jar with a permanent marker.
Check (,/) the appropriate spaces for sample type and requested
analyses as shown on the attached form(s).
Note: If a semi-volatile liquid sample is collected at the same
sampling point, one analysis request sheet can be used
for analyses of both volatile and semi-volatile
compounds.
Chain-of-Custody: List all organic sample(s) (by sample ID # printed on the label) on the
Chain-of-Custody form(s) that go to the organic chemistry laboratory.
v1.~e ( 1) 12.~ ~l 6-!As~ O-o.;-tor us~ ln -1-h! o.naly~1 s e>f \/Cls
KC Ocpartment or Environment, SAMPLE ANALYSIS REQUEST State Laboratory or Public Health
I lcallh, & Natural Resources P.O. Box 28047, 306 N. Wilmington Street
Solid Waste Management Division Raleigh, North Carolina 27611
,ile Number ---------------Field Sample Number _______________ _
Name of Site ---------------Site Location ·-------------------
Collected By _________ _ ID# Date Collected Time --------------------
Agency: Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Checl c~) Inorganic Compounds Results (mg/I)
Environmental Concentrate Comments Arsenic --Barium --__ Groundwater (1) _ Solid (5) Cadmium --..L Liquid ( 6)
Chromium --__ Surface water (2) Lead --Mercury
_Soil (3) Sludge (7) --Selenium --Silver --_ Other (4) Other (8) ------Organic Chemistry Inorganic Chemistry --
Parameter Results(mg/1) Parameter Results(mg/1) (mg/kg) Organic Compounds Results(mg/1) ~ P&T:GC/MS Arsenic benzene ----Acid:B/N Ext. Barium carbon tetrachloride ----MTBE Cadmium chlordane ------Chloride chlorobenzene ------Chromium chloroform ------
--__ Copper o-cresol --Fluoride m-cresol ----= p-cresol --Iron --Lead cresol --------__ Manganese --1,4-dichlorobenzene
--__ Mercury 1,2-dichloroethane
--Nitrate = 1,1-dichloroethylcnc --Selenium 2,4-dinitrotoluene --= heptachlor Silver --Radiochemistry Sulfates hexachlorobenzcnc ----······-··--· Zinc hcxachlorobutadienc ----Parameter Results (PCl/1) _pH hexachloroethanc
__ Gross Alpha __ Conductivity = methyl ethyl ketone
Gross Beta TDS nitrobenzenc ------pentachlorophcnol TOC --
--__ pyridine
M~crobiology --__ tetrachlorocthylcnc
--__ trichloroethylenc
Parameter Results (Col/100ml) __ 2,4,5-trichlorophenol ------2,4,6-trichlorophenol
----= vinyl chloride
cndrin --._,, lindane
Date Received Reported by = methoxychlor
__ toxaphene
Date Extracted Date Reported 2,4-D --_ 2,4,5-TP (Silvex)
Oalc Analy1:cd Lab Number --DIIS 3191 (Revised 2/91)
I-CHEM CERTIFJCATE OF ANALYSIS
CONTROL NO.001080
~,,is is your Certificate of Analysis for I-CHEM SUPERFUND-ANALYZEDTM Product ·which has heen prepared in accNdance
ith I-CHEM Pe,formace-Based Specifications. This product meets or exceeds all analyte specifications estahlished in the U.S .
,.;,P II "Specifications and Guidance/or OhtaininR Contaminant-Free Sample Containers" for use in S11pffji111d and 01her hazardous
waste proRrams. Please refer to the case label for information about the recommended application of this product.
Compound
Acetone
2,2-Dichloropropane
Bromodichloromethane
cis-1,3-Dichloropropene
2-Butanone
Hexachlorobutadiene
n-Butylbenzene
Ouantitation Limit(ug/L)
<5
p-I sopropy Ito! uene
Chlorobenzene
Naphthalene
Chloromethane
I, 1,2,2-Tetrachloroethane
Dibromochloromethane
1,2,3-Trichlorobenzene
1,4-Dichlorobenzene
I , I, I-Trichloroethane
Dich lo rod i fl uoromethane
1,2,3-Trichloropropane
trans-1,2-Dichloroethene
Vinyl Acetate
Xylene (total)
Vinyl Chloride
< I
< I
< I
<5
< I
< I
< I
< I
< I
< I
< I
< I
< I
< I
< I
< I
< I
< I
<5
< I
< I
Glass Sample Containers
for use in the analysis of Volatile Organics
Compound Ouantitation Limit(ug/L)
1,3-Dichloropropane < I
Bromobenzene < I
trans-1,3-Dichloropropene < I
Bromomethane < I
Ethylbenzene < I
sec-Butylbenzene < I
Isopropylbenzene < I
Carbon Tetrachloride < I
Methylene Chloride < 5
Chloroform < I
Styrene < I
1,2-Dibromo-3-chloropropane < I
Toluene < I
Dibromomethane
1, I ,2-Trichloroethane
1,2-Dichlorobenzene
Trichlorofluoromethane
1, 1-Dichloroethane
I J,5-Trimethylhenzene
1,1-Dichloroethene
1,2,4-Trimethylhenzene
cis-1,2-Dichloroethene
< I
< I
< I
< I
< I
< I
<I
< I
<I
Please keep this certificate for your records and to facilitate any necessary correspondence.
If additional information is required, contact our Technical Service Department at
[phone] or [phone] inside California.
R 1
Corporate Quality Assurance Manager @ pn·nted on recycled paper
Compound
Benzene
1,2-Dichloropropane
Bromoform
I, 1-Dichloropropene
tert-Butylbenzene
2-Hexanone
Carbon Disulfide
4-Methyl-2-pentanone
Chloroethanc
n-Propylbenzcne
2 & 4 Chlorotoluene
Tetrachloroethene
Ouantitation Limit(ug/L)
< I
< I
< I
<1
<I
<5
<I
<5
<I
< I
< I
< I
1,2-Dibromocthane (EDB) < I
1.2,4-Trichlorohenzene < I
1,3-Dichlorobenzene <I
Trichlorocthene <1
1,2-Dichloroethane <1
I'
SVOCs -LIQUID
I . ' I
I
I
Sample Condition: Spills/Residues/Concentrates/etc.
Substance: Liquid
Analysis Requested: Semi-volatile organic compounds
Containers:
Preservative:
Sample Labels:
Analysis Forms:
One (1) 125 ml glass jar for use in the analysis of SVOCs
Cool to 4° C
Attach an organic sample label with a unique identification number to
the jar.
Note: If a VOC liquid sample is collected at the same sample
point, the same organic sample ID # can be used to
identify the semi-volatile jar and the VOC jar. Attach
the label to one of the jars and write the ID # from the
printed label on the other jar with permanenet marker.
Check (.I) the appropriate spaces for sample type and requested
analyses as shown on the attached form(s).
Note: If a VOC liquid sample is collected at the same sampling
point, one analysis request sheet can be used for analyses
of both volatile and semi-volatile compounds.
Chain-of-Custody: List all organic sample(s) (by sample ID # printed on the label) on the
Chain-of-Custody form(s) that go to the organic chemistry laboratory.
N.C. Ocpartmcnl of Environment,
I lcalth, & Natural Resources
Solid Waste Management Division
SAMPLE ANALYSIS REQUEST Stale Laboratory of Public Healt h
P.O. Box 28047, 306 N. Wilmington Street
Raleigh , North urolina 27611
,le Number ---------------Field Sample Number _______________ _
Name of Site ---------------Site Location -------------------
Collected By _________ _ ID# ____ Dale Collected __________ Time _____ _
Agency: Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Cnecl (Cc) Inorganic Compounds Results(mg/1)
Environmental Concentrate Comments Arsenic --Barium --__ Ground water (1) _ Solid (5) Cadmium --
/ Chromium
\'/ Liquid ( 6) --__ Surface water (2) Lead --Mercury
_ Soil (3) _ Sludge (7) --Selenium --Silver --_ Other (4) _ Other (8) ------Organic Chemistry Inorganic Chemistry --
Parameter Result.s(mg/1) Parameter Results(mg/1) (mg/kg) Organic Compounds Results(mg/1)
P&T:GC/MS Arsenic benzene -----L Acid:B/N Ext. Barium carbon tetrachloride ----MTBE Cadmium chlordane ------Chloride chlorobenzene ------Chromium chloroform ------
--__ Copper o-cresol --Fluoride m-cresol --------Iron __ p-cresol --Lead cresol ------
--__ Manganese 1,4-dichlorobenzene ----__ Mercury 1,2-dichloroethane
--Nitrate = 1,1-dichloroelhylene --Selenium 2,4-dinitrotoluene --= heptachlor Silver --Radiochemistry Sulfates hexachlorobenzene ----······-··--·-Zinc hexachlorobutadiene ----Results (PCl/1) Parameter _pH hexachloroethane
__ Gross Alpha __ Conductivity = methyl ethyl ketone
Gross Beta TDS nitrobenzene ----= pentachlorophenol TOC --
--__ pyridine
Microbiology --__ tetrachlorocthylcnc
--__ trichloroethylenc
Parameter Results (Col/lOOml) __ 2,4,5-trichlorophenol --
----2,4,6-trichlorophenol
---= vinyl chloride
endrin --lindane --Date Received Reported by __ methoxychlor
__ toxaphene
Date Extracted Date Reported 2,4-D --_ 2,4,5-TP (Silvex)
Date Analyzed Lab Number --I >I IS 31 91 (Revised 2/91)
I-CHEM CERTIFICATE OF ANALYSIS ----------------------------------------·--·--·--·--
CONTROL NO.0010 8 0
This is your Certificate of Analysis for I-CHEM SUPERFUND-ANALYZEDrM Product H-l1ich has h('{'n prepared in accordanrc
th I-CHEM Pe,formace-Based Specifications. This product meets or exceeds all analyte specifications estahlishcd in the U.S.
PA "Specifications and Guidance for Obtaining Contaminant-Free Sample Containers .. for use in S11pc1f1111d and other ha:ardous
irnste programs. Please refer to the case label for information about the recommended application of this product.
Glass Sample Containers
for use in the analysis of Semi-Volatiles, Pesticides, and PCBs
Compound Quantitation Limit(ug/L) Compound Quantitation Limit(ug/L)
Acenaphthene <5 Acenaphthylene <5
Bem:o(a)anthracene <5 Benzo(a)pyrene <5
Benzo(k)fluoranthene <5 Benzo(g,h,i)perylene <5
Benzyl Alcohol <5 4-Bromophenyl-phenylether <5
4-Chloroaniline <5 4-Chloro-3-methylphenol <5
bis-(2-Chloroethyl)ether <5 bis-(2-Chloroisopropyl)ether <5
2-Chlorophenol <5 4-Chlorophenyl-phenylether <5
Di-n-butylphthalate <5 Di-n-octylphthalate <5
Dibenzofuran <5 1,2-Dichlorobenzene <5
1,3-Dichlorobenzene <5 3,3'-Dichlorobenzidine <5
Diethylphthalate <5 Dimethylphthalate <5
4,6-Dinitro-2-methylphenol < 20 2,4-Dinitrophenol < 20
2,6-Dinitrotoluene <5 bis-(2-EthylhexylJphthalate <5
Fluorene <5 Hexachlorobenzene <5
Hexachlorocyclopentadiene <5 Hexachloroethane <5
lsophorone <5 2-Methylnaphthalene <5
4-Methylphenol <5 2-Nitroaniline < 20
4-Nitroaniline < 20 N-Nitroso-di-n-propylamine <5
N-Nitrosodiphenylamine <5 Naphthalene <5
2-Nitrophenol <5 4-Nitrophenol < 20
Phenanthrene <5 Phenol <5
1,2.4-Trichlorobenzene <5 2,4,5-Trichlorophenol < 20
I .2-Diphcnylhydrazine <5 Benzidine <40
t'-DDD <0.02 Endosulfan II < 0.02
4'-DDE < 0.02 Endosulfan Sulfate < 0.02
➔,4'-DDT <0.02 Endrin < 0.02
Dieldrin < 0.02 Endrin Aldehyde < 0.02
Endosulfan I <0.01 Heptachlor <0.01
Methoxychlor <0.10 Endrin Ketone <0.02
Gamma-Chlordane < 0.01 Toxaphene < 1.0
Aroclor-1221 <0.02 Aroclor-1232 < 0.40
Aroclor-1248 <0.20 Aroclor-1254 < 0.20
Aroclor-1262 <0.20 Aroclor-1268 < 0.20
P!eas~ ~eep t~1is certifi_cat~ for y~ur records and to facilitate any necessary correspondence.
add1ttonal 111format10n ts required, contact our Technical Service Department at
/00) 443-1689 or [phone] inside California.
~.~~
Corporate Quality Assurance Manager @ printed on recycled paper
Compound Quantitation Limit(ug/L)
Anthracene <5
Benzo(b )fluoranthene <5
Benzoic Acid < 20
Butylbenzylphthalate <5
bis-(2-Chloroethoxy)methane < 5
2-Chloronaphthalene <5
Chrysene <5
Dibenzo(a.h)anthracene <5
I .4-Dichlorobenzene <5
2,4-dichlorophenol <5
2.4-Dimethylphenol <5
2,4-Dinitrotoluene <5
Fluoranthene <5
Hexachlorobutadiene <5
lndeno( 1.2,3-cd)pyrene <5
2-Methylphenol <5
3-N itroani line < 20
N-Nitrosodimethylamine <5
Nitrobenzene <5
Pentachlorophenol < 20
Pyrene <5
2.4,6-Trichlurophenol <5
Aldrin <0.01
Alpha-BHC < 0.01
Beta-BHC <0.01
Delta-BHC < 0.01
Gamma-BHC <0.01
Heptachlor Epoxide <0.01
Alpha-Chlordane < 0.01
Aroclor-1016 <0.20
Aroclor-1242 < 0.20
Aroclor-1260 < 0.20
METALS-LIQUID
,I
Sample Condition: Spills/Residues/etc.
Substance: Liquid
Analysis Requested: Metals
Containers: One (1) 125 ml glass jar for use in the analysis of metals
Preservative: Cool to 4 ° C
Sample Labels: Attach an inorganic sample label with a unique identification number to
the glass jar.
Analysis Forms: Check (,/) the appropriate spaces for sample type and requested
analyses as shown on the attached form(s).
Chain-of-Custody: List all inorganic sample(s) (by sample ID # printed on the label) on
the Chain-of-Custody form(s) that go to the inorganic chemistry
laboratory.
Note: All inorganic samples (water, soil , sludge, liquid, etc.)
can be listed on the same Chain-of-Custody form(s).
Llt'>~ (t) !25 ml Grla$S J'o.r-for-u~e iV1 ¼e a.nD-lysis ~r-me-b.:s
N.C. Department of Environment, SAMPLE ANALYSIS REQUEST State Laboratory of Public Health
llcalth, & Natural Resources P.O. Box 28047, 306 N. Wilmington Street
Solid Waste Management Division Raleigh, North Carolina 27611
1le Number ---------------Field Sample Number _______________ _
Name of Site ---------------Site Location -------------------
Collected By ----------ID# Dale Collected Time --------------------
Agency: Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Chee.IL. Crc J Inorganic Compounds Results(mg/1)
Environmental Concentrate Comments Arsenic --Barium --__ Groundwater (1) _ Solid (5) Cadmium --
\,/ Liquid (6)
Chromium --__ Surface water (2) Lead --Mercury
_ Soil (3) _ Sludge (7) --Selenium --Silver --_ Other (4) _ Other (8) ------Organic Chemistry Inorganic Chemistry --
Parameter Results (mg/I) Parameter ~sults(mg/1) (mg/kg) Organic Compounds Results(mg/1)
P&T:GC/MS L Arsenic benzene ---_ Acid:B/N Ext. _L Barium carbon tetrachloride --MTBE _ _L Cadmium chlordane ---Chloride chlorobenzene ----L Chromium --chloroform --
--__ Copper o-cresol --Fluoride m-cresol ----= p-cresol --Iron --
--_LLead cresol ----Manganese --1,4-dichlorobenzene
--7 Mercury 1,2-dichloroethane
--Nitrate = 1,1-dichloroethylene 7 Selenium 2,4-dinitrotoluene
_L Silver = heptachlor
Radiochemistry Sulfates hexachlorobenzene ----······-··--· Zinc hexachlorobutadiene
Parameter Results (PCl/1) LPH --hexachloroethane
__ Gross Alpha __ Conductivity = methyl ethyl ketone
Gross Beta TDS nitrobenzene ----= pentachlorophenol TOC ----__ pyridine
Mkrobiology --__ tetrachloroethylene
--__ trichloroethylenc
Parameter Results (Col/100ml) __ 2,4,5-trichlorophenol --
----__ 2,4,6-trichlorophenol
---__ vinyl chloride
endrin --lindane --Dale Received Reported by __ methoxychlor
__ toxaphene
Dale Extradcd Date Reported 2,4-D --
--2,4,5-TP (Silvex)
Oat c Analyl'.cd Lab Number --l>IIS 3191 (Revised 2/91)
I-CHEM CERTIFICATE OF ANALYSIS
CONTROL NO.001080
This is your Certificate of Analysis for /-CHEM SUPERFUND-ANALYZED™ Product which has been prepared in accordance
h I-CHEM Pe,formace-Based Specificatiofls. This product meets or exceeds all analyte specifications established in the U.S.
• > A "Specifications a1Zd Guidance for Obtaining Contaminant-Free Sample Containers" for use in Superfw1d and other hazardous
waste programs. Please refer to the case label for information about the recommended application of this product.
Analyte
Aluminum
Antimony
Detection Limit(ug/L)
< 80
Arsenic
Barium
Barium (Amber HOPE)
Beryllium
Cadmium
Calcium
Calcium (HOPE)
Chromium
<5
<2
< 20
< 50
<0.5
< I
< 500
< 100
<10
Glass and Plastic Sample Containers
for use in the analysis of Metals and Cyanides
A.D.&m
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Potassium (HOPE)
Detection Limit(ug/L}
< IO
<10
< 50
<2
< 100
< IO
<0.2
< 20
< 750
< 100
'lease keep this certificate for your records and to facilitate any necessary correspondence.
additio11a/ information is required, contuct our Tech11ical Service Departme11t at
,800) 443-1689 or [phone] i11side California.
R I
Co,porate Quality Assura11ce Ma11ager @ printed on recycled paper
A.D.&m
Selenium
Silver
Sodium
Sodium (HOPE)
Thallium
Vanadium
Zinc
Zinc (Amber HOPE)
Cyanide
Detection Limit(ug/L)
<2
<5
<5000
< 100
<5
<10
<10
< 500
< IO
I'
TCLP (VOCs/SVOCs) -SOIL/SLUDGE I
I "
JI 1· 'i • t
t.
t
~ 1.', I•
t
•. ,.
; ,
-. I
J -. ,J I, • • I: 1. ' I
i .
. l ) .
'
; 1 • . , I
. l•
i I
I, ' ·1 {,
. I -
(
• . . ' ,:• '. i i·
I ' I 1<
I•
., 'I I l
'I t. •. j .,;
,· ',\ '' I ! ' +, j
j-" ,!-,ii
' 11
' 1·
,) I •. . ' 1 • ··<ii i ' 'I I ·t·
I· . / i; ' 1 . 'i Jf I I ,I
I 'I
Sample Condition: Sediment/Waste Residues/etc.
Substance: Soil/Solid/Sludge/Other
Analysis Requested: TCLP -Volatile (VOCs) and semi-volatile organic
compounds (SVOCs)
Containers:
Preservative:
Sample Labels:
Analysis Forms:
One (1) 125 ml glass jar for use in the analysis of VOCs
and
One (1) 125 ml glass jar for use in the analysis of SVOCs
Cool to 4° C
Attach an organic sample label with a unique identification number to
one of the glass jars and write the sample ID # from the printed label
onto the other glass jar with a permanent marker.
Check (,/) the appropriate spaces for sample type and requested
analyses as shown on the attached form(s).
Note: If only one soil/sludge sample is collected from a
sampling point (i.e., just for volatile analysis; or just for
semi-volatile analysis), then check (,/) the parameters
marked V for volatiles or S for semi-volatiles according
to the type of analysis requested.
Chain-of-Custody: List all organic sample(s) (by sample ID # printed on the label) on the
Chain-of-Custody form(s) that go to the organic chemistry laboratory.
Note: All organic samples (water, soil, sludge, etc.) can be
listed on the same Chain-of-Custody form(s).
;e llJ l'2.~ .r,\ C,-la<.s ~w .fei( Wtt-{)(lo.i'{5($~f V()C,, t C1)1z_c;,....,\ Gi~.SS~llY .for #it o.na.'.y s:«;i of 5\'u,·-s
N.C Ocpartment of Environment, SAMPLE ANALYSIS REQUEST State Laboratory of Public Health
I lcallh, & Natural Resources P.O. Box 28047, 306 N. Wilmington Stn:ct
Solid Waste Management Division Raleigh, Nonh Carolina 27611
.le Number ---------------Field Sample Number _______________ _
Name of Site ---------------Site Location -------------------
Collected By _________ _ ID# Date Collected Time --------------------
Agency: Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Chelt €~(( (3),(J.),(~\(1), ot(€) Inorganic Compounds Results (mg/I)
Environmental Concentrate Comments Arsenic --Barium
\/ Solid (5) --__ Groundwater (1) Cadmium --Chromium --__ Surface water (2) _ Liquid (6) Lead --
~ Soil (3) _L Sludge (7)
Mercury
--Selenium --Silver
~ Other (4) £ Other (8) --------Organic Chemistry Inorganic Chemistry
\J-::. \lo lt1.t\ le s $:: $Crn't· yd('!_ t i te .s
Parameter Results(mg/1) Parameter Rtsults(mg/l)(mg/kg) Organic Compounds Results(mg/1)
i:::._ P&T:GC/MS V Arsenic 1/ benzene V --~ Acid:B/N Ext. 5 Barium 7 carbon tetrachloride V --L chlordane MTBE Cadmium s ------Chloride ...i:::::_ chlorobenzene \l ----Chromium ...i:::._ chloroform v ----__ Copper L a.cresol s
--Fluoride _£ m-cresol <; --
--Iron L p-cresol -~ --
--Lead L cresol C: --
--__ Manganese .L.. 1,4-dichlorobenzene V
--__ Mercury y 1,2-dichloroethane V
--Nitrate 1/ 1,1-dichloroethylene \I --Selenium ✓ 2,4-dinitrotoluene s --Silver 7 heptachlor s --Radiochemistry Sulfates L hexachlorobenzene ~ --······-··--·-Zinc ..k::'.'._ hexachlorobutadiene $ --Parameter Results (PCl/1) _pH ...JC... hexachloroethanc ~
__ Gross Alpha __ Conductivity _.L methyl ethyl ketone Y.
Gross Beta TDS _L nitrobenzcnc s ----TOC L pentachlorophenol s --
--~ pyridine s
Microbiology --v telrachloroethylene V
--L trichloroethylene V
Parameter Results (Col/lOOml) L._ 2,4,S-trichlorophenol s ------.JL._ 2,4,6-trichlorophenol s.
---L vinyl chloride '1_
_L cndrin ~
_.t'.'._ lindane s
Date Received Reported by L methoxychlor s L toxaphene s
Date Extracted Dale Reported L2,4-D s L 2,4,5-TP (Silvex) s
Dale Analy,.cd Lab Number --l>IIS 3191 (Revised 2/91)
1-CHEM
Glass Sample Containers
CERTIFICATE OF ANALYSIS
CONTROL NO.001080
for use in the analysis of Semi-Volatiles, Pesticides, and PCBs
_ompound Ouantitation Limit(ug/L)
<5 Acenaphthene
Benzo(a)anthracene
Benzo(k)fluoranthene
Bem.yl Alcohol
4-Chloroaniline
bis-(2-Chloroethyl)ether
2-Chlorophenol
Di-n-butylphthalate
Dibenzofuran
1,3-Dichlorobenzene
Diethylphthalate
4,6-Dinitro-2-methylphenol
2,6-Dinitrotoluene
Fluorene
Hexach lorocyclopentadiene
Isophorone
4-Methylphenol
4-Nitroaniline
N-Nitrosodiphenylamine
2-Nitrophenol
Phenanthrene
1,2,4-Trichlorobenzene
1,2-Diphenylhydrazine
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
1ethoxychlor
,amma-Chlordane
Aroclor-1221
Aroclor-1248
Aroclor-1262
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
< 20
<5
<5
<5
<5
<5
< 20
<5
<5
<5
<5
<5
<0.02
<0.02
<0.02
<0.02
<0.01
<0.10
<0.01
<0.02
< 0.20
< 0.20
Compound
Acetone
2,2-Dichloropropane
Bromodichloromethane
cis-1 J -Dichloropropene
2-Butanone
Ouantitation Limit(ug/L)
<5
< I
< 1
< I
<5
Hexachlorobutadiene < I
n-Butylbenzene < I
p-lsopropyltoluene < I
Chlorobenzene < I
Naphthalene < I
Chloromethane < I
I, 1,2,2-Tetrachloroethane < I
Dibromochloromethane < I
1.2,3-Trichlorobenzene < I
1,4-Dichlorobenzene < I
I, I, I -Trichloroethane < I
Dichlorodifluoromethane < I
1,2,3-Trichloropropane < I
trans-1,2-Dichloroethene < I
Vinyl Acetate < 5
Xylene (total) < I
Vinyl Chloride < I
Compound Ouantitation Limit(ug/L)
<5 Acenaphthylene
Benzo(a)pyrene
Benzo(g,h,i)perylene
4-Bromophenyl-phenylether
4-Chloro-3-methylphenol
bis-(2-Chloroisopropyl)ether
4-Chlorophenyl-phenylether
Di-n-octylphthalate
1,2-Dichlorobenzene
3,3'-Dichlorobenzidine
Dimethylphthalate
2,4-Dinitrophenol
bis-(2-Ethylhexyl)phthalate
Hexachlorobenzene
Hexachloroethane
2-Methylnaphthalene
2-Nitroaniline
N-Nitroso-di-n-propylamine
Naphthalene
4-Nitrophenol
Phenol
2.4,5-Trichlorophenol
Benzidine
Endosulfan II
Endosulfan Sulfate
Endrin
Endrin Aldehyde
Heptachlor
Endrin Ketone
Toxaphene
Aroclor-1232
Aroclor-1254
Aroclor-1268
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
< 20
<5
<5
<5
<5
< 20
<5
<5
<20
<5
< 20
< 40
<0.02
<0.02
< 0.02
<0.02
< 0.01
< 0.02
< 1.0
<0.40
<0.20
<0.20
Glass Sample Containers
for use in the analysis of Volatile Organics
Compound Ouantitation Limit(ug/L)
1,3-Dichloropropane < I
Bromobenzene < I
trans-1 ,3-Dichloropropene < I
Bromomethane < I
Ethylbenzene < I
sec-Butylbenzenc < 1
Isopropylbenzene < I
Carbon Tetrachloride < I
Methylene Chloride < 5
Chloroform < I
Styrene < I
1,2-Dibromo-3-chloropropane < I
Toluene < I
Dibromomethane < I
I, 1,2-Trichloroethane < I
1,2-Dichlorobenzene < I
Trichlorofluoromethane < I
I, 1-Dichloroethane < I
1,3,5-Trimethylbenzene < I
I, 1-Dichloroethene < I
1,2,4-Trimethylbenzene < I
cis-1,2-Dichloroethene < I
Please keep this certificate for your records and to facilitate any necessary correspondence.
If additional information is required, contact our Technical Service Department at
(800) 443-/689 or [phone] inside California.
Ra 1
C01porate Quality Assurance Manager
Compound Ouantitation Limit(ug/L)
Anthracene < 5
Benzo(h)fluoranthene < 5
Benzoic Acid < 20
Butylbenzylphthalate < 5
bis-(2-Chloroethoxy)methane < 5
2-Chloronaphthalene < 5
Chrysene < 5
Dibenzo(a.h)anthracene < 5
1.4-Dichlorobenzene < 5
2.4-dichlorophenol < 5
2,4-Dimethylphenol < 5
2,4-Dinitrotoluene < 5
Fluoranthene < 5
Hexachlorobutadiene < 5
lndeno(l .2,3-cd)pyrene < 5
2-Methylphenol < 5
3-Nitroaniline < 20
N-Nitrosodimethylamine < 5
Nitrobenzene < 5
Pentachlorophenol < 20
Pyrene < 5
2.4,6-Trichlorophenol < 5
Aldrin < 0.01
Alpha-BBC < 0.01
Beta-BBC < 0.01
Delta-BBC < 0.01
Gamma-BBC < 0.01
Beptachlor Epoxide < 0.01
Alpha-Chlordane < 0.0 I
Aroclor-1016 < 0.20
Aroclor-1242 < 0.20
Aroclor-1260 < 0.20
Compound
Benzene
1.2-Dichloropropane
Bromoform
I, 1-Dichloropropene
tert-Butylbenzene
2-Bexanone
Carbon Disulfide
4-Methyl-2-pcntanone
Chloroethane
Ouantitation Limit(ug/L)
<l
<l
< I
< I
< I
<5
< I
<5
<I
n-Propylbenzene < I
2 & 4 Chlorotoluene < I
Tetrachloroethene < I
1.2-Dibromoethane (EDB ) < I
1.2.4-Trichlorobenzene < I
1,3-Dichlorobenzene < I
Trichloroethene < I
1,2-Dichloroethane < I
TCLP (METALS) -SOIL/SLUDGE
,
(
'l L
~
1 l . ' . '
I -
I :
r
Sample Condition: Sediment/Waste Residues/etc.
Substance: Soil/Solid/Sludge/Other
Analysis Requested: TCLP -Metals
Containers: One (1) 125 ml glass jar for use in the analysis of metals
Preservative: Cool to 4 ° C
Sample Labels: Attach an inorganic sample label with a unique identification number to
the glass jar.
Analysis Forms: Check (.I) the appropriate spaces for sample type and requested
analyses as shown on the attached form(s).
Chain-of-Custody: List all inorganic sample(s) (by sample ID # printed on the label) on
the Chain-of-Custody form(s) that go to the inorganic chemistry
laboratory.
Note: All inorganic samples (water, soil, sludge, etc.) can be
listed on the same Chain-of-Custody form(s).
use (1) llf:i m\ er1a$S J'C,t ,,-tor use ir1 #?e o.rolysiJ o( rne-b(s-
K c. Ocpartmenl or Environment, SAMPLE ANALYSIS REQUEST State Laboratory or Public lleallh
I lcalth, & Natural Resources P.O. Box 28047, 306 N. Wilm ington Street
Solid Waste Management Division Raleigh, North Cuolina 27611
le Number ---------------Field Sample Number _______________ _
Name of Sile Site Location ----------------------------------
Collected By ----------ID# Date Collected Time --------------------
Agency: Hazardous Waste Solid Waste __ Supcrfund TCLP Compounds --
Sample Type l heik-t~er-6\L~\(_;)~·111 o, (<?) lnor:ganlc Compounrui Results (mg/I)
Environmental Concentrate Comments ✓ Arsenic
7 Barium
__ Ground water (1) JL._ Solid (5) 7cadmium
1/ Chromium
__ Surface water (2) Liquid (6) vtead
/
L Mercury
L Soil (3) _L_ Sludge (7) ..lL. Selenium
..!:... Silver
L Other (4) V' Other (8) ------Organic Chemistry Inorganic Chemistry --
Parameter Results(mg/1) Parameter Result, (mg/I) (mg/kg) Organic Compounds Results(mg/1)
_P&T:GC/MS .L Arsenic benzene --Acid:B/N Ext. , Barium carbon tetrachloride ----1::__ --
I MTBE _.L_ Cadmium chlordane --Chloride chlorobenzene ------..L Chromium chloroform ------__ Copper o-cresol --Fluoride m-cresol ----= p-cresol Iron -----r
--__1{_Lcad cresol --
--Manganese --1,4-dichlorobenzene
--V Mercury 1,2-dichloroethane
--Nitrate = 1,1-dichloroethylene
\/ Selenium 2,4-dinitrotoluene
_L Silver = heptachlor
Radiochemistry Sulfates hcxachlorobenzene ----······--·--·-Zinc hexachlorobutadiene ----Parameter Results (PCl/1) _pH hexachlorocthane
__ Gro5s Alpha __ Conductivity = methyl ethyl ketone
Gross Beta TDS nitrobenzcne ----= pentachlorophenol TOC ----__ pyridine
M~crobiology --__ tetrachlorocthylene
--__ trichloroethylene
Parameter Results (Col/lOOml) __ 2,4,5-trichlorophenol ------2, 4,6-t richlorophenol
----= vinyl chloride
endrin --lindane
Date Received Reported by = methoxychlor
__ toxaphene
Date Extracted Date Reported 2,4-D --_ 2,4,5-TP (Silvex)
Oatc Analy1ed Lab Number --l>IIS 3l'Jl (Revised 2/91)
I-CHEM CERTIFICATE OF ANALYSIS
CONTROL NO. 0 0 1 0 8 0
This is your Certificate of Analysis for I-CHEM SUPERFUND-ANALYZEDrn Product which has been prepared in accordance
ith I-CHEM Pe,formace-Based Specifications. This prod11ct meets or exceeds all analyte specifications established in the U.S .
. PA "Specifications and G11idancefor Obtaining Colllaminam-Free Sample Containers" for use in Superfund and other hazardo11s
waste programs. Please refer to the case label for illformatioll about the recommellded application of this product.
Analyte
Aluminum
Detection Limit(ug/L)
< 80
Antimony < 5
Arsenic < 2
Barium < 20
Barium (Amber HOPE) < 50
Beryllium < 0 .5
Cadmium < I
Calcium < 500
Calcium (HOPE) < JOO
Chromium < I 0
Glass and Plastic Sample Containers
for use in the analysis of Metals and Cyanides
Analyte
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Potassium (HOPE)
Detection Limit(ug/L)
<10
<10
< 50
<2
< 100
< 10
<0.2
< 20
< 750
< 100
Please keep this certificate for your records and to facilitate any necessary correspondence.
-additio11a/ i11formation is required, contact our Technical Sen•ice Departme11t at
1800) 443-1689 or [phone] inside California.
R l
Corporate Quality Assurance Manager @ printed on recycled paper
~
Selenium
Silver
Sodium
Sodium (HDPE)
Thallium
Vanadium
Zinc
Zinc (Amber HOPE)
Cyanide
Detection Limit(ug/L)
<2
<5
< 5000
< 100
<5
< JO
<10
< 500
<10
Attachment - B
EXAMPLE OF SLUDGE AND SURFACE WATER SAMPLING SCENERIOS
COMPLETE SLUDGE SAMPLE
VOLATILES ----·--·---~-s -/ -. ---
---82.,35 ------
125 ml gl~ss jar
for use in the
analysis of voes
_)
("
125 ml glass jar
for use in the
analysis of SVOCs
SOLID & HAZARDOUS IIASTE HCHT BRANCH -ORGANIC Sa■ole No: 008235 Si le No:Nll?C>OIC>()IOol 0;,te: lo/6/qo
Site Naw: Crtntralor w=;.
Si le Location: ~;~ O".J S-{
Collector: Snm P/tr Tlw: Q330
1437--
SEMI-VOLATILES
4 l
ORGANIC
L.fsted on the
chain-of-custody
for the organic
laboratory
INORGANIC
J
Listed on the
chain-of-custody
for the inorganic
laboratory
125 ml glass jar for use in
the analysis of metals
SOLID & IIAZAROOUS IIASTE HGHT BRANCH -INORGMHC
Sa■ole No: 009U7 Site No:Hr()('('IC'<'IC'<'I Date: 10/1S/'lr,
Site Na■e: ~11t'mlc f, /,1(. S-/
Si le Location: ,,:y,,le/ (,/v
.._ __ c_ol_l_ector: ,5am Pter Ti"": IJ830
KC. Department of Environment,
Health, & Natural Rewurcei;
Solid Waste Management Division
S~1PLE ANALYSIS REQUEST State Laboratory of Public Health
P.O. Box 28047, 306 N. Wilmington Street
Raleigh, North Carolina 27611
Site Number_......1..:N=C=D____;;~...;;O;..:./_~..;;....;../......;..()O..:;....;../ ____ _ Field Sample Number_---:::8...:;;2:a..3_5 __________ _
Name of Site C-,mera~r-I Inc .
Collected By ~ Pier
Site Location 1.,.U.,PfTO 1 / -. _\-1-.,,/ Ci'fy ---t------r------------
lD # _0_0 __ Date Collected ltJ/ I':, /9 0 Time 0830
Agency: V Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Inorganic Compounds Results (mg/I)
Environmental Concentrate Comments Arsenic --Barium
_Groundwater (1) Solid (5) S-J --Cadmium --Chromium --__ Surface water (2) Liquid (6) Lead --Mercury
_ Soil (3) V Sludge (7) --Selenium --Silver --_ Other (4) _ Other (8) --
--
--Organic Chemistry Inorganic Chemistry --
Parameter Results (mg/I) Parameter Results(mg/1) (mg/kg) Organic Compounds Results (mg/I)
v' Pt T:GC/MS Arsenic ./ benzene --.JC_ Acid:B /N Ext. Barium v carbon tetrachloride --..L.. chlordane MTBE Cadmium ----Chloride ~ chlorobenzene ----Chromium v-chloroform ----✓ o-cresol --__ Copper
Fluoride ...L m-cresol ----Iron 1_ p-cresol ----Lead v cresol ------__ Manganese v 1,4-dichlorobenzene
--__ Mercury v 1,2-dichloroethane
Nitrate L 1,1-dichloroethylene ----Selenium --v" 2,4-dinitrotoluene
✓ heptachlor Silver --Radiochemistry Sulfates L.... hexachlorobenzene --Zinc ..L.. hexachlorobutadiene --Parameter Results (PCi/1) _pH v" hexachloroethane
__ Gross Alpha __ Conductivity __!C_ methyl ethyl ketone
Gross Beta TDS V nitrobenzene ----..L. pentachlorophenol TOC --
--..1:::._ pyridine
Microbiology --L tetrachloroethylene
--L trichloroethylene
Parameter Results (Col/lOOml) v 2,4,5-trichlorophenol --
----v 2,4,6-trichlorophenol
----_L vinyl chloride
v endrin
v lindane
Date Received Reported by _L methoxychlor v toxaphene .
Date Extracted Date Reported ✓ 2,4-D
V 2,4,5-TP (Silvex)
Date Analyzed Lab Number --C:PDB9E
N.C. Department of Environment,
Health, & Natural Rcsourcei;
Solid Waste Management Division
SAMPLE ANALYSIS REQUEST State Laboratory of Public Health
P.O. Box 28047, 306 N. Wilmington Street
Raleigh, North Carolina 27611
Site Number NCO ~OJ ~OJ ()O I Field Sample Number Cfi/-37
Name of Site ~t:EY. Inc.. I Site Location W~' Qly
Collected By ~m Pter ID# OC> Date Collected t.~L,,;/q~ Time e:JlE3~ ,
Agency: V Hazardous Waste Solid Waste __ Superfund TCLP Compounds -- --
Sample Type Inorganic Compounds Results(mg/1)
Environmental Concentrate Comments V Arsenic
v Barium
Ground water (1) _ Solid (5) $-/ ...i::::::.. Cadmium v Chromium
Surface water (2) _ Liquid (6) v Lead
VSludge (7)
..J:::_ Mercury
Soil (3) v Selenium
V Silver
Other (4) _ Other (8) ------Organic Chemistry Inorganic Chemistry --
Parameter Results(mg/1) Parameter Results (mg/I) (mg/kg) Organic Compounds Results (mg/I)
P&T:GC/MS ✓ Arsenic benzene --7Barium --_ Acid:B/N Ext. carbon tetrachloride --_L, Cadmium MTBE chlordane ----Chloride chlorobenzene ----✓ Chromium chloroform ------__ Copper o-cresol ----Fluoride m-cresol ------Iron __ p-cresol ---L.Lead cresol ----
--__ Manganese --1,4-dichlorobenzene
--_L Mercury 1,2-dichloroethane
Nitrate = 1,1-dichloroethylene ----V Selenium 2,4-dinitrotoluene --_LSilver __ heptachlor
Radiochemistry Sulfates hexachlorobenzene ----Zinc hexachlorobutadiene ----Parameter Results (PCi/1) _pH hexachloroethane --__ Gross Alpha __ Conductivity __ methyl ethyl ketone
Gross Beta TDS nitrobenzene ------TOC __ pentachlorophenol --
--__ pyridine
Microbiology --__ tetrachloroetbylene
--__ trichloroethylene
Parameter Results (Col/lOOml) __ 2,4,5-trichlorophenol --
----__ 2,4,6-trichlorophenol
----__ vinyl chloride
endrin --lindane --Date Received Reported by __ methoxychlor
__ toxaphene
Date Extracted Date Reported 2,4-D --_ 2,4,5-TP (Silvex)
Date Analyzed Lab Number --C:PD89E
COAf PLETE SURFACE H'ATER SAMPLE
A . ORGANICS
l
Listed on the
chain-of-custody
for the organic
laboratory
,::;,,. N:,o,..-. G-en~r(\fr-...-r.n,.
1·•:"11i"••· Co r,~c,I Cilq C:i1r •: W(DOOIOol f'l0 1
(Y'\
N
c:-.,.,,f,. lflfl· '123~ Fie-lei Ir>· W-1 8 1 r"'"f'
"" --..!::.J..0Jr, ;-,~ """"~H~cl~-.-,----
(.,,,..Jrr-,: ,'),t"' fl~,-Arntly,;;i~: VDA
W-1
•nL 1[) \ IIMMlf)OUS w~~TF Hr.HT ~RMlr.11
sa.,ole tin: 0013236 Si te 110:N/(ll"C'lrell"'r/
Site N.ame: 6r11Pr(llrr1 /,ic
SI te l ocation: rqp,lt1 / (,I.(
Collector: ~ PJu
11Rr.MIIC
r., Ir: 'l'/11/lr
vJ . I
VOL.ATILES
(()
N
(i ,,. M ,,.,.. r: r n.-r<1fc•· I n r.
(2) 40 ml glass
vials
Co r 1\ol C, I t\ i:,,,. ,. w,ono1ootr(l 1
c:.-. .. .,,,,. IM'• 7?'-3b riC'ld Ir>: W -1 (,;:it-', r.~-.-
n:,,,.~tif">I":~ r-,,..~-__,tt .... c."-'1--,-----
~i,"'''"t: J 1t "" pi,.,-Annlyc:i,;;: VO A
'N -/
(2) .1-lf ter amber-
glass b o ttles
c:,,,. u,,,...... (;.(n'!r"f"r ,Tnc.:.
l n<:-ot i,...,-Ca p, \ol (1 fq C:i t i:-•· fJ'O(lOIOo\0<11
c;:,""''" 1r 1-12 3" ri tld 11'1:_y-J-1 6), r"'"" ""' 10/ij Jr,~;;;;. =0'!50 _ r,e,-__ r:,/0..
,,""'('\Cl s""' fl,r --------•r,nlyc:ic;: __ SVQ~ -
N.C. Department of Environment,
I lcalth, & Natural Resources
Solid Waste Management Division
SAMPLE ANALYSIS REQUEST State Laboratory of Public Health
P.O. Box 28047, 306 N. Wilmington Street
Raleigh, North Carolina 27611
Site Number NuD WI CQ.L ct>' Field Sample Number __ ....,,'.8"-'2:.=¼='------------
Nam e of Site {tf:&r_a l:o~
Colle cted By ~ Pl«
111,e,,
ID#
Site Location {R.pt'it:t/ 0-ly
--='---Date Collected ;q/25/10 ~ Time 0956
Agency: ✓ Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Inorganic Compounds Results(mg/1)
Environmental Concentrate Comments Arsenic --Barium w-1 --__ Ground water (1) _ Solid (5) Cadmium --Chromium
_L Surface water (2) --_ Liquid (6) Lead --
--Mercury
_ Soil (3) _ Sludge (7) Selenium --Silver --_ Other (4) _ Other (8) ----
--Organic Chemistry Inorganic Chemistry --
Parameter Results(mg/1) Parameter Rrsults(mg/l)(mg/kg) Organic Compounds Results(mg/1)
✓ P&T:GC/MS Arsenic benzene ----V Acid:B/N Ext. Barium carbon tetrachloride ----MTBE Cadmium chlordane ------Chloride chlorobenzene ------Chromium chloroform ------
--__ Copper o-cresol --Fluoride m-cresol ----= p-cresol --Iron --Lead cresol ------
--__ Manganese 1,4-dichlorobenzene --
--__ Mercury 1,2-dichloroethane
--Nitrate = 1,1-dichloroethylene --Selenium 2,4-dinitrotoluene ----Silver __ heptachlor --Radiochemistry Sulfates hexachlorobenzene ----·····-···~···-· Zinc hexachlorobutadiene ----Paramt'tl'r Results (PCl/1) _pH hexachloroethane
__ Gross Alpha __ Conductivity = methyl ethyl ketone
Gross Beta TDS nitrobenzene ------TOC __ penlachlorophenol --
--__ pyridine
Microbiology --__ tetrachloroethylene
--__ trichloroethylene
Paramell'r Results (Col/lOOml) --__ 2,4,5-trichlorophenol
----__ 2,4,6-trichlorophenol
----__ vinyl chloride
endrin --lindane --Date Received Reportcd~by methoxychlor --
--toxaphene -D;1lc ExlractcJ Dale Reported 2,4-D --
--2,4,5-TP (Silvex)
Dale J\naly1.cd Lab Number --DI IS 11')1 (Revised 2/91)
COMPLETE SURFACE WATER SAMPLE (continued)
B. /NORGANICS
Listed on the
chain-of-custody
for the inorganic
laboratory
( 1) 1-li ter
plastic jar
Note:
SOLIO I HAZARDOUS WASTE HGH T PRANCH -INORG~N!C
Sa11ole Ho: 0 09~38 Si te No:fiC!)C'CICt/0.:>1 Dale:'o/,~/1t
Site Na■e : 6PNr(l.h:,,, Inc YI-I
Sit. Location: (A/l,/r/ Gf<j
Collector: ~,., P1u TiH: 0'150
If measurements of pH,
temperature, and specific
conductivity are taken in
the field, water should
be collected in another
cubetainer. This water
should be disposed of
after the measurements
are taken and not sent
to the laboratory.
METALS
w - /
NON-HAZARDOUS INORGANICS
( 1) 1-li ter
[ plastic cubetainer
l\:.C. Department or Environment,
I lcallh, & Natural Resources
Solid Waste Management Division
SAMPLE ANALYSIS REQUEST State Laboratory or Public Health
P.O. Box ~7, 306 N. Wilmington Strci:t
Raleigh, North Carolina 27611
Site Number NCD C:Ol 001 60! Field Sample Number 91,:i'd
Name of Site &ef1era. m0 !flc. Site Location cAfJ,'/21 oty
Collecied By cf:Am Pier ID# a, Date Collected LOilS /J.o Time ofso I I
Agency: ✓ Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Inorganic Compounds Results(mg/1)
Environmental Concentrate Comments Arsenic --Barium
w-1 --__ Groundwater (1) _ Solid (5) Cadmium --
V Surface water (2)
Chromium --_ Liquid (6) Lead --Mercury
Soil (3) _ Sludge (7) --Selenium --Silver --_ Other (4) _ Other (8) --
----Organic Chemistry Inorganic Chemistry --
Parameter Results(mg/1) Parameter Rtsults(mg/l)(mg/kg) Organic Compounds Results (mg/I)
_ P&T:GC/MS ./ Arsenic benzene
7 Barium --Acid:B/N Ext. carbon tetrachloride ----Ji.. Cadmium MTBE chlordane ----V Chloride chlorobenzene --V Chromium --
--chloroform --✓ Copper --o-cresol --V Fluoride m-cresol ------
--_£ Iron __ p-cresol
V Lead cresol --✓ Manganese --
----1,4-dichlorobenzene
--~ Mercury 1,2-dichloroethane
--~ Nitrate = 1,1-dichloroethylene
~ Selenium --2,4-dinitrotoluene
__i,L Silver __ heptachlor
Radiochemistry __iL Sulfates hexachlorobenzene --. ····-·······-·--~ _JL_ Zinc hexachlorobutadiene --Parameter Results (PCl/1) ✓ pH hexachloroethane
__ Gross Alpha ✓ Conductivity = methyl ethyl ketone
Gross Beta _LTDS nitrobenzene ----TOC __ pentachlorophenol ----__ pyridine
Microbiology --__ tetrachloroethylene
--__ trichloroethylenc
Parameter Results (Col/lOOml) --__ 2,4,5-trichlorophenol
----__ 2,4,6-trichlorophenol
----__ vinyl chloride
cndrin --lindane --Date Received Reported_ by methoxychlor · = toxaphene
D:1lc Extractc.:LI Date Reported 2,4-D --
--2,4,5-TP (Silvex)
Dale Analy1.cd Lab Number --l>IIS WJI (Revised 2/91)
NC-DEHNR
Dh·ision or Solid Waste Management
D Superfond Section
,£1' Hazardous Waste Section
Solid Waste Section
Organics Lab: t/
Inorganics Lab: ---
CHAIN OF CUSTODY RECORD
Project Name: ( .:_ c;. rJ _J ;,-L 11 _,_
Site ID# (NCO#) /IJv,) :>J I o:i' I :u /
Location: l>1 i.,. 1··-/ •, I C, f5-1 U C r V.' Address: J,5=,JO &r,J,,;;t _,,,,J f:-0 ,..--I' f.j
Sample Types: Soil Water
Field Sample 2 ~ 3 S::
Numbers
Sampled by: S .:-u. 1 ~ k. r -------------Sam p I er ID __ ____;o~o ________ _
Telephone:_( 1'1 ,r)_::;_~_·-~=-'-_-_/ ,_1 / _________ _
Date Sampled: 10/,,c j ,:)CJ ______ .,......_._, -----------
Time Sampled:
Waste -----
Relinquished by:_~;:.;;;.....:,·-1=,".;....·'.-...... h'-' .... ~d"""_,,,., ____________ _
(Signature)
Received by: Date: Time:
(Signature)
Relinquished by: Date: Time:
(Signature)
Received by: Date: Time:
(Signature)
Relinquished by: Date: Time:
(Signature)
Received by: Date: ----Time: -----(Signature)
Results Reported: Date: ----Time: -----(Signature)
(J\:\COCR.FRM)
Page _!_of _L
SOLID WASTE MANAGEMENT DIVISION
Receipt for Samples
Firm Address
Firm Owner, Operator, or Agent Title
SAMPLE COLLECTED SAMPLE TYPE
NUMBER DATE:TIME WATER:soIL:oTHER
SJ ..::_ .. !Olr/9 J D~,..:: :,
~ ' -le I '/: .-;,, •' ·'.-: ~f ~ 0 :/ .) . -·-, ,.,
Receipt for the sample(s) described
above is hereby acknowledged:
Signature of Inspector
Title
Comments:
·I , d ,, . i/✓ -
. !-)/ /.-f I -, 1 t
DUPLICATE SAMPLE SAMPLE LOCATION
OFRD:ACPT:RJCTD ONSITE:OFFSITE
✓ (./ ✓
-✓ ./ ,/
Receipt/rejection of duplicate or
split samples is hereby acknowledged:
Title
------------------------------------
(/\:\COCR.FRM)
NC-DEHNR
Dh-ision of Solid Waste Management
D Superfund Section
'pr. Hazardous Waste Section
Jolid Waste Section
Organics Lab: ---Inorganics Lab: v/
CHAIN OF CUSTODY RECORD
( Z:€./1 f r~ fu, -Pier Project Name: ,L -,c Sampled by: ~,J v/,
Site ID# (NCD#) ) Sampler ID 0 ':) ucD. OQ/ (2()/ 00 (_
Location: I.AG. , fo L Cr-tL1 AF Telephone: (111 ) .'-·,:: ,.,_ -/!/ I __,;__,l '
i. d , . J1 'p, ;<J -......._
Address: ;} ; oo I [.1 _,;. ,-(,-( « £ ...Ji ,r k Date Sampled: o e::. 1..1..a
Time Sampled: ' 7
Sample Types: Soil Water ✓ Waste Other .~l ,dyc
Remarks: 11;5. ·~ -•=u_Jo~ ~s n 1 C3 = -,=o k{ ·w ·I ) ,,..
Field Sample q_1 j '7 lttf.5 ?
• ··,mbers
Relinquished by: ~// J:J½/r Date: 1)/;: //-·· Time: 1) ! --F) ~o , < ~
(Signature) 7
------------------------------------------------------------------------------------------------------------------------------------------------
Received by: Date: Time:
(Signature)
Relinquished by: Date: Time:
(Signature)
------------------------------------------------------------------------------------------------------------------------------------------------
Received by: Date: Time:
(Signature)
Relinquished by: Date: Time:
(Signature)
------------------------------------------------------------------------------------------------------------------------------------------------
Received by: Date: Time:
(Signature)
Results Reported: Date: Time:
(Signature) -
(J\:\COCR.f-RM)
Page / of / ~-
SOLID WASTE MANAGEMENT DIVISION
Receipt for Samples
Name of Firm Firm Address
Firm Owner, Operator, or Agent Title
SAMPLE COLLECTED SAMPLE TYPE
NUMBER DATE:TIME WATER:soIL:OTHER
{jL(~ 1 1D/lj/i(--. ,-i ~. D
q/j 6 I:)/;:,,, I i" ,, 'i ,' i) /
I
Receipt for the sample(s) described
above is hereby acknowledged:
Signature of Inspector
Title
Comments:
_ I t 'f ,,~
./ J
DUPLICATE SAMPLE SAMPLE LOCATION
OFRD:ACPT:RJCTD ONSITE :OFFSITE
✓ -;/ ,/
/ ,/ ,____.,,,--
Rece1pt/reJect10n of duplicate or
split samples is hereby acknowledged:
Signature of Firm Owner, Operator,
or Agent
Title
----------------------------------
(A:\COCR.FRM)
Attachment -C
SAMPLE CONTAINERS AND PRESERVATION PROCEDURES
FOR GROUND WATER MONITORING
pH
Specific conductance
TOX
Cnlonde
Iron
Manganese
Sodium
Phenols
Sulfate
Arsenic
larium
Ca~tum
Chromium
Lead
Mercury
Selenium
Si her
Fluoride
IOtrate/Nllr ~te
Recomiiended
Conta1nerb
Preservative Ha• ,mum
Holding Time
lnd1cators pf Ground-Water Contam1nat1o~C
T, P, G F ,el d determined
T, P, C, r ,e 1 d determined
G. ambe ~. T-11ned Cool 4°C . d
cape H( 1 to pH d
G, amber . T-11ned Coo 1 4°C . add 1 ml of
septc1 or caps 1. lH sodium sulfite
C.round -Water 0ual ,tr Cnaractcr1st1O
T. P, G 4 °(
T. p Field acid1f1eo
to pH < 2 wi th HN 03
G 4°C/H SO 2 4 lo pH <2
T. p ' G cool . 4°c
EPA jnter im 0rinktng Wate r cnaracter1 5t1c ,
T, p
Oark Bottle
T. p
T. P . G
Total Metals
Field &Cldlfled lo
pH <2 w,tn HN03
D 1 s SP 1v e d Met a 1 s
l . Field filtration
(0 .45 micron)
2. Ac1d1f7 to pH <2
wllh HN03
Cool . 4°C
11.ont inueo)
hone
hone
28 da ys
7 da ys
28 da :o
6 mont n~
28 da ys
28 da ,v s
6 mont hs
6 months
28 days
14 da .vs
H1n1mum llolume
ReQuired tor
Ar.alys1s
25 ml
1 OC m1
4 • 15 ml
4 • 15 ml
5 0 rr 1
200 ml
500 ml
5 0 rr, 1
1. 000 ml
1. 000 ml
300 ml
l . 00 0 ~1
5ompl~ Con-tainers and fk«rva-nc,r, P~cedures tfJr" {frc,und y../afu X,nii?>r·,n1
(~n+inud)
Parameter
£ndr1n
L1ndane
Hetho•ychlor
To.achene
2.4 D
2.4,S TP Silve•
Radium
Gross Alona
Gross Beta
Col1form bacteria
Cyanide
0,1 and Grease
s~; v o 1 at , 1 e .
nonvolati1e organics
Volatiles
Rec OtTTnen de d
Conta,nerb
T. G
Preservative
Coo 1. 4°C
r ,e1d acid1f1ed to
OH <2 1ontn Ht1O3
Ma• 11T1Um
Holdinq Time
~ :l~ys
6 months
0!.he• Grouno-wate· Cha racter, st 1c:s of Intere~
f'. G
1 . G
G, l-1,r,ed
Cocl. 4°C . NaO'i to
OH >12 . 0 .6 g
ascorbic ac ,dr
Cool' 4°( H2SD4 to
p,; < 2
Cool . 4°C
Cool. 4°C
2 S d~ yS
MinilTllJ'Tl Volume
Reouired for
Analysis
2.000 m1
1 ga 11 or
20 0 m l
SO G m~
1 CC, ml
t O m 1
6( ml
1References : Test Method< for Evaluating Solid waste -Pnys1cal/Chem1cal Metnods . SW-846
(2nd edit,on . 1982).
Methods for Chemical Analrs1s of Water and Wastes . [PA-600/4-7 9-020
Standard Hcthod~ for the Exam1nat1on of Water and wastewater . 16th edition (1985).
bconta,ner Types :
P = Plastic (polyethylene)
G Glass
T Fluorocarbon res,ns (PTFE . Teflon'. FEP, PFA. etc .)
PP= Polypropylene
~ple CM-ra.ir'\tfS arid fhservafi'Dri 'ih>uduf"t~ ,,, Cir~nd Wafer ~ni-hriY>j
. ( C1nli n~f.d)
'••sed on the requirements for detection 1110nitoring (§26S.93), the owner/operator must
collect • suff;cient volume of ground water to 1llow for the 1n1lysa of four separate
replicates .
d5h1pp;ng containers (cooling chest with ice or ice pack) should be certified as to the 4°C
temperature at time of sample placement into these containers. Preservation of samples
reQuires that the temperature of collected samples be adjusted to the 4°C irnnediately after
collection . Snipping coolers irust be at 4°C and maintained at 4°C upon placement of samp le
and during shipment . Maxlmum-m1n1m..,m thermo-neters are to be placed into the shipping chest
to record temperature history . Chain-of-custody forms will have Shipp1ng /Rece1ving ano
In-transit (max/min) temperature boxes for recording data and verif1cat1on.
100 not allow any head space In the container.
'use ascorb i c acid only 1n the presence of oxid1z1ng agents .
51Max1m..,m holding time 1s 24 hours ..-nen sulfide 1s present . Optionally, all samples may be
tested with lead acetate paper before the pH adJustment in oroer to determine if sulf1oe 1s
present . Jf sulfide 1s present. it can be remo ved by addition of ca6m1um nitrate powder
until I negative spot test 1s obtained. The sample is filtered and then NaOH is added to
pH 12 .
Attachment - D
ANALYTICAL METHODS FOR ORGANIC AND INORGANIC COMPOUNDS
N.C. Department of Environment,
Health, & Naniral Resources
Solid Waste Management Division
SAMPLE ANALYSIS REQUEST State l.aborator)' of Public Heallh
P.O. Box 28047, 306 K Wilmington Street
Raleigh, J\;orth Carolina 27611
Site Number ---------------Field Sample Number _______________ _
Name of Site Site Location ----------------------------------
ID# Date Collected Time Collected By ------------------------------
Agency: Hazardous Waste Solid Waste __ Superfund TCLP Compounds ----
Sample Type Inorganic Compounds
Environmental Concentrate Comments Arsenic --Barium --Ground water (1) Solid (5) Cadmium --Chromium --Surface water (2) _ Liquid (6) Lead --__ Mercury
_ Soil (3) _ Sludge (7) Selenium --Silver --_ Other (4) _ Other (8) --
--
--Organic Chemistry Inorganic Chemistry --
Parameter N'lalt+i~I MdilC<t # Parameter Anc,./'i-t i'cal Me#iod # Organic Compounds
P&T:GC/MS 6240 a: Arsenic 1~~g,7 ~ benzene ------_ Acid:B/N Ext. 8Z?O u) Barium carbon tetrachloride ----MTBE Cadmium '1131 0 chlordane --f:r.oci□ ----eos c LJ) Chloride '/0?: ~ chlorobenzene ------1,,indoaG: eoso © Chromium chloroform --=~~~. --
=~O( eoe o Q) __ Copper o-cresol --I~~ ~ Fluoride ~gJ ~ m-cresol ----_z,-4-0 Iron __ p-cresol --_ t,4,5,-,p Lead '1~21 (i) cresol ------__ Manganese l,(2()_.t ® --1,4-dichlorobenzene
--__ Mercury 'rj_ 1.Q U2 --1,2-dichloroethane
Nitrate 1?~r g 1, 1-dichloroethylene ------Selenium 2,4-dinitrotoluene ----Silver __ heptachlor --Radiochemistry Sulfates 272,'t ti) hexachlorobenzene ----Zinc ~} i hexachlorobutadiene
Results (PCi/1) ----Parameter _pH hexachloroethane
__ Gross Alpha __ Conductivity t~:) ~ --methyl ethyl ketone
Gross Beta TDS --nitrobenzene ------TOC __ pentachlorophenol ----__ pyridine
Microbiology --__ tetrachloroethylene
References
SW-846 Test Methods for Evaluating Solid Waste.
EPA-600/4-79-020 March 1979, Methods of Chemical
Analysis of Water and Waste.
Standard Methods for the Examination of Water
and Wastewater -15th edition.
EPA-600/4-79-020 Update December 1982, Methods of
Chemical Analysis of Water and Waste.
Results(mg/1)
Results(mg/1)
Attachment -E
..,
PRACTICAL QUANTITATION LIMITS FOR ORGANIC COMPOUNDS
TABLE 2. PRACTICAL QUANTITATION LIMITS (PQL) FOR VOLATILE ORGANicsa
Practical
Quant1tat1on
I " ' • 1 L1m1tsb l?~·u
Ground water Low Soil/Sediment
Volatiles CAS Number ug/L ug/Kg
1-. Chloromethane 74-87-3 10 10
2. Bromomethane 74-83-9 10 10
3. Vinyl Chloride 75-01-4 10 10
4. Chloroethane 75-00-3 10 10
5. Methylene Chloride 75-09-2 5 5
6. Acetone 67-64-1 100 100
7. Carbon Disulfide 75-15-0 5 5
8. 1,1-01chloroethene 75-35-4 5 5
9. 1,1-Dichloroethane 75-35-3 5 5
10. trans-1,2-Dichloroethene 156-60-5 5 5
11. Chloroform 67-66-3 5 5
12. 1,2-Dichloroethane 107-06-2 5 5
13. 2-Butanone 78-93-3 100 100
14. 1,1,1-Trichloroethane 71-55-6 5 5
15. Carbon Tetrachloride 56-23-5 5 5
16. Vinyl Acetate 108-05-4 50 50
17. Bromodichloromethane 75-27-4 5 5
18. 1,1,2,2-Tetrachloroethane 79-34-5 5 5
19. 1,2-Dichloropropane 78-87-5 5 5
20. trans-1,3-Dichloropropene 10061-02-6 5 5
21. Trichloroethene 79-01-6 5 5
22. Oibromochloromethane 124-48-1 5 5
23. 1,1,2-Tr1chloroethane 79-00-5 5 5
24. Benzene 71-43-2 5 5
25. cis-l,3-01chloropropene 10061-01-5 5 5
26. 2-Chloroethyl Vinyl Ether 110-75-8 10 10
27. Bromoform 75-25-2 5 5
28. 2-Hexanone 591-78-6 50 50
29. 4-Methyl-2-pentanone 108-10-1 50 50
30. Tetrachlotoethene 127-18-4 5 5
8240 - 4
Revision o Date Sept-em ...... b_e_r_l....,9'""'8~6
TABLE 2. -Continued
Volatiles
31: Toluene
32. Chlorobenzene
33. Ethyl Benzene
34. Styrene
35. Total Xylenes
CAS Number
108-88-3
108-90-7
100-41-4
100-42-5
Practical
Quant1tation
Limitsb
Ground water Low Soil/Sediment
ug/L
5
5
5
5
5
ug/Kg
5
5
5
5
5
asample PQLs are highly matrix-dependent. The PQLs listed herein are provided
for guidance and may not always be achieveable. See the following 1nformation
for further guidance on matrix-dependent PQLs.
bpQLs listed for soil/sediment are based on wet weight. Normally data is
reported on a dry weight basis; therefore, PQLs will be higher, based on the
% moisture in each sample.
Other Matrices:
Water miscible liquid waste
High-level soil & sludges
Non-water miscible waste
Factorl
50
125
500
1PQL = [PQL for ground water (Table 2)] X [Factor]. For non-aqueous
samples, the factor is on a wet-weight basis.
8240 - 5
Revision O Date Sept-em~b_e_r_1 __ 9 __ 8~6
TABLE 2. PRACTICAL QUANTITATION LIMITS (PQL) FOR SEMIVOLATILE ORGANICS**
Practical Quantitation
Limits*
Ground Water Low Soil/Sedimentl
Sem1volatfles CAS Number ug/L ug/Kg
Phen·o l 108-95-2 10 660
b1s(2-Chloroethyl) ether 111-44-4 10 660
2-Chlorophenol 95-57-8 10 660
1,3-Dichlorobenzene 541-73-1 10 660
1,4-Dichlorobenzene 106-46-7 10 660
Benzyl Alcohol 100-51-6 20 1300
1,2-0ichlorobenzene 95-50-1 10 660
2-Methylphenol 95-48-7 10 660
b1s(2-Chloroisopropyl)
ether 39638-32-9 10 660
4-Methylphenol 106-44-5 10 660
N-N1troso-01-N-propylamine 621-64-7 10 660
Hexachloroethane 67-72-1 10 660
Nitrobenzene 98-95-3 10 660
Isophorone 78-59-1 10 660
2-Nitrophenol 88-75-5 10 660
2,4-0imethylphenol 105-67-9 10 660
Benzoic Acid 65-85-0 50 3300
bis(2-Chloroethoxy)
methane 111-91-1 10 660
2,4-Dichlorophenol 120-83-2 10 660
1,2,4-Trichlorobenzene 120-82-1 10 660
Naphthalene 91-20-3 10 660
4-Chloroan11ine 106-47-8 20 1300
Hexachlorobutadiene 87-68-3 10 660
4-Chloro-3-methylphenol 59-50-7 20 1300
2-Methylnaphthalene 91-57-6 10 660
Hexachlorocyclopentadiene 77-47-4 10 660
2,4,6-Trichlorophenol 88-06-2 10 660
2,4,5-Tr1chlorophenol 95-95-4 10 660
8270 - 5
Revision 0
Date September 1986
TABLE 2. PRACTICAL QUANTITATION LIMITS {PQL) FOR SEMIVOLATILE ORGANICS**
(Continued)
Pract1cal Quant1tat1on
Limits*
Ground Water Low So11/Sedimentl
Sem1volat11es CAS Number ug/L ug/Kg
2-Chloronaphthalene 91-58-7 10 660
2-N1troanil1ne 88-74-4 50 3300
01methyl phthalate 131-11-3 10 660
Acenaphthylene 208-96-8 10 660
3-N1troanil1ne 99-09-2 50 3300
Acenaphthene 83-32-9 10 660
2,4-Dinitrophenol 51-28-5 50 3300
4-Nitrophenol 100-02-7 50 3300
Df benzofuran 132-64-9 10 660
2,4-Dinitrotoluene 121-14-2 10 660
2,6-Dfnitrotoluene 606-20-2 10 660
01ethylphthalate 84-66-2 10 660
4-Chlorophenyl phenyl
ether 7005-72-3 10 660
Fl uorene 86-73-7 10 660
4-Nitroani 1 f ne 100-01-6 50 3300
4,6-0initro-2-methylphenol 534-52-1 50 3300
N-Nitrosodfphenylamine 86-30-6 10 660
4-Bromophenyl phenyl ether 101-55-3 10 660
Hexachlorobenzene 118-74-1 10 660
Pentachlorophenol 87-86-5 50 3300
Phenanthrene 85-01-8 10 660
Anthracene 120-12-7 10 660
D1-n-butylphthalate 84-74-2 10 660
Fl uoranthene 206-44-0 10 660
Pyrene 129-00-0 10 660 Butyl benzyl phthalate 85-68-7 10 660 3,3'-Dichlorobenzfdine 91-94-1 20 1300 Benzo(a)anthracene 56-55-3 10 660 bfs(2-ethylhexyl)phthalate 117-81-7 10 660
8270 - 6
Revisfon O
Date September 1986
TABLE 2. PRACTICAL QUANTITATION LIMITS (PQL) FOR SEMIVOLATILE ORGANICS**
(Continued)
Practical Quantitation
Limits*
Ground Water Low Soil/Sedimentl
Semi-Volatiles CAS Number ug/L ug/Kg
Chrysene 218-01-9 10 660
Oi-n-octyl phthalate 117-84-0 10 660
Benzo(b)fluoranthene 205-99-2 10 660
Benzo(k)fluoranthene 207-08-9 10 660
Benzo(a)pyrene 50-32-8 10 660
Indeno(l,2,3-cd)pyrene 193-39-5 10 660
01benz(a,h)anthracene 53-70-3 10 660
Benzo(g,h,i)perylene 191-24-2 10 660
*PQLs listed for soil/sediment are based on wet weight. Normally data is
reported on a dry weight basis, therefore, PQLs will be higher based on the
% moisture in each sample. This is based on a 30-g sample and gel permeation
chromatography cleanup.
**Sample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achieveable.
Other Matrices Factor-1
Medium-level soil and sludges by sonicator
Non-water-miscible waste
lPQL = [PQL for Ground Water (Table 2)] X [Factor].
8270 - 7
7.5
75
Revision 0 Date Sept-em_,.b_e_r_1=-=9=-=3=5
Attachment - F
INSTRUCTION MANUAL FOR PH/TEMPERATURE/CONDUCTIVITY METER
·POLY-PRAM •
MULTI-PARAMETER INSTRUMENTS
1NSTRUCT10N BOOKLET
PRESTO-TEK CORPORATION
7 321 NoJtth F.i.gue1roa St1te et
Lo~ Angef.u, CA 90041 USA
(213) 257-75 _85
Cable. AddJtu~: PRESTEK
TWX:~910 321 4542 PRESTO TEK LSA
•
TABLE OF CONTENTS
INTRODUCTION.
OPERATION. . . . . . . .
Batteries . . . .
CONDUCTIVITY SECTION .
Calibration Procedure.
Outline Drawings
TEMPERATURE SECTION
Operation
Calibration.
pH SECTION
.
Introduction to pH •.
.
.
.
. .
. . .
. .
. . . . .
.
.
.
.
Page
1
2
2
4
5
7
8
8
10
Operation. . . . . . . . . . . 10
Calibration. . . . . . . ... 12
BUFFER SOLUTION CHART ..
MILLIVOLT SECTION
Operation. . . . . . . . . . .
Calibration ........... .
pH, MILLIVOLT SIMULATOR.
ACCESSORIES SECTION.
ORDERING INFORMATION.
WARRANTY . . . . . .
13
14
14
15
15
16
16
INTRODUCTION
Ten POLY-PRAM instruments provide portable, multi-
parameter measurements of conductivity in three ranges
to 200,000 micromhos, pH, Millivolts, and temperature.
This ma~ual contains instructions for operation,
calibration, and maintenance. The models covered in
this manual are as follows:
MODEL PARAMETERS MEASUREMENT RANGES
NUMBERS MEASURABLE pH / fflV TEMP., 'C CONDUCTIVITY, micromhos
DP-30 conductivity 0 200 : 0 2.000 : 0-20.000
DP-31 cond. 0-2.000; 0 20,000: 0 200.000
DP -32 cond .. temp --15 to 100 0 200; 0-2.000 : 0 20.000
DP-33 cond. temp -15 to 100 0 2.000; 0 20.0JO: 0-200,000 ·
DP-34 cond. pH 0.00 -14.00 0-200: 0-2.000; 0-20.000
DP-35· cond. pH 0.00 -14 .00 0-2.000; 0-20.000: 0-200,000
DP-36 cond . pH
& temp 0.00-14 .00 -15tol00 0-200 ; 0-2.000; 0 20.000
DP 37 cond. pH
& temp . 0.00 14 .00 -15 to 100 0-2,000; 0-20.000; 0 200.000
DP -38 cond .. pH 0.00 14 .00
millivolt, temp :=1999mv -15 to 100 0-200: 0-2.000: 0 20.000
DP 39 cond., s,H 0.00-14.00
millivolt. temp := 1999 mv -15 to 100 0-2.000 : 0 20,000, 0 200.000
·· Manual pH temperature 1d1usl
The new POLY-PRAM instruments are provided with an
LCD display. Four, ~-inch (1.3 cm) high, bold black
numerals on a light background--read results in direct
sunlight. pH may be read to .Ol; Millivolts to +1.0 Mv;
and temperature to .1°c. Read conductivity to .1 rnicromho
on the 0-200 scale; 1.0 on the 0-2000; 10.0 on the 0-20,000
and 100.0 on the 0-200,000 scale--ten times greater
readability than conventional, dial-type instruments.
pH measurements indicate the degree of acidity or
alkylinity of a solution. The Millivolt scale may be used
with specific ion probes, for measuring dissolved gases,
and for measuring oxidation reduction chemical reactions.
The conductivity ranges provide measurements of high purity
demineralized water on the 0-200 scale; tap and well
waters on the 0-2000 scale; brackish waters and chemical
solutions on the 0-20,000 scale; sea water is approx.
70,000 rnicrornho, so the 0-200,000 scale will measure
highly saline waters and concentrated chemical solutions.
POLY-PRAM instruments are virtually shock proof,
moisture resistant, and will provide years of satisfied
use if the proper care and procedures in this booklet
are followed.
-1-
OPERATION
The following test procedure is recommended when
performing measurements with the POLY-PRAM instruments.
BATTERIES
Check battery voltage by rotating the range function
switch (knob) to the "BAT'' position and press the Test
switch.
The instrument operates on a rechargeable battery,
YUASA, Type F-50 nickel-cadmium cell with a nominal
rating of 9.6 volts at SO Milliampere hours. The unit
will be energized and ready to operate if the battery
voltage is below 9 volts with the battery charger
plugged in. The battery will be on trickle charge
in all but the "BAT" position. When the battery
voltage is below 9 volts, the unit will not operate
properly. Recharge with the selector switch in
the "BAT" position for fast charge. ( In the "BAT"
position, the battery is on full charge and will
require approximately 16 hours to be fully charged.)
Full charge is obtained when the battery voltage
measures 11.2 volts with the charger plug removed
from the unit.
WARNING: 00 NOT CHARGE THE BA'ITERY LONGER THAN
16 HOURS WHEN THE SELECTOR SWITCH IS IN THE "BAT"
POSITION, as the battery life will be drastically
reduced or possibly ruined.
The required batteries may be ordered from the
PRESTO-TEK Corporation, ordering infonnation follows.
IMPORTANT
Your POLY-PRAM is the first digital, multi-
parameter instrument combining conductivity, pH,
Millivolts, temperature, and dissolved oxygen; and
due to high sensitivity, certain notations should
be made as follows:
-2-
•
l. DO NOT STIR SOLUTION WITH PROBES WHEN PERFORMING
TESTS, as end point becomes difficult to reach.
2. IMMERSE ALL PROBES AT LEAST TWO INCHES (5 cm) INTO
SOLUTION. Move probe in an UP and DOWN MOTION in
test solution to disperse fluid which may have
been left on probe from prior testing, and to
remove air bubbles.
3. ALLOW 10 TO 15 SECONDS FOR CONDUCTIVITY, pH and
MILLIVOLT READINGS to stabilize.
4. ALLOW 10 TO 30 SECONDS FOR TEMPERATURE and DISSOLVED
OXYGEN READINGS to stabilize.
5. DO NOT HOLD TEST BUTTON DOWN WHEN MAKING A BATTERY
VOLTAGE READING, as display will not stabilize due
to indication of battery discharge.
6. RINSE PROBES IN DISTILLED WATER AFTER USE--NEVER
ALLOW PROBE TO DRY OUT WITH RESIDUAL TEST FLUID
LEFT ON PROBES.
7. WHEN PERFORMING HIGH PURITY CONDUCTIVITY MEASURE-
MENTS (low range on DP-30, 32, 34, 36, 38 and 40),
PRESS TEST BUTTON WITH PROBE DRY TO DETERMINE
OFF-SET, IF ANY. Subtract off-set reading from
measurement results. Off-set results from probe
contamination. For cleaning procedure, refer to
PROBE CLEANING, in the CONDUCTIVITY SECTION of
this manual.
8. CHECK BATTERY VOLTAGE BY ROTATING THE RANGE FUNCTION
SWITCH (knob) TO THE "BAT" POSITION AND PRESS THE
TEST SWITCH.
9. Keep conductivity probe 2" from botton of container
or reading will be low.
10. When usihg the 200 uM conductivity scale, be sure
the probe is clean. A dirty probe will contaminate
the solution and the last digit will change as the
contaminate is dissolved inside the probe.
-3-
CONDUCTIVITY SECTION
l. The CONDUCTIVITY PROBE SHOULD BE CLEAN. Rinse
in deionized or distilled water before and after
use.
2. Insert probe in solution to be tested, making sure
probe is inserted to a depth of at least 1~ inches
(3.8 cm). Gently move up and down to remove all
air bubbles from probe. Air entrainment causes
inaccurate readings.
3. Rotate the range function switch on one of the three
conductivity ranges available. If the conductivity
range is not known for the fluid being tested, start
with the low range. Press the test button for reading
and wait for display to stabilize, which is typically
B to 10 seconds. If the display blanks out with the
figure "1" on the left side of the display, overrange
is indicated meaning the test fluid has a higher
conductivity than range selected. Rotate range knob
to next higher range. For greatest resolution, use
lowest range for which display does not show 1.
4. IMPORTANT: After each test, rinse probe in distilled
water before testing the next test fluid so as not to
mix test fluids. After final use of the instrument,
rinse probe in demineralized water. If probe is allowed
to dry with test fluid left thereon, resultant residue
will cause inaccuracies with subsequent testing.
5. PROBE CLEANING: The probes should be shiny bright.
Probes that have become coated may be cleaned by
rinsing in warm demineralized water and then rubbing
the electrodes with a Q-Tip or Kleenex. If this fails,
immerse probe in 10% hydrochloric acid for one minute,
followed by demineralized water rinsing, and rub with
a Q-Tip or Kleenex until electrodes are shiny bright.
If the coating is comprised of organic residue such as
oils, etc., this can best be removed by rinsing probe
in methanol or isopropyl alcohol, or by washing with
a non-abrasive soap. Again, follow with a derniner-
alized water rinse and rub until shiny bright.
WARNING: NEVER USE ABRASIVE SOAP OR SCRAPER OF ,ANY
TYPE, as the precious metal plating on the electrode
may be damaged, resulting in inaccurate test readings.
-4-
•
CALIBRATION PROCEDURES
Calibration of models DP-30, 32, 34, 36 and 38 requires
three standard solutions of 150: 1,500: and 15,00 micromhos
for the low, middle and high ranges, respectfully. The
models DP-31, 33, 35, 37 and 39 require calibration
solutions of 1,500: 15,000: and 150,000 micromhos for the
low, middle and high ranges, respectfully. Refer to
ACCESSORIES SECTION, which follows, for ordering infor-
mation, if needed.
The calibration procedure for the CONDUCTIVITY
SECTION is identical for all POLY-PRAM models: and for any
model, the calibration of any range is independent of the
other ranges. To begin the procedure, make sure the
electrodes are shiny bright, clean. Examine the probe
surfaces and make sure there are no breaks in the precious
metal-plated surfaces. If probes are damaged, instrument
should be returned to the PRESTO-TEK Corporation at
7321 N. Figueroa St., Los Angeles, CA 90041 for repair.
To calibrate, proceed as follows:
1. Remove the four screws on the bottom of the case and
gently remove cover. Refer to the outline drawing
which follows.
2.
To calibrate the low range, make sure the probe is
dry, as residual demineralized water from cleaning
will introduce an error in the calibration. Now,
insert the probe to a depth of 1~ inches (3.8 cm) in
the low range calibration solution and stir gently
until all air bubbles are removed brom the probe.
With the test button depressed, adjust R40 with a
small screwdriver until the display corresponds with
the value of the colution.
Rinse probe in demineralized water and dry. Insert
probe in the appropriate calibration solution for
the mid range, and with the test button depressed,
adjust R39 until the display corresponds with the
calibration solution.
-5-
3. Rinse probe in dernineralized water and dry. ·Proceed
with the high range calibration using the appropriate
solution by adjusting R38.
4. · BATTERY VOLTAGE CALIBRATION: This step requires
an accurate voltmeter, VOM or DVM. Place the leads •
from the above across the battery, while in place,
and adjust R27 until the POLY-PRAM reading
corresponds with the display of the calibration
meter.
,
-6-
AUTOMATIC
TEMP, ADJUSTMENT
BATTERY
CHARGER
TEW.ZER
H/2 pl:I_ CAl/8/fAnON
(PANEi. NOUVrED)
CONDUCTIVITY
PROIE COMVECTION
IUI lt~J MC
K~O.A"I
( CONDVC'17Y1T'Y
AOcAJSrJ
R8 ~ERO OP-AMP
(FOR FACTORY pH ADv.)
R6pHGMIAIMJS19
RH1rtVAl>tlUS18
MANUAL
pH /:!~RATION TEMP. ADJUSTMENT
( PANEL HOVNTED)
COM>l/CT/Vm
PROBE CONNECT/ON
Rlj
TENP. ZERO AWtJSr
R1'1
7EMP.1Drf C AfNIJSr
1? BAT.
A/MIST
IUB .tit MC
X/fJl,X/0, ,K/ ( CONDU:nvnr
AtWV.ST)
1?8cERO OP-AHP
(FOR FACTORY pH ADIi.)
R /4 R6 pH GAW AIM/Si
JIANUAL TEMP. ADJUsr
-7-
TEMPERATURE SECTION
OPERATION
POLY-PRAM models DP-32, 33, 36, 37, 38 and 39
contain temperature fW1ctions. The temperature probe
used in these models utilizes a dual, precision
thermistor. The measuring range is from -1s0 c to f
100°c, with an accuracy range of +.1s0 c, with display
resolution of .1 degree centigrade. CAUTION: The
0
I
probe should not be used at temperatures above 100 C,
as this may result in a permanent change in the
characteristics of the thermistor with resultant
temperature measurement inaccuracy.
For temperature tests, plug the probe into the
jack marked "TEMP". With models DP-32 and 39, rotate
the range function switch to "T" and depress the Test
Button. With models DP-36, 37, 38 and 39, rotate the
range fW1ction switch to the extreme counterclockwise
position. Rotate the upper left switch to the temp-
erature position and depress the Test Button to obtain
a test reading.
When testing liquids, typically the response time
for stable readings is 10 seconds from normal room
temperature to either o0 c or 100°c, and in air, the
response time is typically 30 seconds.
CALIBRATION
For accurate temperature calibration, use PRESTO-
TEK simulator, Model TC-01, or return to the factory.
Ordering information for the ~C-01 simulator follows
in the ACCESSORIES SECTION. To use the temperature f
simulator, plug it into the temperature jack and
set selection switches to the temperature measurement f
position on the POLY-PRAM instrument. Then set the
simulator control knob to o0 c, and press the Test
Button. Refer to the outline drawing preceeding, and
adjust Rl9 until the displa6 reads 000. 0. The
simulator is next set at 100 C and R24 is adjusted
to provide a reading of 100°c, which completes the
temperature calibration.
-8-
l\n approximate temperature calibration may be
accomplished by using a bath of melted ice and by
testing in boiling bath of water. Understand that
dissolved solids depress melting points and
atmospheric pressure variations effect the boiling
temperature of water.
It is suggested that ice made from demineralized
water be used in dernineralized water to calibrate
at the o0 c point. Allow sufficient time with
stirring of the water and ice to achieve temperature
equilibrium. Use gently boiling water to calibrate
at 100°c. Use the adjustments as indicated in the
first paranraph above, allowing 10 seconds probe
contact with the water.
-9-
PH SECTION
INTRODUCTION TO pH
Models DP-34 and 35 require manual temperature ad-
justment for pH correction due to temperature variations,
and knobs are provided to allow a dial set of the temp-
erature of the fluid being tested. The temperature ad-
justment range is o-100°c.
t-bdels DP-36, 37, 38 and 39 possess automatic pH
correction due to temperature variations over a range of
-1soc to 100°c.
All POLY-PRAM instruments with pH measurement capability
are equipped with a calibration adjustment control knob.
pH and temperature probe cleanliness is important. With
Model~ DP-34 and 35, only the pH probe is utilized in
making pH measurements. With t,x>dels DP-36, 37, 38 and 39,
both the pH and temperature probes are used. Rinse probes
in demineralized water both before and after measurements.
Replace the pH probe in the plastic bottle or probe tip
cover provided.
PERMA-PROBE, Model 85060, is provided with the POLY-PP.AN
instruments. The PERMA-PROBE is provided with a permanent
fill of reference solution and will last for several years
under normal usage, before replacement is necessary. If a
refillable electrode is desired, the PRESTO-TEK Model
85059 should be ordered. This probe requires periodic re-
fill with solution 80117. NOTE: A complete selection of
optional probes are listed in the PRESTO-TEK Laboratory pH
Electrode Catalogue, Form EL.
OPERATION: When performing pH tests with M::>dels DP-34
and 35, use the following test procedure. NOTE: Best re-
sults are obtained when test and buffer solutions are at
the same temperature.
l. Connect the electrode to the instrument only finger
tight--.00 NOT USE A TOOL.
2. Insert pH probe and thermometer in the buffer solution.
For greatest accuracy, the b--.....ffer solution used should
be within 2 pH units of the
-10-
solution to be measured. Set the temperature
adjust knob to correspond with the temperature
of the buffer solution.
3. From the Buffer Solution Chart, which follows,
determine the pH, and with the Test Button de-·
.Pressed, rotate calibrate adjust knob until the
display corresponds with the pH of the buffer
solution at the temperature of the buffer solution.
The reading should stabilize within 10 to 15 seconds.
4. Remove probe and thermometer from buffer solution,
rinse with demineralized water, dry, and insert in
test sample. Allow temperature to stabilize, then
set temperature knob to correspond with the temper-
ature of the test solution. Depress test button
and read results, allowing 10 to 15 seconds for
the display to stabilize.
When performing pH tests with models DP-36, 37, 38
and 39, use the following test procedure. Only a buffer
solution is needed, and greatest accuracy is achieved
by using a buffer solution which is within 2 pH W1its
of the fluid to be tested.
1. Plug in temperature probe in the proper jack and
connect pH probe only finger tight--DO NOT USE A
TOOL.
2. Insert both the pH and temperature probes in the
buffer solution. Rotate function selector knob to
the full counterclockwise position and set the
left-hand knob to the temperature position.
3. Depress the Test Button and obtain the temperature
reading, allowing time for the display to stabilize.
4. Refer to the Buffer Solution Chart, which follows,
to obtain the pH value of the buffer solution at
the temperature of the buffer solution.
5. Rotate left-hand knob to the pH position and press
the Test Button. Using the pH calibrate knob, rotate
until display corresponds with the buffer pH value.
-11-
6. Remove pH and temperature probes from buffer
solution, rinse in demineralized water, and
place in the solution to be tested.
WARNING: DO NOT TEST IN ANY FLUID OVER l00°c
IN TEMPERATURE. Depress Test Button and allow
10 to 15 seconds for the display to stabilize.
Read test results.
7. After reading results, rinse probes with deminer-
alized water and return pH probe to the plastic
bottle or insert in the tip cover provided.
CALIBRATION
For accurate pH calibration, use the PRESTO-TEK
Model 100 or 115 pH simulator. Further explanation
of the PRESTO-TEK simulators follows, as well as
ordering information, in the ACCESSORIES SECTION.
For the DP-34 and DP-35, set the controls of the
simulator for pH measurement mode and the temperature
control to 25°c. Plug in the pH simulator to the
POLY-PRAM instrument, with pH control set at 7 pH
and the temperature control at 25°c. Depress the
Test Button and adjust DP-34 or DP-35 front panel
calibration control for display indication of 7.00.
Then set the pH simulator to "l" and, with the Test
Button Depressed, adjust R6 for a display indication
of 1.00.
Calibration of the pH section of the DP-36, 37,
38 and 39 requires either a 25°c temperature bath or
the PRESTO-TEK Model TC-01 temperature simulator.
Place temperature probe in 2s 0 c bath or plug the
TC-01 simulator into the POLY-PRAM instrument, and
plug in the pH simulator. Then set pH at 7 and the
temperature simulator at 25°c. Depress the Test
Button and adjust front panel calibration control
for a display indication of 7.00. Now, set the pH
simulator at a pH of 1 and adjust R6 for a display
indication of 1.00.
-12-
BUFFER SOLUTION CHART
(TEMPERATURE CORRECTION CHART)
Buffer solution for standardizing the instrument
to the electrode, prior to use, is provided with each
instrument when shipped from the factory. Additional
qu_anti ties are available in 2 oz. plastic bottles by
ordering direct from factory by Part Number. Solutions
stored for more than one year should be checked against
fresh buffers. NOTE: Deterioration is greatest for
high pH buffers.
All buffer solutions change pH with temperature.
Below is pH vs. temperature tabulation for the three
standard buffers provided by the PRESTO-TEK Corporation.
pH 4 .01 .!_.01 Red pH 7.00 .!_.01 Grn. pH 10.01 ~.01 Blue
P/N 80114 P/N 80115 P/N 80116
Phthalate Buffer Phosphate Buffer Carbonate Buffer
oc ~ E!! E!!
0 4.00 7.12 10.32
5 10.25
10 4.00 7.06 10.18
15 10.12
20 4.00 7.02 10.06
25 4.01 7.00 10.01
30 4.02 6.99 9.97
35 9.93
40 4. 04 6.98 9.89
45 9.86
50 4.06 6.97 9.83
60 4.09 6.98
70 4.13 6.99
80 4.16 7.00
90 4.21 7. 02
95 4.23 7.03
CAUTION: pH 10. 01 Blue buffer --absorption of
atmospheric co2 will lead to degradation of product.
-13-
MILLIVOLT SECTION
OPERATION
Use of the Millivolt option makes possible the
measurement of voltages from Oto +1999 Millivolts
with one Millivolt resolution and an accuracy of
+0.1\ of full scale. There is no offset or temp-
erature compensation required for this function.
The input impedance is a minimum of 5 x 105 megohms.
Millivolt readings are obtained by rotating the
range function switch to the extreme counterclockwise
position and setting the upper left switch to the
Mv position. The probe to be used is plugged into
the connector marked pH. By depressing the Test
Button, the input signal will be displayed along
with the proper polarity sign. Utilization of
the Millivolt section provides measurements of
oxidation reduction potentials with combination
ORP probes, dissolved gas, or specific ion measure-
ments. These probes are available from the PRESTO-TEK
Corporation.
CALIBRATION
IMPORTANT: The pH section must be calibrated
prior to that of the Mv section. Refer to the
calibration procedures contained in the pH SECTION.
A PRESTO-TEK Model 110 or 115 pH simulator is
required for this procedure, or the instrument should
be returned to the factory. Set the instrument
range function switch to the extreme counterclockwise
position, connect the pH simulator to the pH input,
and set simulator for a pH of 14, which corresponds
to a Millivolt reading of -414, and a temperature
of 2s 0 c. Now depress the Test Button and adjust R14
for a display indication of -414, which completes
the calibration of the Millivolt section.
PH, MILLIVOLT SIMULATOR
These devices are quite useful in the calibration
of_ the pH and Millivolt sections of the POLY-PRAM
instruments. In addition, when difficulties arise
with pH measurement and control, the probe is at fault
the majority of the time. Slow response, instrument
instability and inaccurate measurements are symptomatic
of possible probe malfunction. Knowing whether or not
the probe is faulty saves lost testing time while
instruments are returned for repairs unnecessarily,
return and shipping costs and losses, and repair costs.
The PRESTO-TEK Corporation offers a Model 115
(9 volt battery powered) and a Model 110 (110 volt
line operated) pH simulators. These units may be
connected to a pH meter or controller, allowing
testing at pH values of O -14 in 1 pH units, or
over a Millivolt range of 315 to -414 Millivolts.
The use of a simulator traces the problem to the
instrument or the probe.
Also, buffer solutions age or become contaminated
with use. The simulator will also test the accuracy
of buffer solutions when used with a pH instrument
when the pH probe is functioning satisfactorily.
Ordering information follows in the ACCESSORIES
SECTION.
ACCESSORIES SECTION
MODEL or
ITEM DESCRIPI'ION PART NO.
Cond. Probe For use with cond. ranges 80352
lov ranges 0-200; 0-2.000; 0-20,000 uM
cond. probe For use with cond. ranges 85347
hi'lh ran~es 0-2000~ 0-20.000; 0-200,000 uM
Temp. probe Epoxy encased--accuracy ±-15% 85303
PE~}~-PROBE Plastic-encased, permanent 85060
nH electrode* filled, combination electrode
Power 115 volt, 0 cycle by
220 volt, 50 cycle.
Temperature Plugs into POLY-P
Simulator instrument.
pH; Millivolt Connects to .P0LY-P , instru-
Simulator ment--model '115 with a 9 volt
battery; model 110 for 110
volt 60 c cle ewer su 1
8522
TC-01
80261
115 V
85260 110-;
8026
NOTE: Other dissolved gas and specific ion electrodes
a.re available--consult catalogue or price sheets.
ORDERING INFORMATION
. 0,ule.JU, ma.y be pho ne.d ht tell 61[.e.e 6't,om anywh.eJLe
.irL t.he CDnt.ine.n.tal U.S. (except Cal.l6oJLJU.4} by cUa.llng
[phone]. 1n Ca.Ll6oJr.n.i..a., cLi..a1. [phone],
olt. mail. you.It oJt.dvr. t:..o t:he. a..ci.dJr..uh i, hown on t:he 6't,o nt
CDVeJL. I
Cable Ad.dJt.Uh : PRESTEIC
TIIJX Addlr..e..61>: 910 321 4 54 2 PRESTO TEIC LSA
··•···•······················ flJATGWITY
AU equipne.n.t ii, 6u.1Ly ~ 601L a
pe/Llod o 6 one IJeAll 46 bJ de6ech in
ma:tvLia.t OIL woltkman6h..ip. Equ.lpne.n.t Jte.-
tLvr.ned .u p!te.pai..d tc ~ 6a.ctDIUj. 16 .ln
t:he. op.i..n-lon 06 t:he. {,acl.DIUJ, 6ttltwt.e. MW
·· tWt. t;c ma.te/Llal. OIL &00Jtkman6h..ip, ll.epa/.JL OIL
11.e.plo.wne.nt wlU be nule. 11.llthou:t chtvr.ge.
.tWf JLt.twr.n.e.d at no cluvt.ge.. A nolt.nlal.
.-6 tJt v.i.ce. chtvt.ge wlU be nule. 601t. 11.qXL,iJu,
m de due. tc mi6 .t1t.e.abne..nt, no!Unt1l wtcVL,
Dll. mde on e.quipme.n:t out o 6 mM4nty.
-16-
·:_ &EPA
United States
Environmental Protection
Agency
Toxic Substances
Office of
Toxic Subs:ances
Washington DC 20460
E?A-550/5-25-0i 7
May, 1986
FIELD MANUAL . FOR .
GRID SAMPLING OFRECElVED
PCB SPILL SITES TQ~AY 14 ;993
VERIFY CL'EANUP HtAOFNEWYORK
@ Printed on Recyc!ed Paper
t-::
I .
I ' .,
r ·
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PREFACE
This Interim Report was prepared for the Environmental Protection
Agency under EPA Contract No. 68-02-3938, Work Assignment 37. The work
assignment was directed by Mitchell D. Erickson. This report was prepared
by Gary Kelso and Dr. Erickson of Midwest Research Institute (MRI). David C.
Cox of the Washington Consulting Group, 1625 I Street, N.W., Washington, D.C.
20006, contributed to the sampling design (Section 5.0) and compositing strat-
·egies (Appendix) sections under subcontract to Battelle Columbus Laboratories,
Subcontract No. F4138(8149)435, EPA Contract No. 68-01-6721 with the Design
.. and~.Deve lopment . .Br.anch ,-Expo.sure .. Evaluaiion .Di.vision.
This report· is a revision of a previous draft report entitled
"Field Manual for Verification of PCB Spill Cleanup11 (Draft Interim Report
No. 3, Task 37, EPA Prime Contract No. 68-02-3938, June 27, 1985). Both
English and metric units are used in this document, where appropriate. EPA
field inspectors will most commonly measure the site in English units; there-
fore these units were used for the site measurements in this report.
The EPA Work Assignment Managers, Daniel T. Heggem, Richard A. Levy,
and John H. Smith, as well as Joseph J. Breen and Cindy Stroup of the Office
of Toxic Substances, provided helpful guidance. Ms. Joan Westbrock and
Mr. Ted Harrison of MRI and Mr. David Phillippi and Mr. Robert Jackson of
EPA Region VII assisted in the field validation of this manual.
App~ov}ctf . ~.
ftA c-(7U a
Joht'E. Going, Di rector
Chemical Sciences Department
May 1986
ii
MIDWEST RESEARCH INSTITUTE
/Pc~AA-1 f ~ bl--u;~1 C. Const~;v
Program Manager
...
,
I
\..
FIELD MANUAL FOR GRID SAMPLING OF PCB
SPILL SITES TO VERIFY CLEANUP
By
·-Gary L. -Kelso
Mitchell 0. Erickson
MIDWEST RESEARCH INSTITUTE
and
David C. Cox
WASHINGTON CONSULTING GROUP
INTERIM REPORT NO. 3
WORK ASSIGNMENT 37
EPA Contract No. 68-02-3938
MRI Project No. 8501-A(37)
and
EPA Contract No. 68-01-6721 WCG Subcontract to Battelle Columbus Laboratories
No. F4138(8149)435
Prepared for
U.S. Environmental Protection Agency
Office of Toxic Substances
Field Studies Branch (TS-798)
401 M Street, S.W.
Washington, DC 20460
Attn: Mr. Daniel T. Heggem, Work Assignment· Manager Or. Joseph J. Breen, Project Officer Richard A. Levy, Work Assignment Manager Cindy Stroup, Project Officer
r-· \
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I
9.0
10.0
11. 0
TABLE OF CONTENTS (Concluded)
Documentation and Records ...
9.1
9.2
9.3
9.4
9.5
9.6
9.7
Equipment Preparation Log Book.
Sample Codes ..
Field Log Book ....... .
Site Description Forms . . . .
Chain-of-Custody Forms~ .•.
Sample and Analysis Request Forms.
Field Trip Report.
Validation of the Manual
References
Appendix -Strategies for Compositing Samples.
' . .. •· ...
. · .· ~ .. , .
· i V .... . ·.· .... •
Paae -
40
40
40
41
41
42
42
43
43
45
A-1
r I .
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No.
1
2
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
LIST OF TABLES
Title
Required Number of Grid Samples Based on the Radius
of the Sampling Circle ............. .
Geometric Parameters of the Hexagonal Grid Designs,
for Sampling Radius r .....
LIST OF FIGURES
Title
Examp l e PCB spill site diagram.
Example spill cleanup site diagrammed in the same plane
Locating the center and sampling radius of the example
spill cl eanup site. . . . . . . ..
Method to find center and radius of the sampling circle
Locating the center and sampling circle radius of
irregularly shaped sp_i 11 areas. . .
Location of sampling points in a 7-point grid
Location of sampling points in a 19-point grid.
Location of sampling points in a 37-point grid.
Construction of sampling grid on a site diagram
Sampling locations on the example PCB spill site.
Scale diagram of PCB spill site
Determining center (C) and sampling radius (r) of
sampling circle . . . . . . . . . . . .
Diagram of 19-point grid superimposed on the PCB spill
site. . . . . . . . . . . .
V
Paae --
12
15
8
10
11
13
14
16
17
18
19
21
25
-26 ·'
29
-!
In order to ensure that the inspectors understand and practice good
safety procedures, a training and education p_rogram should be established and
a health and safety .manual provided by the responsible EPA officer. The pro-
gram should inform inspectors of the potential hazards of exposure to PCBs,
and the proper safety procedures to follow when sampling PCB spill sites.
4. 0 -SAMPLING .EQUIPMENT.AND .-MATERIALS
The equipment and materials required to sample a PCB spill site
will vary with the types of samples to be taken. The general lists of equip-
ment and materials given below must be adjusted for the specific requirements
of each spill .. The lists include personnel equipment, sampling equipment~nd
materials, and documentation materials which should be t~ken to the spill site
by the EPA inspector. These equipment and materials must be assembled prior
to making the site visit, and all sampling containers and sampling equipment
must be precleaned.
4.1 Personnel Equipment
The inspector should take the following personnel equipment to the
spi 11 site:
• Disposable rubber gloves
Plastic overshoes
• · Safety glasses
Impervious paper-like coveralls
· Hardhat
• Safety shoes
First-aid kit
· Other safety equipment specified by safety officer
4
·• r.·-..
r
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...
4.2 ·: Samoling-~guipmen~ and Aaterials
Since the types of samples to be taken at a spill site may vary from
site to site, the following sampling equipment and materials should be taken:
,. 'Prec1eaned glass sample jars with Teflon-lined caps
A1u~{~um f~-il (solvent-rinsed)
.• .-CoAtai-ner. e_f-J>eagent-grade 'solvent (i-s.ooctane is .recommended)
• _Box. ~r 11 cm fiiter paper (e.g., Whatman 40 ashless or Whatman
·. so: s~ar tabs)
GauteP.ads
. StatnJ ess stee_l forceps
·• si~iriless st~eT templates (10 cm x 10 cm square)
· 1 Sta,_nf~~s stee 1 trowels, Teflon scoops, or 1 aboratory spatulas
·' : (pr,e:~i eaned)
· 501·1:· -c~'.t.ing .devices (such as King-tube samplers or piston corers) .... ·. !._. . .
• -Harii'nie·r~.and chisel ~ .; ·. :H?\~t);;· ~n-d . dri 11
.. Prii.rji'-ng ·· _shears
--s~i:i-.ri•l'e~s . steel buckets
· DH~i~b-~ e ·-wiping cloths
• · _'p}~-~;{/.:di:s~osab 1 e bags
........ ·: ::!ilt:•~::s:::is
·: -: ·-Jc'e-:(¢h~:·sts cor1t_aining ice or ice packs and secured with padlocks
... ·_.:; :_: ;~·(.:-~~i~lf!n~1,_ m_~ps
· .. •: ·: n~~~p_e_
.·. ::·.-;·:;/:"-j\iialii~~·-•wa.1;.er s~~pling equipment (such as pumps, siphons,
..... #. •• # :. • • .,. : .:~ ~t· !~~~-~(----~ _ _. __ ... ". . "'. .-... : . . . .
.... :,_··r:".::".::_gt~s:s:~-;s·ampl ing jars with attachments, etc.)
·::-< .··/~.¢J~j}i~-pf di ~t;i i~d ~at~r . · ·· ·-
. ': _. ·,\·:'·~tl'lA:l;~s •'stee 1 . ini x:i ng bowls and spoons . \il}if tijt •. : .•
. . i}if i;;/ ..
. _:_ ~----\: . .\;~~It{~·_
5
r . ' . I
l -
r
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site:
4.3 Documentation Materials
The following documentation materials should be taken to the field
Field log book
• Chain-of-custody forms
• Site description forms
· Sample analysis request forms
· Sample bottle labels
· Camera with film
· Yellow TSCA PCB marks
4.4 Trip PreDaration
The EPA field inspector must assemble all the neces~ary equipment
and materials prior to making_the field sampling trip. Special attention
should be given to assuring that all of the equipment and materials are avail-
able, and that the sample containers and sampling equipment have been properly
precleaned. The equ i pment preparation should be documented in a log book
(Section 9.1) pri or to making the trip.
5.0 SAMPLE DESIGN
The methods to be used for determining the sample point locations
at a PCB spill si te are given in this sec\ion, and are based upon a hexagonal
grid sample design which was recommended in the report 11 Verification of PCB
Spill Cleanup by Sampling and Analysis.11 Although the grid design involves
more samples and a more complicated layout than the usual grab sampling meth-
ods, the grid design is essential to obtaining a representative sample of the
site and greatly increases the chance ~f detecti~g high levels of PCB contam-.,
ination when they exist. For example, when 4% of the PCB spill site remains
contaminated at 50 ppm after cleanup, analysis of samples from a 37-point
6
grid has a 98% chance of detection of this contamination level, while analysis
of six random grab samples from the site has only a 3% chance of detection
(Boomer et al. 1985).
The hexagonal grid sampling design is to be laid out within a sam-
ple circle centered on the spill site, and extending just beyond its boun-
daries. Preparation of the design requires the following steps:
Steo 1: Diagram the Cleanup Site
Stee 2: Diagram All Cleanup Surfaces in the Same Plane
Stee 3: Find the Center and Radius of the Sampling Circle
Step 4: Determine the Number of Grid Sample Points to Use
Steo 5: Lay Out the Sampling Points on the Diagram Constructed in
Step 2
Steo 6: Lay Out the Sampling Locations on the Site
Step 7: Consider Special Cases and Use Judgment for Sample Points
The discussion which follows gives the methods to be used in accom-
plishing each step of the hexagonal grid sampling design, using a three-·
dimensional spill surface as an example. Following this discuss i on, a simple
example of laying out the sample ·design on a rectangular two-dimensional sur-
face is given.
5.1 Steo 1: Diaaram the Cleanuo Site
Draw a scale diagram of the cleanup site on graph paper, including
vertical surfaces (walls, fences, etc.), noting important dimensions and dif-
ferent types of surfaces (sod, cement, asphalt, etc.). Such a di agram may
sometimes be found in records of the cleanup. If not, site measurements
should be taken. Great accuracy (e.g., using surveying instruments) is not
necessary, however; the use of a tape measure and pacing sh·ould be adequate.
An example diagram is shown in Figure 1 on a scale of 1 in. = 4 ft.
7
~ i
~·
/'
f-
J I
Wall {Concrete)
4' :·-· :;Scale: ~-....;....-----1
Figure 1. Example PCB spill site diagram .
. :-_--.-··
I ! --. 8
i ,--
' -
I
r The site diagram should include as many reference points as neces-
sary to relocate the spill area in the future, if necessary. For example,
a spi~l site in an open field should be located with respect to nearby struc-
tures such as roads, telephone poles, buildings, etc. The direction of north
should be indicated on the diagram .
. If available, a detailed drawing or a survey plot of the spill site
.shoul~~b~.obtiined from the individual(s) ~hat cleaned the site.
5.2 . Stec 2: Diagram All Cleanup Surfaces in th~ Same Plane
The purpose of this second diagram is to determine and show the
dimensions of the total cleanup area, including vertical surfaces, so that
the required sample size can be found. The diagram also facilitates the
determination of .sampling locations on vertical surfaces. Constructing the
diagram is analogou~ tp flattening a cardboard box. All vertical surfaces
are placed in the same plane as the adjoining horizontal surfaces. Figure 2,
also on a scale of 1 in. = 4 ft, shows the example spill cleanup site dia-
grammed in the same plane. The actual site dimensions are shown in feet.
5.3 Step 3: Find the Center and Radius of the Samolino Circle
In practice, the contaminated area from a spill will be irregular
in shape. In order to standardize sample design and layout in the field,
~amp.les are collected within a circular area surrounding the contaminated
area. "The sampling circle is, approximately, the smallest circle contain-
ing all cleanup surfaces diagrammed in Step 2.
A recommended procedure for finding the center and radius of the
sampling circle is illustrated in Figure 3 and is described below:
1. Draw the longest dimension, L1 , of the site diagram in Step 2.
2. Find the midpoint, P, of L1 .
9
F i
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I I I I I I ' I I I I I
I I \ \ I I I I I
I I I I ' I \I I I
I \I \ I
I \ \ I
I I I ~ I '{ I Di:t
I I I I I I \ I 15-l/2· I
I I I I I I I ' I \ I
I I I I I \ ' I ' I I I I I\ \I Wall Driveway
( Concrete) (Asphalt) I I I I ' I ~ I I ' ' I I I
I I I I I I I t..ot ' I I\ f\ I I I I ( Dirt) I \ \ I
I I I I I I \ I -I
I I I I I I ), .,,.,.,.
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I I I I I I /AI I
I I I I I I I I I I V // I
I S(dewalk (Concrete) I~ / I I I
7'-----a·----
4 I Scale:---
Figure 2. Example spill cleanup site
diagrammed in the same plane.
10
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I!/ I I I l/i / vi
IA I I V _v I 7-1/2' .11 I I I /AI I
VI I I I I I l I V /v I
I I I . I~ V
~ 7 I 8' I
4' · Scale: ------
Figure 3. Locating the center and sampling radius of the
· example spill cleanup site.
11
~
r
3. Draw a second dimension, L2 , through~ perpendicular to L1 .
L2 extends to the boundaries of the site diagram.
4. The midpoint, C, of L2 is the center of the sampling circle.
5. The distance from C to either end of the longest dimension, L1 ,
is the sampling radius, r.
Figure 4 illustrates the application of this procedure to a site
with an irregular shape, and Figure 5 shows the procedure for a variety of
irregularly shaped areas. These figures show that the center and radius
determined are generally reasonable.
5.4 · Step 4: Determine the Number of Grid Sample Points to Use
The number of grid samples to be taken at a site depends upon the
radius of the sampling circle, which is determined from the scale diagram
shown in Figure 3. The number of samples to be taken at a spill site should
increase as the radius of the sample circle increases. The reason for this
is that the probability of detecting residual PCB contamination at a given
site increases as the number of grid samples increases. Table 1 shows the
required number of grid samples for sampling circles with a radius of 4 ft or
less (seven samples); greater than 4 ft to 11 ft (19 samples); and greater
than 11 ft (37 samples).
Table 1. Required Number of Grid Samples Based
on the Radius of the Sampling Circle
Sampling radius, r (ft)
> 4 -11
> 11
12
Number of Samples
7
19
37
~
~--
r
~-
,--
I
. !--
L1
(a) Draw longest dimension, L1,
on site diagram.
e
(c) Drc_wline, L2, throughP
perpendicular to L l.
p
(b) "find. midpoint, P, of L1. ·
(d) The midpoint, C, of L2 is the
center of the sampling circle.
(e) The distance from C to the end of L1
is the sampling radius, r.
-. · ..
Figure~-Method to find center and radius of the sampling circle.
13
Figure 5. Locating the center and sampling circle radius of
irregularly shaped spill areas.
14
f
r-=
I r-
The radius, r, for the example site is 3-1/4 in. in Figure 3. Thus,
the actual site sampling radius is 13 ft (3-1/4 in. x 4 ft/in.) and the num-
ber of grid samples required is 37 .
Figures 6, 7, and 8 illustrate the hexagonal grid sampling design
for the three sample sizes given in Table 1, for a sampling radius of 4, 10,
and 20 ft, respectively.
5.5 Step 5: Lay Out the Sampling Points on the Diagram Constructed in
Step 2
The geometric properties of the hexagonal designs can be used in
many ways to lay out the sampling points. Perhaps the simplest way to pro-
ceed is as follows. Defines to be the distance between adjacent points and
u to be the distance between successive rows of the design. The distances
sand u are given in terms of the sampling radius, r, in Table 2 below for
the given number of samples defined by the radius rule and listed in Table 1.
Table 2. Geometr.ic Parameters of the Hexagonal Grid Designs,
for Sampling Radius r
Distance, s, between Distance, u, between
Number of samples adjacent sample points successive rows
7 0.87r 0.75r
19 0.48r 0.42r
37 0.30r 0.26r
The recommended method _for laying out the sample points of the
hexagonal grid on the scale diagra_m is illustrated in Figure 9 and is de-
scribed below.
1. Draw a diameter of the sampling circle on the scale diagram.
The orientation of the diameter (e.g., east-west) should be chosen to maximize
the number of sample points which fall within the spill area, when practical.
15
_;
1--
4
3
r
i L
2
1
y 0
1 1 [ ___
2
3
1
4
I I
\ --
□ □
□ ■c 0
□ 0
4 3 2 . 1 0 2 3
X
The outer boundary of the contaminated area
is assumed to be 4 feet from the center ( C)
of the spi II site.
Figure 6. Location of sampling points in
a 7-point grid.
16
,--10 I I
8 -□ □ □ -
6
4 □ □ □ a
2
y 0 □ □ ■C □ □
2
4 □ ·a a a
6
8 : □ a □
10
10 •·--: a .. --·6 _ ..... -4 ---··· 2 -1-•• a 2 ·• 4 . 6 8 10
:" X
The outer boundary of the contcminoted area is c!Sumed to be
10 feet from· the center (C) of the spill site.·
~ ~: .
Figure 7. Location of sampling points in a 19-point grid.
17
' ~-
I I
f _·
f ... · 20
' -16 □ □ □ □ L.-
I 12 ' I -□ □ □ □ □
8 i .
'
□ □ □ □ □ □ 4
y 0 □ □ □ ■C □ □ □
4 □ □ □ □ □ □
8
□ □ □ □ □
12
16 □ □ □ □
: --· -.. -. _,_ -· ..
20
20 16 12 8 4 0 4 8 12 16 20
X
~ . ,':. .
The outer boundary of the contaminated area is assumed to be
20 feet from the center ( C) of the spi 11 site.
, . .,.,,. ·-....
Figure 8. Location of sampling points in a 37-point g~id.
18
I
r ;
! .
I --, L ••
. ; .. ::
Figure 9 . . -... •, . .; !
■C
o-s--:::-s --=--s --::i
{midpoint)-!
C • Cl I
{a) Center of _cleanup crea, C.
(b) Middle row of grid points
located di~tance, s, apart.
. --{ c) Next t°'n'O grid rows perpendicular
distance, u, from middle row.
( d) Completed 19 sample point srid .
Construction of sampling grid on a site diagram.
i .:
19
F I
i
)--
\.
A transparent overlay like Figures 6, 7 and 8 (using the appropriate scale)
may be helpful in determining the orientation of the diameter.
2. Place the center po~nt of the hexagonal design at the center (C)
of the sampling circle. Lay out the middle row of the design along the diam-
eter with successive points a distance, s, apart.
3. To lay out the next row, find the midpoint between the last two
sample points of the middle row and move a distance, u, perpendicular to the
middle row as shown in Figure 9. This is the first sample point of the next
row. Now lay out t he remaining points at distances from each other. By
systematically fol l owing this plan, the entire design can be laid out.
Figure 10 shows the sample point locations for the 37 grid points
for the example PCB spill site diagrammed previously in Figures 1, 2, and 3.
On the diagram, r = 3-1/4 in. so from Table 2 the grid spacing is s = 0.30r =
1 in. and the distance between the rows is u = 0.26r = 7/8 in.
In Figure 10, a horizontal diameter is drawn through C. Sampling
locations 1 through 7 are marked 1 in. apart. To lay out the next row of the
design, we first find location 8. Point Dis the midpoint between locations
3 and 4. Then, as described, location 8 is a vertical distance u = 7/8 in.
(3 ft 6 in. on the site) above 0. Now locations 9 through 13 are laid out
1 in. apart. In the same way, locations 14 through 18 are found. Continuing
so, the entire grid is marked on the diagram.
All _of the sample points in Figure 10 are numbered (1 to 37). Any
type of numbering system can be used, but the points must each be identified
so that the location of the samples _taken can be identified by reference to
the diagram points.
Note that sampling locations 4, 7, 8, 13, 23, 34, 35, 36, and 37
are outside the cleanup area. Of these, locations 4, 8, 23, 34, and 35 do
not correspond to· a physical location--all are in 11 thin air,11 so to speak--
and samples cannot be collected at these locations. Locations 36 and 37 are
concrete samples; locations 7 and 13 are dirt samples (from Figure 2).
20
I i I
r
L .
_ --LSampling Circle ------~ ~
/ ""
/
I
I
(I!,
18
~
19
D
9
□ 17
-
20
D
10
0
16
C
21
D
11
D
15
-22
0
12
j_ r = 13' ---m----e--~---~-
4 D . 3 2 ~s = 4 ,_j5
\ g
\
\
D
24
·□
32 .
D 25
D
31
D
26
D
30
D
27
~
\
\
\ .
\°icmeter
D 28
17
/
I
I
/
,-□. 0 0 D /.
~....... 35 36 ~
.........__ --------~
4' Scale: i-------1
Figure 10. Sampling locations on the example PCB spill site.
21
L
The orientation of the sample circle diameter shown does not ac-
tually maximize the number of points falling within the spill area, since a
45° clockwise rotation would result in only 8 points lying outside the spill
area instead of the 9 points shown. However, a 45° orientation would make
the sample points very difficult to locate on the actual site with little to
gain by the addition of one more sample point within the spill area.
5.6 Step 6: Lay ·Out the ·Sampling tocations on the Site
To locate the sample points on the site, use the same procedure as
was used to construct the diagram of the sample points in Step 5, but use a
tape measure or pacing, as appropriate, to measure distance. Since s = 1 in.
in the diagram (Figure 10), thens= 4 ft on the site. Similarly, u = 3 ft
6 in. on the site. It may be helpful to show the actual distances (in ft) on
the diagram before laying out the site sample points. For example, the sam-
ples on the wall are most easily found by measuring the distance on the scaled
diagram from one end of the wall and the height above the driveway, and then
converting these measurements to find the actual location on the wall. Con-
sider point 32, for example. On Figure 10, it is located approximately 3/4 in.
above the driveway and 5/8 in. from the left edge of the wall. On the site,
then, this point is 3 ft above the driveway and 2-1/2 ft from the left edge
of the wall.
The PCB spill site should be considered contaminated until labora-
tory analyses of ·the samples taken verify the site is clean. Therefore, cau-
tion should be exercised when marking the sample points on the site to prevent
possible cross-cori~amination. ·The inspector should make minimum contact with
the spill surfaces. One method for accompli~hing this would be to cover the
surfaces with plastic sheeting.
22
)-
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5.7 Step 7: Consideration of Special Cases
5.7.1 Sample Points Outside the Soill Cleanuo Area
Samples from points outside the spill area should generally be col-
lected, although taking these samples is at the discretion of the inspector.
Collection of these samples permits the EPA to check the contamination of
samples .outside .the .. spill..ar..ea designated by the party responsible for the
cleanup. This provides a mechanism for assessing whether the spill area was
underestimated by the cleanup crew.
In cases where the contaminated area is very different from a cir-
cle (e.g., a very elongated ellipse) the sampling circle may be a poor ap-
proximation of the contaminated area, and a moderate to large percentage of
the sampling points may fall outside the contaminated area. If the sampler
is certain that the spill boundaries truly represent the contaminated area
(i.e., there is definitely no contamination outside of this area), then it
is permissible to disregard those sampling points falling outside the con-
taminated area. However, it is still good practice to collect such samples
because the effort required to return to the site and sample again (should
these samples be needed for any reason) is much greater than the effort re-
quired while on site.
5.7.2 Sample Locations Which Do Not Physically Exist
The grid can also indicate sample locations which do not physically
exist on the real site. These locations are in "thin air11 so to speak and
cannot be sampled. The number of samples to be collected is adjusted down-
ward for these samples; replacement locations are not needed.
5.7.3 Judamental Samples
The inspector's best judgment should be used to collect samples
where residual PCB contamination is suspected. These samples would be
collected in addition to those from the sampling grid. Examples of extra
23
I '-··
I I .
sampling points include suspicious stains outside the spill area, cracks or
crevices, or any area where the inspector suspects inadequate cleanup.
5.7.4 Sampling Small Areas
The ·grid sample desig~ ipecifies that seven samples should be taken
in areas which have a sample circle radius of less than 4 ft. In cases where
the spill area is very small, -fewer than seven .samples ~an be taken at the
discretion of the EPA inspector .
5.8 Examole of Laying Out the Sample Design
This section summarizes the step-wise procedures required to deter-
mine the locations of the grid sample. points at a PCB spill site. The example
used is a simple 8 x 10 ft rectangular spill site.
Steps 1 and 2: Measure and Diagram the PCB Spill Cleanuo Site
The PCB spill cleanup site must first be measured (usually with a
tape measure). Then the site should be drawn to scale on graph paper. In
this example, the site is assumed to be an 8 x 10 ft rectangle, as shown in
Figure 11. A scale of 1 in.= 2 ft is used.
Step 3: Determine the Center and Radius of the Samolina Circle
The center and radius of the sampling circle is-determined on a
separate diagram as follows, and is illustrated in Figure 12:
1. Draw the site diagram to scale (same as Figure 11).
2. Draw a line representing the longest dimension, L1 , of the
site diagram.
3. Find the midpoint, P, of L1 •
24
. -· r~
i [~,-..
:
r-
I I
r:..:_
. r--:
\
. !
I
r --
I -
'
I .
i ' , ..
I L __
I ·-
N
~
Soil 8'
....... -----------10'-----------......llol
Scale
Figure 11. Scale diagram of ·pcs spill site.
25
r· I . l .
• I
i
l __ -
\_:
W-----------10'-----------~
2'
Scale
Figure 12. Determining center (C) and sampling radius (r)
of sampling circle.
26
8'
1·
I
1-
i I
!
4. Draw a second line, L2 , perpendicular to L1 , through point P.
Line · L2 must extend to the boundaries of the site.
5. Find the midpoint, C, of line L2 • Point C is the center of the
sampling circle. (In this example, points P and C coincide,
but will not coincide for many other types of configurations.)
6.. -Measure··the· distance··from··point C -to ·e;ther -end of L1 , which
is the sampling radius, r. The distance, r, should be measured
to the nearest 1/16 in.
7. Scale radius, r, up to actual size. In this example, the
radius, r, is 3-1/4 in. on a scale of 1 in.= 2 ft, or 6-1/2 ft ·
(3-1/4 in. x 2 ft/in.).
Step 4: ·Find the Numbei of Grid Samples to be Used
-.. ··-... -.
. _The number of samples to be taken in a hexagonal grid depends upon
the length of the sa~pl°ing ra~ius; as shown in Table 1 and repeated here.
Sampling Radius, r (ft) Number of Samples
~-4 7
.. ·:::, 4 ·-11 19
> 11 37
· .Since the radius in this example is 6-1/2 ft, the number of sampling · ... · .· ..
~6ints ·would ·be ·l9.
Step 5: Plot the Samoling Points on the Site Diagram
. .
.T~~ ~a~plin~ ~oints in a grid row are a distance, s, apart; and the
gri~ rows .are a dista.nce, u, apart. The distances s and u are determined from
th~ fallo~i~g ~abi~~
27
l -,
r r
r .
,---
i
I -I
!
I -i. _·
Number of Samples
7
19
37
Distance, s, Between
Adjacent Sample Points
0.87 r
0.48 r
0.30 r
Distance, u, Between
Adjacent Rows
0.75 r
0.42 r
0.26 r
In this example, the distance, s, between the points in a row is
1-9/16 in. [(0.48) x (3.25 in.)] on the diagram, or about 3 ft 2 in.
[(1-9/16 in.) x (2 ft/in.)] on the actual site. Th~ distance, u, between
rows is 1-3/8 •in. [(0 .42) x (3.25 in.)] on the diagiam, or about 2 ft 9 in.
[(1-3/8 in.) x (2 ft/in .)] on the actual site.
The center point of the grid lies on the center, C, of the sampling
circle. Construct the hexagonal grid and superimpose it o~er the site diagram
(constructed .on a third piece of graph paper), as illustrated in Figure 13 for
this example. The middle row of the grid (points 1 through 5) should be
oriented to maximize the number of sample points which lie within the bound-
aries of the spill cleanup site.
It should be noted that adjacent rows are staggered, and that the
sample points ·of one row are located midway (horizontally) between the sample
points of the other row.
Step 6: Mark the Sample Points on the Site
Starting at the center, C, of the spill cleanup site, mark the mid-
dle row points a distance of 3 ft 2 in. apart. Locate the adjacent rows a
distance (u) of 2 ft 9 in. from the middle row, and mark the four sample
points in each of these rows a distance of 3 ft 2 in. apart. Complete the
site sampling grid -with the other two rows of sample points. -·· -· · ·
6.0 .. SAMPLE COLLECTION, HANDLING ANO PRESERVATION
After the sampling grid has been diagrammed on the site description
forms and laid out on the site, a sample must be taken at each grid point.
28
I·-1-
I I
I
I
,-
I
. I
I . ,-
0
1
□ 6
D 13 ..
2'
Scale
□ 10
□ 2
. □.
17 ..
... :.."". . .
□ 7
0
14
-=· ,-.
□ □ 11 12
u = 1-3/8" = 2'9"
. /(midpoint)
~-,/
D
18 .
0
15
0
19
□ 9
□ 16
· .. ·:: Figure 13 .. Diagram of 19-point grid sup·erirnposed on the
PCB spill site.
29
N
t
□ 5
. .. ----• I
l -
L--
Until the samples have been analyzed, the entire area must be assumed to be
contaminated with residual PCBs. Therefore, appropriate measures must be
taken to protect workers and the general public, prevent cross-contamination
of s~mpl~s, and prevent contamination of the surrounding area during sampling.
Detailed contamination prevention procedures should be given in the staff
training (Section 3.0 and 8.2).
PCB spill sites will vary widely in nature, and the types of media
to be sampled may include soil, sod, water, hard surfaces, and vegetation.
This section presents some general methods that can be used to sample these
different media .. These sample collection, handling and preservation tech-
niques are provided for information; other techniques may also be used. Ad-
rlitional sample collection guidance documents are also available (Mason 1982;
USEPA 1981).
6.1 Surface Soil Samp1ing
When surface soil (or sand) is to be_sampJed, the sample area should
be marked by a 10 cm x 10 cm (100 cm2 ) template. The soil should be scraped
to a depth of about 1 cm with a stainless steel trowel, scoop, or spatula to
yiel6 about 100 g of soil. If more soil is required, the area should be ex-
pande~ withriut increasing the depth of soil obtained. The soil sample should
be placed in a precle~ned glass bottle, the bottle capped, the sample bottle
label filled out and attached, and a yellow TSCA PCB mark affixed. The bottle
sho~ld be ~ealed in a plastic sample bag and placed in an ice chest containing
ice (to keep the sample at about 4°C). If samples are to be analyzed soon,
the cold storage requirements may be relaxed as long as sample integrity is
maintained. The sample collection data should be entered in the field log
book and on.the chain-of-custody form. ,,
The template used to mark surface soil samples, the scoop or spatula
used to take· the sample, and the rubber gloves worn by the inspector are all
' sources of cross;..contamination between samples. Ideally, a different template,
scoop,-and pair of rubber gloves should be used to take each sample. The
30
L
template and scoop may then be placed in a plastic bag to be taken back to the
laboratory to be cleaned for the next field sampling job. The rubber gloves
should be discarded into a plastic bag which will be disposed of as PCB-
contaminated material if any samples exhibit PCB contaminatior..
If a·sufficient number of templates or scoops are not available to
use only one item per sample, then each of these equipment items must be
thoroughly cleaned between samples. The template and scoop should be thor-
oughly rinsed with solvent and wiped with a disposable wiping cloth (which
should be discarded _ jnto the plastic bag intended for disposal of PCB-
contaminated materials).
6.2 Soil Core-Sampling
When core:samples of sod or soil are needed, the samples may be taken
using a coring device ~uch as a piston corer or King-tube sampler. Core sam-
ples ~hould be _taken toe depth of about 5 cm. The soil core can be pushed
out into~ preclean~d gla~~ ~oitl~ ~nd ·capped, or the tube containing the sam~
ple can be wrapped in solverit-rinsed ·aluminum foil, depending upon the type·
of __ c~r_in_g devi:e used. The sampi_e ~hould be prope~ly la_beled, a yeil.ow .TSCA
PCB mark . affixed, and _placed .in an ice chest ·(to keep ·the sample about 4°C); .
. :If samples "are _ to ·be a"nalyzed soon,· the cold storage requirements may be re-:
laxed as lo~g ~s s~mp·l~ integr_ity is maintained. The sample collection data _.
s~ould b·e ente·;·e:ci "i~"the .fie.id log book and ·on the chain-of-custo~y form ..
Core .~am~les ·of soil or.sod should .b~ taken .with individual ~ore
.tubes for ~a~h-~am~le. If_ this is_ not possibl~, then the coring device should
be ri~sed with. iolv~~t ~nd wip~d with a disposable wipe cloth to remov~ any -~-
visible particles ·b~for.e t~king anot.her sample. After each.-sarn"ple, r:ubber .:; ,,
gloves a·~d ·wip.e ~-lath sh~~ld .. be .di.scarded into a plastic bag intended for dis-_-. . . . .. . . . ..... · ... · .
posal of PC~-co~timinaied materials.
31
'' I !
6.3 Water Sampling
PCB spills on water may result in a surface film (particularly when
the PCBs are dissolved in hydrocarbon oils) or sink to the bottom (particu-
larly when· the PCBs are in askarel or other heavier-than-water matrix). When
a surface film is suspected (or visible), the water surface should be sampled.
Otherwise, a water sample. should be .taken near the bottom of the body of water.
6.3.l Surface Sampling
Surface water samples should be collected by lowering an open, pre-
cleaned glass sample bottle horizontally into the water at the designated sam-
ple collection point. As water begins to run into the bottle, slowly turn
the bottle upright, keeping the lip just under the surface so that only surface
water is collected. Lift the bottle out of the water, wipe the outside with
a disposable wiping cloth, and cap the bottle. Label the bottle, affix a
yellow TSCA PCB mark, and put the bottle in an ice chest (to keep the sample . . . .
at about 4°C). · If samples are to be analyzed soon, the cold storage require-
ments may be relaxed as long as sample integrity is mainta i ned . The sample
collection data should be entered in the field log book and on the chain-of-
custody form. The wiping cloth and rubber gloves should be discarded into a
plastic bag used for disposal of PCB-co~taminated materials .
6.3.2 Subsurface Sampling
Water near the bottom of the body of water should be sampled by
lowering a sealed sampler bottle to the required.depth, remo~ing the bottle
top, allowing the bottle to fill, and removing the bottle from the water .
Tran~fe~ the subsurface sample into a precleaned glass bottle and cap. Wipe ~
the -~ottle with a disposable ~iping cJoth, fill out and label the sample b?t-
tle, affix a yellow TSCA PCB mark, and put the sample bottle in ary ice chest.
If samples are to be analyzed soon, the cold storage requirements may be re-
:1xed as long as sample integrity is maintained. The sample collection data
,~ould be entered into the field log book and on the chain-of-custody form.
32
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The wiping cloth and rubber gloves should be discarded into a plastic bag
used for disposal of PCB-contaminated materials.
To prevent cross-contamination of samples, separate sampler bottles
should be used to take the samples. Alternatively, the sampler bottle can be
rinsed three times with distilled water, solvent-rinsed, and air7dried between
samples.
Sometimes the above approaches to water sampling are not feasible.
In these cases, other equipment such as siphons, pumps, dippers, tubes, etc.,
may be used to collect a water sample and transfer it to a precleaned glass ·
sample bottle. The sampling system should be constructed of glass, stainless
steel, Teflon, or other inert, impervious, and noncontaminated materials.
Water samples taken with siphons, dippers, tubes, pumps, etc., may become
cross-contaminated if the equipment is not cleaned between samples. Equipment
cleaning may be achieved in most cases by flushing the equipment with dis-
tilled water and solvent.
6.4 Surface Sampling
Samples of hard surfaces may be taken by two methods: (a) wipe
sampling and (b) destructive sampling. Wipe samples are taken of any smooth
surface which is relatiy~ly nonporous (such as rain gutiers, automobiles, and
aluminum siding), while destructive sample~ are taken of hard porous surfaces
(such as concrete, brick, asphalt, and wood). Both wipe and destructive sam-
ples may be taken if it is not known whether the surface is porous or not.
6.4.1 Wipe Sampling
A wipe sample is taken by first applying a suitable solvent (such
as isooctane) to a piece of 11 cm filter paper (e.g., Whatman 40 ashless or
Whatman 50 smear tabs) or gauze pad. The moistened filter paper or gauze
pad is then held with a pair of stainless steel forceps or rubber gloves and
33
rubbed thoroughly over a 100-cm2 area (delineated by a template) of the sam-
ple surface to obtain the sample. The filter or pad is placed in a precleaned
sample bottle, which is then capped, labeled, affixed with a yellow TSCA PCB
mark, and placed in an ice chest (to keep the sample at about 4°C). If sam-
ples, are to be analyzed soon, the cold storage requirements may be relaxed
as long as sample integrity is maintained. The sample collection data are
entered into the field log book and on the chain-of-custody form.
The template should be thoroughly rinsed with solvent and wiped
with a disposable wiping cloth. The rubber gloves worn when taking wipe sam-
ples and the wiping cloth should be discarded into a plastic bag for disposal
6f Pcs:contaminated materials.
6.4.2 Destructive Sampling
Wipe sampling is not appropriate on some porous surfaces, such as
wood, asphalt, concrete, and brick, which will absorb the PCBs. In some
cases, these surfaces can be sampled by taking a discrete sample such as a
piece of wood or pav i ng brick. Otherwise, chisels, drills, hole saws, etc.,
can be used to remove sufficient sample for analysis . ·samples less than 1 cm
d~~p ~ho~ld be taken and placed in a glass sample bottle or solvent-rinsed
alum1n~m foil. Each sample container should be labeled, affixed with a yellow
I . TSCA _PCB mark, and pl aced in an ice chest. If samples are to be analyzed soon,
'the .cold storage requirements may be relaxed as long as sample integrity is . .
mai~tained .. Sample collection data should be entered into the field log book
and ~n the chain-of-custody form.
Equipment used to take samples of wood, asphalt, etc., should be
cleaned with solvent and wiped between samples. Also, rubber gloves and wipe
cloths should be discarded into a plastic disposal bag intended for PCB-.
contaminated materials.
,/
I'
34
f '
(:
I
!
r -
; '
6.5 Veaetation Sampling
The sample design or visual observation may indicate that samples
of vegetation, such as tree leaves, bushes, and flowers, are required. In
this case, th~ sample may be taken with pruning shears, a saw, or other suit-
able tool, and placed in a precleaned glass bottle, which should be capped,
labeled, a~fixed with a yellow TSCA PCB mark, and placed in an ice chest.
If samples are to be _ analyzed soon, the cold storage requi-r-ements may be re-
laxed as long as sample integrity is maintained. The sample collection data
should be entered into the field log book and on the chain-of-custody form.
After each sample is taken, the pruning shears should be rinsed with
solvent and wiped with a disposable ~ipe cloth to prevent cross-contamination
between samples. Also, rubber gloves and wipe cloths should be discarded into
a plastic disposal bag intended for PCB-contaminated materials.
6.6 Comoositing Strategies
Compositing is the pooling of several samples to form one sample
for chemical analysis. In many circumstances it may be desirable to com-
posite samples to reduce the number of (often costly) analyses needed. The
t · suggested strategies for compositing samples are given in the appendix .
. 7.0 QUALITY ASSURANCE
Quality assurance must be applied throughout the entire sampling
program, inc1uding_sample design and sample collection, handling,_and preser-
vation.,_, Each EPA office must develop a quality assurance plan (QAP) accord~ . ., . . . . . . . ..... _. .. -·-.. .. .
in_g ~o:~PA guideli~es (USEPA 1980). The QAP must b~ submitted t~ the re~-
gion_al :QA officer or. other appropriate QA official for approval prior to
saTpl_i~g PCB spill sites.
35
The elements of a QAP (USEPA 1980) include:
Title page
Table of contents
Project description
Project organization and responsibility
QA objectives for measurement data in terms of precision, accuracy,
completeness, representativeness, and ··comparability
Sampling procedures
Sample tracking and traceability
Calibration procedures and frequency
Analytical procedures
Data reduction, validation, and reporting
Internal quality control checks
Performance and system audits
Preventive maintenace
Specific routine procedures used to assess data precision,
accuracy, and completeness
Corrective action
Quality assurance reports to management
Each EPA inspector who will sample PCB spill sites should understand
and conform with all elements of the QAP.
8.0 QUALITY CONTROL
Each EPA office that samples PCB spill sites must operate a formal ,,
quality control (QC) program. The minimum requirements of this program con-
sist ·of ·preparing field blanks .for the laboratory; sampling without contam-
ination of· samples; maintaining a rigid chain-of-custody procedure for the
samples; and fully documenting the entire sampling program a~d maintaining
records of the documentation.
36
The quality control measures taken by each EPA office should be
stipulated in the QA plan. The QC measures discussed below are given as ex-
amples only. EPA offices must decide which of the following measures, and
additional measures, will be required for each situation.
8.1 Field Blanks
Field blanks are given to the laboratory to-demonstrate that the
sampling equipment has not been contaminated. A field blank may be generated
by using the sampling equipment to obtain a clean sample of solids or water.
For example, the scoop or soil coring device can be used to obtain a clean
solids blank sample. The water sampling equipment can be used to collect a
blank sample using laboratory reagent grade water. These field blanks should
be obtained both before and after field sampling.
Field blanks for wipe samples should be obtained in the field by
wetting a clean filter paper with the solvent and storing the wetted paper in
a clean sample jar.
One empty glass sample bottle and one filled with solvent should
also be given to the laboratory as field blanks.
8.2 Samolina Without Contamination
Samples collected from PCB spill sites which have been cleaneq up
may become contaminated in two ways: (a) dirty sample containers, and (b)
cross-contamination of samples from the use of contaminated sampling equip-
ment. The first type of contamination can be eliminated by properly pre-
-cleanin~ all sample c6~tainers prior to making the sampling trip. All ~la~s ·
jars should be washed with soap and water, rinsed three times with distilled
water, rinsed with solvent (isooctane is recommended), baked in an oven at
350°C for l h, and iealed with a Teflon-lined cap. All aluminum foil used
should be rinsed with solvent.
37
The sampling equipment should be precleaned before the site visit
by rinsing with solvent and thoroughly wiping the equipment down. Cross-
contamination during sampling can be avoided by using a separate sampler (such
as a scoop, spatula, corer, etc.) for each sample, or cleaning the sample
equipment between samples. Methods that can be used to clean the equipment
between· samples are given in the sample collection, handling, and preservation
discussion (Section 6.0).
8.3 Sample Custody
As part of the quality assurance plan, the chain-of-custody proto-
col must be described. A chain-of-custody provides defensible proof of the
'sample, and data integrity. The less rigorous sample traceability documenta-
tion merely provides a record of when operations were performed, and by whom.
Sample traceability is not acceptable for enforcement activities.
Chain-of-custody is required for analyses which may result in legal
proceedings, and when the data must be subject to legal scrutiny. Chain-of-
custody provides conclusive written proof that samples are taken, transferred,
·prepared, and analyzed in an unbroken line as a means to maintain sample in-
tegrity. A sample is in custody if:
It is in the possession of an authorized individual.
It is in the field of vision of an authorized individual.
It is in a designated secure area.
It has been placed in a locked container by an authorized
individual.
A typical chain-of-custody protocol contains the following elements:
1.· Unique sample identification numbers.
38
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2. Records of sample container preparation and integrity prior to
sampling.
·3_ Records of the sample collection, such as:
-Specific location of sampling.
Date of collection.
-Exact time of collection.
-Type of sample taken (e.g., water, soil).
-Initialing each entry.
-Entering pertinent information on chain-of-custody record.
Maintaining the samples in one's possession or under lock and
key.
-Transporting or shipping the samples to the analytical laboratory.
-Filling out the chain-of-custody records:
Chain-of-custody records accompanying the samples.
4. Unbroken custody during shipping. Complete shipping records
must be retained; samples must be shipped in locked or sealed (evidince tape)
containers. ~he addressee should be notified and prepared to receive the ·
samples from the shipper.
8.4 Oocumentati~~ of Field Sampling
In order to as~ure th~t the field sampling project has been
thoroughly documented, the documents described in the next section should be
used to maintain the quality of the project.
39
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9.0 DOCUMENTATION AND RECORDS
Each EPA office is responsible for preparing and maintaining com-
plete records of the field sampling operations. A detailed documentation plan
should be prepare~ as a part of the QAP, and should be strictly followed. The
following written records should be maintained for each field sampling opera-
ti on:
Equipment preparation log book
Sample codes
Field log book
Site descripti9n forms
Chain-of-custody forms
Sample analysis request forms
Field trip report
9.1 Equipment Preparation Loa Book
A log book should be maintained which lists the sampling equ i pment
taken to each spill site. A detailed description of the cleaning and prepara-
tion procedures used for the sample collection equipment (templates, scoops,
glass bottle, etc.) should be recorded.
9.2 Sample Codes
Each sample should be assigned a unique sample code and labeled
accordingly when collected. The sample code should contain information on
the _ site and which sampling point the ~ample represents. This sample code .•
must be used to _ identify all sample records. --·-----·
Each sample must also be labeled with a yellow TSCA PCB mark as
described in 40 CFR 761.45 until it is determined to be PCB free.
40
9.3 Field Log Book
The EPA inspector should maintain a field log book which contains
all information pertinent to the field sampling program. The notebook should
be bound and entries be made in ink by the field insp ~~tor. All entries
should be signed by the inspector.
At a minimum, the log book should include the following entries:
Owner of spill site
Location of spill site
Date(s) of sample collection
Exact times of sample collection
Type of samples taken and sample identification numbers
Number of samples taken
Description of sampling methodology
Field cbservations
Name and address of field contact
Cross-reference of sample identification numbers to grid sample
points (shown on site description forms)
Since sampling situations will vary widely, no specific guidelines
can be given as to the extent of information which should be entered into the
field log book. Enough information should be recorded, however, so that some-
one can reconstruct the sampling program in the absence of the field inspector.
The field log book should be maintained in a secure place.
·9_4 Site Description Fo~~s ·
Serialized site descript~on forms should be used to record the con-
ditions of the site, provide sketches of the site, and show the location of
the gr{d sampling points. The grid. samplin~ points-should be sh6wn on di-
mensioned drawings and numbered. These forms should be accompanied by
41
~ photographs (preferably Polaroid-type photographs) of the site. Each form
and photograph should be signed and dated by the EPA inspector.
9.5 Chain-of-Custody Forms
Chain-of-custody forms should be completed and accompany the samples.
These forms should contain the following information:
Project site
Sample identification number
• Date and time of sample collection
Location of sample site
Type of sample (soil, water, etc.)
• Signature of sample collector
Signatures of those who relinquish and those who receive the
samples, and date and time that samples change possession
Inclusive dates of possession
9~6 ~Sample and Analysis Request Forms
A sample analysis request form should accompany the samples de-
livered to the laboratory. The field inspector should enter the following . ,.-..
information on t he form:
Project site
• Name of sample collector
· Sample identification numbers
• Types of samples (soil, water, etc.)
Location of sample site for each sample
• Analysis requested [analyte (i.e., total PCBs), met.hod, desired
method detection limit, etc.],
_____ • QC requirements (replicates, lab blanks, lab spikes, etc.) ... !•.· •
,; .Special handling and storage requirements
42
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The laboratory personnel receiving the samples should enter the
following information on the form:
• Name of person receiving the samples
Laboratory sample numbers
· Date of sample receipt
• Sample allocation
Analyses to be performed
9.7 Field Tr ip Report
The EPA inspector should prepare a brief field trip report to be
maintained on file. The report should provide information such as the proj-
ect site, date(s) of sampling, types and number of samples collected, any
problems encountered, any notable events, and specific reference to the other
documents listed above.
10.0 VALIDATION OF THE MANUAL
A previous draft of this manual entitled 11 Field Manual for Verifi-
cation of PCB Spill Cleanup11 (Draft Interim Report No. 3, Task 37, EPA Prime
Contract No. 68-02-3938, June 27, 1985) was used in a brief field validation
study.·· The primary purposes of the study were to: (1) determine the degree
of difficulty of understanding the grid sampling designs in the field manual;
(2) determine the amount of time and degree of difficulty required to lay out
the sampling grids on simulated PCB spill sites; and (3) identify any concerns
-or problems that may arise in implementing the field manual. To achieve these
g~als,_simulated PCB spill_ sites were constructed for the exerc~se. Four ~er-··
sons (Mr. David Phillipp{ and Mr. Robert Jackson of the EPA Region VII Office ·
and Ms~ Joan Wes t brook and Mr. Ted Harrison of MRI) were selected to ·1ay out
the sampling grids on the spill sites after they had read the field manual .
. .
These four persons had no prior association with developing the field manual.
Other persons from EPA and MRI acted as observers since they were intimately
familiar with the field manual.
43
I •.
Four simulated spill sites having the following characteristics
were laid out:
A rectangle (3 ft x 6 ft)
A parallelogram (about 3 ft on a side)
A circle (about 12 ft diameter)
A square (6 ft on a side)
The first two sites required seven grid sample points, and the other two re-
quired 19 grid sample points.
Each of the four 11 inspectors11 laid out the grid sample points on
two of the four sites after constructing the designs on graph paper. In all
cases the sample points were laid out correctly with little or no difficulty
in 30 min or less. Each inspector commented that there was little or no dif-
ficulty in performing the exercises.
As a final exercise, a large irregular simulated PCB spill site
was constructed, and all attendees participated in laying out the 37 grid
sample points. The spill site was designed so that some sample points were
located on the floor and two adjacent walls to make the exercise relatively
difficult. The 37 grid sample points were laid out correctly with relative .
ease in about 45 min. Some discussions were requir~? to decide how to treat
sampli~g poin~s which fell in the overlap where the two walls intersected.
It was concluded from the exercise and discussions which followed
that: (1) the field manual is easy to follow and understood by people un-
~ ·. :~
familiar with the manual prior to reading it; (2) the grid sample points are
never 11 perfectly11 laid out (with the sampl~ points precisely aligned) so that
some degree of rando~ness is built into the sample designs; (3) the time re-
quired to lay out the gr~d.sample points after the boundaries of the spill
site have been determined is relatively short (less than 1 h); and (4) using
-· this manual, the grid sample points can be correctly laid out by inexperienced
people.
44
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i
11.0 REFERENCES
Boomer BA, Erickson MD, Swanson SA, Kelso GL, Cox DC, Schultz BO . 1985
(August). Verification of PCB spill cleanup by sampling and analysis (second
printing). Interim report. Washington, DC: Office of Toxic Substances, U.S.
Environmental Protection Agency. EPA-560/5-85-026.
Mason BJ. 1982 (October). Preparation of ·soil sampling··prot-ocol: tech-
niques and strategies. ETHURA, McLean, VA, under subcontract to Environ-
mental Research Center, University of Nevada, for U.S. Environmental
Protection Agency, Las Vegas.
USEPA. 1980. U.S. Environmental Protection Agency. Guidelines and specifi-
cations for preparing quality assurance project plans . Office of Monitoring
Systems and Quality Assurance, QAMS-005/80.
USEPA. 1981 (March). U.S. Environmental Protection Agency. TSCA Inspection
Manual.
45
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APPENDIX
STRATEGIES FOR COMPOSITING SAMPLES
L._.
A-1
APPENDIX
This appendix gives suggested strategies for compositing samples
taken from PCB spill sites which are sampled using the grid sampling methods
described in the text of the report. Compositing may result in a savings of
analysis time and cost. Sample compositing is not required and should be
used only if time or cost savings may result. The ~trategies for -forming
composites are as follows:
1. Composite only samples of the same type (i.e., all soil or all
water). Since the composite must be thoroughly mixed to ensure homogeneity,
certain types of samples such as asphalt, wipe samples, wood samples and
other hard-to-mix matrices should not be composited.
2. Do not form a composite with more than 10 samples, since in
some situations compositing a greater number of samples may lead to such low
PCB levels in the composite that the recommended analytical method approaches
its limit of detection and becomes less reliable.
3. For each type of sample, determine the number of composites to
be formed using the table below.
Number of samples
2-10
11-20
21-30
31-37
Number of composites
1
2
3
4
As much as possible, try to form composites of equal size. For
example, if ~7 soil samples are taken, then four composites could be formed
using 9, 9, 9, and 10 samples apiece.
A-2
I .
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L
4. · To the extent possible, composite adjacent samples. If resi-
dual contamination is present, it is likely that high PCB levels will be
found in some samples taken close together.
Be.cause of the large number of situations that may be encountered
in practice, it is not possible to specify compositing strategies more pre-
_cisely. The laboratory and field staff should exercise judgment in all cases.
A-3
-, ·-1 I ·-j I j
I
I . TECHNICAL REPORT DATA (Plccu re::d /Nun,crions 011 the ,e,·,-nc before com{'leting)
1. AE:>ORT NO. 12. IJ. REcIPIENT'S AccessI oi-.Nc. EPA-560/5-86-017
.:. ,I,L: .l.NO SUBTITLE 5. REPORT OATE
Field Manual for Grid Sampling of PCB Spi 11 Sites May 1986
to Verify Cleanup 6. PERFORMING ORGANIZATION COOE
8501-A(37)
7. Al.;THORlSl 8. PERFORMING ORGANIZATION REPO;:;, :-.c.
Gary L. Kelso, Mitchell D. Erickson, David C. Cox* Interim Report No . 3
t
9. PERFORMING ORGANIZATION NAME ANO AOOAESS 10. PROGRAM ELEMEN, NO. Midwest ·Research Institute *Washington Consulting Work Assignment No. 37 425 Volker Boulevard Group 11. CONTAACT/CiA,:,.N, 1-<0.
Kansas City, MO 64110 1625 I Street, N.W . EPA Contract No. 68-02-3938
Washington, DC 20006 .
12. SPONSORING AGENCY NAME ANO AOORESS 13. TYPE OF RE?OAT A N O PEFIIOO COVEFIEC Field Studies Branch, TS 798 Interim, May 1985-May 1986
Office of Toxic Substances, U.S. EPA 14. SPONSORING AGENCY COOE
401 M Street, S.W. Washington, DC 20460
15. SUPPLEMENTARY NOTES The EPA work assignment managers are Daniel ·T. Heggem and Richard A Levy.
The EPA project officers are Dr. Joseph J. Breen and C. R. Stroup.
16. AeSTFIACT
The purpose of this manual is to provide detailed, step-by-step guidance to EPA
staff for using hexagonal grid sampling at a PCB spill site. Guidance is given for
preparing the sample design; collecting, handling, and preserving the samples taken;
maintaining quality assurance and quality controi; and documenting and reporting the
sampling procedures used. An optional strategy for co~positing samples is given in
the appendix. :
This is a companion document to the report "Verification of PCB Spill Cleanup
by Sampling and Analysis" (EPA 560/5-85-026, August 1985, Second Printing). This
11how-to 11 report concentrates on detailed guidance for field sampling personnel and
does not attempt to provide background information on the techniques presented. The
types of field samp l ing situations discussed in this manual are those typically found
when a PCB spi 11 results from a PCB article, PCB container, or PCB equipment spill.
Unusual PCB spill situations, such as elongated spills on higways from a moving
vehicle, large spills in waterways, and large, catastrophic spills, are not addressed.
17. KEY WORDS ANO DOCUMENT ANALYSIS . ,
l . OESCRIPTORS b.lOENTIFIEFIS/OPEN ENOEO TERMS ,. COSATI Fi..:IJ.'GNU!)
PCBs, polychlorinated biphenyls, spills,
spi 11 cleanup, field manual, sampling
::. ::,STAI auT:GN STATEMENT 19. SECURITY Cl.ASS / flu.r R~portJ 121. 55. OF PAu:.S Unclassified
Unlimited 20. SETURIT)' C,l..ASS ,rhu P<lf~I Linc ass1f1ed 122 .. i>RICE
EPA ,arm 2220-1 (9·7l)
United States
Environmental Protection
Agency
Toxic Substances
Ottice ot
T-:>xrc Substa~ces
Washington DC 20460
·VE-RIFICATION OF
. .
E?-=-•::;J:5-3:-::~
Au~:.is:. l 985
PCB SPILL CLEANUP
BY SAMPLING
AND ANALYSIS
10
8 ■ ■ ■
6
4 II ■ ■ ■
2
y 0 ■ ■ ■ ■
2
4 ■ ■ ■ ■
6
8 . . ~ . . a ■ ■ . ,
10 ' ' 10 8 6 4 2 0 2 4 6 8 10
X
~:: Printed on Recvcled Paoer • ·r . •
.r.,
VERIFICATION OF PCB SPILL CLEANUP BY
SAMPLING AND ANALYSIS
By
Bruce A. Boomer
Mitchell 0. Erickson
Stephen E. Swanson
Gary L. Ke 1 so
MIDWEST RESEARCH INSTITUTE
and
David C. Cox
Bradley D. Schultz
WASHINGTON CONSULTING GROUP
INTERIM REPORT NO. 2
WORK ASSIGNMENT 37
EPA Contract No. 68-02-3938
·MRI Project No. 8501-A(37)
and
EPA Contract No. 68-01-6721 WCG Subcontract to Battelle Columbus Laboratories
No. F4138(8149)435
Prepared for:
U.S. Environmental Protection Agency Office of Toxic Substances
Exposure Evaluation Division (TS-798) .. 401 M Street, S.W.
Washingto8, DC 20460
Attn: Mr. Daniel T. Heggem, Work Assignment Manager Or. Joseph J. Breen, Project Officer Richard A. Levy, Work Assignment Manager Joseph S~ Carra, Project Officer
r I -
PREFACE
This Interim Report was prepared for the Environmental Protection
Agency under EPA Contract No. 68-02-3938, Work Assignment 37. The work as-
signment is being directed by Mitchell 0. Erickson. This report was prepared
by Dr. Erickson, Bruce A. Boomer, Gary L. Kelso, and Steve E. Swanson of
Midwest Research Institute (MRI). The sampling design (Section IV.A) was
written by David C. Cox and Bradley 0. Schultz of the Washington Consulting
Group, 1625 I Street, N.W., Washington, O.C. 20006, under subcontract to
Battelle Columbus Laboratories, Subcontract No. F4138(8149)435, EPA Contract
No. 68-01-6721 with the .Design and Development Branch, Exposure Evaluation
Division. The EPA Task Managers, Daniel T. Heggem, Richard A. Levy and John H.
Smith, as well as Joseph J. Breen, Joseph S.Carra, and Martin P. Halper, of
the Office of Toxic Substances, provided helpful guidance and technical in-
formation .
Approved: · q o.,v-.-vi) t ,l~
James L. Spigarelli, Director
Chemical and Biological Sciences
Department
ii
MIDWEST RESEARCH INSTITUTE
{4/~
Clarence L. Haile
Oe ~nager
ohn E. Going
Program Manager
TABLE OF CONTENTS
I. Introduction.
I I. Summary . . .
III. Overview of PCB Spills and Cleanup Activities
A. Introduction to PCB Spills and Cleanup.
1. Current Trends ....... . 2. Limitations of This Overview.
8. Components of the Cleanup Process.
1. Health and Safety ..... . 2. Reporting the Spill . . . . . .
3. Quick Response/Securing the Site. 4. Determination of Materials Spilled/Cleanup
Pl an. . . . . . . . . . . . . . . . . . 5. Cleanup Procedures ........... . 6. Proper Disposal of Removed PCB Materials.
7. Sampling and Analysis
8. Remedial Action .
9. Site Restoration ...
10. Records . . . . . . .
11. Miscellaneous Considerations.
IV. Guidelines on Sampling and Analysis
A. Sampling Design. . . . . .
1.
2.
3.
4.
5.
Proposed Sampling Design.
Sample Size and Design Layout in the Field. Judgemental Sampling .....
Compositing Strategy for Analysis of Samples. Calculations of Average Number of Analyses, and Error Probabilities
8. Sampling Techniques.
1. Solids Sampling
2. Water Sampling.
3. Surface Sampling.
4. Vegetation Sampling
C. Analytical Techniques ..
1. Gas Chromatography (GC)
2. Thin-Layer Chromatography (TLC)
3. Total Organic Halide Analyses .
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P2.ae -
l
1
3
3
3
3
4
4
4
6
6
6
7
7
8
8
8 ·g
9
9
9
16
20
23
24
40
40
41 · . ,
41
42
42
42
49
50
TABLE OF CONTENTS (concluded)
D. Selection of Appropriate Methods
1. Criteria for Selection ..
2. Selection of Instrumental Techniques.
3. Selection of Methods. . .
4. Implementation of Methods
E. Quality Assurance ...
1. Quality Assurance Plan ..
2. Quality Control .
F. Documentation and Records.
G. Reporting Results ..
V. References.
.. .....
Paae -
50
50
50
51
53
54
54
55
58
59
60
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I
I. INTROOUCTI ON
The U.S. Environmental Protection Agency (EPA) under the authority
of the Toxic Substances Control Act (TSCA) Section 6(e) and 40 CFR Section .
761.60(d), has determined that polychlorinated biphenyl (PCB) spills must be
controlled and cleaned up. The Office of Toxic Substances (OTS) has been re-
quested to provide written guidelines for cleaning up PCB spills, with par-
ticular emphasis on the sampling design and sampling and analysis methods to
be used for the cleanup of PCB spills.
This work assignment is divided into two phases. The reports of
Phase I are presented in Draft Interim Report No. 1, Revision No . 1, 11 Cleanup
of PCB Spills from Capacitors and Transformers,11 by Gary L. Kelso, Mitchell
D. Erickson, Bruce A. Boomer, Stephen E. Swanson, David C. Cox, and Bradley
0. Schultz, submitted to EPA on January 9, 1985. Phase I consists of a review
and technical evaluation of the available documentation on PCB spill cleanup,
contacts with EPA Regional Offices and industry experts , and preparation of
preliminary guidelines for the cleanup of PCB spills. The document was aimed
at providing guidance in all aspects of spill cleanup for those organizations
which do not already have working PCB spill cleanup programs.
Phase II, reported in this document, reviews the available sampling
and analysis methodology for assessing the extent of spill cleanup by EPA en-
forcement officials. This report includes some of the information from the
Phase I report, incorporates comments on the Phase I report and the general
issue which were received at a working conference on February 26-27, 1985,
and addresses the issue from the perspective of developing legally defensible
data for enforcement purposes.
This report, intended primarily for EPA enforcement personnel, out-
lines specific sampling and analysis methods to d~termine compliance with EPA
policy on the cleanup of PCB spills. The sampling ~nd analysis methods can
be used to determine the residual levels of PCBs at a spill site following
the completion of cleanup activities. Although the methodologies outlined in
this document are applicable to PCB spills in general, specific incidents may
require special efforts beyond the scope of this report. Future changes in
EPA policy may affect some of the information presented in this document.
Following a summary of the report (Section II), Section III presents
an overview of PCB spills and cleanup activities. The guidelines on sampling
and analysis (Section IV) includes discussion of sampling design, sampling
techniques, analysis, and quality assurance.
I I. SUMMARY
This report presents the results of Phase II of this work assign-
ment . Phase I consisted of a review and technical evaluation of the avail-
able documentation on PCB spill cleanup, contacts with EPA Regional Offices,
and preparation of preliminary guidelines for the cleanup of PCB spills.
1
;---
Phase II (this document) reviews the available sampling and analysis methodol-
ogy for assessing the extent of spill cleanup by EPA enforcement officials.
The report incorporates some of the inform~tion from the Phase I report and
general issues received at a working conference on PCB spills.
The EPA has set reporting requirements for PCB spills and views PCB
spills as improper disposal of PCBs. Cleanup activities have not been stan-
dardized since PCB spills are generally unique situations evaluated on a case-
by-case basis by both the PCB owner (or his contractor) and the responsible
EPA Regional Office. Components of the cleanup process may include protect-
ing the health and safety of workers; reporting the spill; quick response/
securing the site; determination of materials spilled; cleanup procedures;
proper disposal of removed PCB materials; and sampling and analysis. The
level of action required is dependent on the amount of spilled liquid, PCB
concentration, spill area and dispersion potential, and potential human expo-
sure ..
A sampling design is proposed for use by EPA enforcement staff in
detecting residual PCB contamination above a designated limit after a spill
site has been cleaned. The proposed design involves sampling on a hexagonal
grid which is centered on the cleanup area and extends just beyond its bound-
aries. Guidance is provided for centering the design on the spill site, for
staking out the sampling locations, and for taking possible obstacles into
account. Additional samples can be collected at the discretion of the sam-
pling crew.
Compositing strategies, in which several samples are pooled and
analyzed together, are recommended for each of the three proposed designs.
Since an enforcement finding of noncompliance must be legally defensible, the
sampling design emphasizes the control of the false_ oositive rate, the proba-
bility of concluding that PCBs are present above the al1owableTTmit when, in
fact, ~hey are not.
Sampling and analysis techniques are described for PCB-contaminated
solids (soil, sediment, etc.), water, oils, surface wipes, and vegetation. A
number of analytical methods are referenced; appropriate enforcement methods
were selected based on reliability. Since GC/ECD is highly reliable, widely
used, and is included in many standard methods, it is a primary recommended
method for most samples. Secondary methods may be useful for confirmatory
analyses or for special situations when the primary method is not applicable.
Quality assurance (QA) must be applied throughout the entire moni-
toring program. Quality control (QC) measures, including protocols, certifi-
cation and performance checks, procedural QC, sample QC, and sample custody
as appropriate, should be stipulated in a QA plan.
2
III. OVERVIEW OF PCB SPILLS ANO CLEANUP ACTIVITIES
A. Introduction to PCB Soills and Cleanun
The EPA has e~tablished requirements for reporting PCB spills based
on the amount of material spilled and disposal requirements for the spilled
PCBs and materials contaminated by the spill. Under TSCA regulations [40 CFR
761.30(a)(l)(iii) and 40 CFR 761.60d], PCB spills are viewed as improper
disposal of PCBs. Although specific PCB cleanup requirements are not
established in the TSCA regulations, each regional administrator is given
authority by policy to enforce adequate clean-up of PCB spills to protect
human health and the environment.
1. Current Trends
Due to regional variations in PCB spill policy and the lack of a
national PCB cleanup policy, PCB cleanup activities have not been standardized.
Individual companies owning PCB equipment and contract cleanup companies have
developed their own procedures and policies for PCB cleanup activities keyed
to satisfying the requirements of the appropriate EPA Regional Office. In
addition, the EPA Regional Offices typically have provided suggestions for
companies unfamiliar with PCB cleanup.
PCB spills are generally viewed as unique situations to be evaluated
on a case-by-case basis by both the PCB owner (or his contractor) and the EPA
Regional Office. However, a general framework is often used to approach the
problem. Most cleanup activities involve quick response, removal or cleaning
of suspected contaminated material, and post-cleanup sampling to document
adequate cleanup. Major considerations involved in the cleanup process in-
clude minimizing environmental dispersion, minimizing any present or future
human exposure to PCBs, protecting the health and safety of the cleanup crew,
and properly disposing contaminated materials.
In general, the involvement of EPA Regional Offices is limited to
phone conversations often incl~ding a follow-up call to receive the analytical
results of the post-cleanup sampling. If the EPA representative is not satis-
fied with the reported data, additional documentation, sampling and analysis,
or cleanup (followed by further sampling and analysis) may be requested.
In cases of special concern (e.g., large spills), EPA Regional Of-
fices may work more closely with the PCB owner or contractor in planning the
cleanup, sampling and analysis activities, and on-site inspections.
2. Limitati ons of This Overview
The general discussion in this chapter refers to the procedures, .,
policy, and considerations that seem to be widely used at present by PCB
owners and spill cleanup contractors in meeting the requirements of the EPA
Regional Offices. The activities described do not involve EPA regulations or
policy except where indicated, since the EPA has not established requirements
on PCB cleanup procedures.
3
Table 1 categorizes PCB spills into approximate levels of action
for PCB spill cleanup based on concern. Potential environmental problems in-
crease with increases in PCB concentrations _, amount of spilled liquid, spill
area and dispersion potential, and potential human exposure. The three spill
types presented in Table 1 are based on very rough estimates. 11 Severity11 in·
one key item such as human exposure could raise a spill to a Type 3 (i. e.,
requiring special attention). On the other hand a spill of a large volume of
·liquid may be considered a Type 2 spill due to a relatively low concentration
of PCBs. The three categories are only approximate and are intended to demon-
strate the flexibility needed in responding to PCB spills. EPA Regional Of-
fices should provide guidance on spill cleanup activities whenever questions
develop.
The situati~ns described in this chapter are limited to recent PCB
spills of similar magnitude to the reported spills associated with PCB oil
transformers and capacitors (i.e., Type 2 in Table 1). Unusually severe spill
incidents (Type 3 in Table 1) involving large volumes of PCBs, a large spill
area, a high probability of significant human exposure, and/or severe en-
vironmental or transportation scenarios may require special considerations,
beyond the scope of this discussion.
All spills from regulated equipment are typically subject to the
detail of effort outlined in this chapter. Although cleanup of smaller spills
(Type 1 in Table 1) is required if the concentration of PCBs in the spilled
material is 50 ppm or greater, the spill and the cleanup activities normally
are not reported to EPA.
Future changes in EPA policy may invalidate some of the discussions
appearing in this chapter. For example, if EPA adopts any type of formal
categorization scheme for PCB spills, some of the assumptions made in this
chapter may become inappropriate.
B. Components of the Cleanuo Process
1. Health and Safety
Protection of the health and safety of the clean-up crew during the
PCB cleanup operation is an important concern. References discussing health
and safety considerations relevant to some PCB spill incidents include NIOSH
Criteria for A Recommended Standard for Exposure to Polychlorinated Biohenyls
(PCBs) (1977c) and Health Hazards and Evaluation Reoort No. 80-85-745 (NIOSH
1980). The appropriate level of health and safety protection is dependent
upon the specifics of the spill.
2. Reoortina the Spill
If the regulatory 1 i mi ts are• exceeded, the spi 11 must be reported
to Fede.ral, State, and local authorities as applicable. Under EPA regulations
[Fed. Reg. 50:13456-13475], spills over 10 lb must be reported to The National
Response Center. The toll free phone number is [phone].
4
U1 Table 1. /\pproximate Levels of /\ction for rcn Spill Cleanup Oased on Concern '. ' Approximate gallons of spilled liquid /\rea of spill (sq ft) rco concentration in spilled liquid (ppm) Types of spilled liquid Type 1 < 1 < 125 < 500 Mineral oil (or variable) Categories of increasing concern Type 2 Type 3 > 1 . > 5 250 (avg.) > 1,000 ?: 50 Variable or high Variable Variable, Askarel -·· 1 -···-,· Exposure scenario · Various Various Special concern for higli Notes: · Type 1 spill is usually not reported. · }:y~ spill is reported and discussed _in this chapter. }:y~e 3 spill is not discussed in this chapter and may require special EPA assistance. exposure situations .;. "Severity" in one key item may raise the spill to a higher risk category. ,.
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3. Quick Resoonse/Securina the Site
Quick response is desirable to mitigate the dispersion of the
spilled material and to secure the site. Federal regulations require that
cleanup actions commence within 48 hr of discovery of a spill [40 CFR
761.30(a)(l) (iii)]. More rapid response is highly preferable.
A quick response allows removal or cleaning of the PCB-contaminated
material before it is dispersed by wind, rain, seepage, and other natural
causes or by humans or animals. In securing the site, the cleanup crew
determines the spill boundaries, prevents unauthorized access to the spill
site, and notifies all parties involved.
The methods used to secure the site will vary on a case-by-case
basis, .depending on the specific circumstances. The extent of the spill is
usually determined by visual inspection with the addition of a buffer area
that may include PCBs finely dispersed from splattering. Evaluating the ex-
tent of the spill involves considerable judgment, including consideration
of the cause of the spill, weather conditions, and specifics of the site.
Field analysis kits may aid the crew in determining the extent of
the spill in some instances. The field kits, when used properly, can serve
as a screening tool. The need for quick ~esponse has limited the usefulness
of the more accurate field analytical techniques such as field gas chroma-
tography. Practical problems associated with availability of the equipment
and trained staff, set-up time, and cost have limited the use of such tech-
niques at this time.
4. Determination of Materials Soilled/Cleanuo Plan
After securing the site, the response crew will either (a) immedi-
ately proceed with the cleanup operation, or (b) identify the materials
spilled and formulate an appropriate cleanup plan. A suitable cleanup plan
can be developed by identifying the type of PCB material (i.e., mineral oil,
PCB oil, Askarel) and considering such factors as the volume spilled, area
of the spill, and site characteristics.
Based on reasoning similar to Table 1, the crew leader can determine
the necessary level of effort in accordance with the policy of the PCB owner
and the EPA Regional Office. He can determine if additional guidance is
needed, plan the sampling and analysis, and make other decisions related to
the level of effort and procedures needed.
5. Cleanuo Procedures
The cleanup procedure may include, but may not necessarily be limited
to, the following activities:
Removal or repair of failed/damaged PCB equipment,
Physical removal of contaminated vegetation;
6
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Physical removal of contaminated soils, liquids, etc.,
Decontamination or physical removal (as appropriate) of con-
taminated surfaces, and
Decontamination or removal of all equipment potentially con-
taminated during the cleanup procedures.
Encapsulation may be employed only with EPA approval.
The specific procedures used in a cleanup are selected by the PCB
owner or the -cleanup contractor. Key considerations include removal of PCBs
from the site to achieve the standards required by the EPA region, company,
or other applicable control authority; avoidance of unintentional cross con-
tamination or dispersion of PCBs from workers' shoes, contaminated equipment,
spi 11 ed cleaning sol vents, rag_s_!.. __ an~ ~1::her sources; and protection of workers'
health.
The cleanup crew shall make every possible effort to keep the spilled
PCBs out of sewers and waterways. If this has already occurred, the crew needs
to contact the local authorities. Water is never used for cleaning equipment
or the spill site.
. A simple PCB spill cleanup may involve the removal of the leaking
equipment, removal of contaminated sod and soil by shovel, cleaning pavement
with an absorbant material and solvents, and decontamination or disposal of
the workers' equipment (shovels, shoes, gloves, rags, plastic sheets, etc.).
More complicated situations may include decontamination of cars, fences,
buildings, trees and shrubs, electrical equipment, or water (in p~ols er
bodies of water). ·
In some cases, adequate decontamination of surfaces (pavements,
walls, etc.) may not be possible. An alternate to physical removal of the
surface material is encapsulation of the contaminated area under a coating
impervious to PCBs. (EPA approval would be required.)
6. Proper Oisoosal of Removed PCB Materials
All PCB-contaminated materials removed from the spill site, must be
shipped and disposed in accordance with relevant Federal, State, and local
regulations. TSCA Regulations [40 CFR 761.60] outline the requirements for
the disposal of PCBs, PCB articles, and PCB containers in an incinerator,
high efficiency boiler, chemical waste landfill, or an approved alternative
method. Facility requirements for incineration and chemical waste landfills
are presented in 40 CFR 761.70 and 40 CFR 761.75, respectively. Applicable .,
Department of Transportation regulations are listed in 49 CFR 172.101.
· 7. Samoling and Analysis
Although sampling and analysis will be discussed in detail in Chap-
ter IV, this discussion gives an overview of applicable considerations and
current practice. Sampling and analysis may not alway~ be needed (especially
for the spills described as Type 1 in Table 1), ·but enforcement authorities
or property owners may ask for proof that the spili site has been adequately
7
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I decontaminated. This can be accomplished by taking a number of samples repre-
sentative of the area contaminated by the spill. Samples should repreient
the full extent of the spill, both horizontal ~nd vertical, as well as the
types of materials in the spill area (soil, surfaces, water, etc.).
Sampling design and technique as well as sample handling and preser-
vation should incorporate acceptable procedures for each matrix to be sampled
and concern for the adequacy and ~ccuracy for the samples in the final analysis.
Analysis of the samples for PCB content should be performed by
trained personnel using acceptable procedures with due consideration of qual-
ity assurance and quality control.
Further discussion of sampling and analysis (applicable to EPA en-
forcement activities) appears in Chapter IV.
8. Remedial Action
If the analysis results indicate the cleanup was not in compliance
with designated cleanup levels, additional cleanup is needed. Additional
sampling can pinpoint the location of remaining contaminated areas if the
original sampling plan was not designed to identify contaminated sub-areas
within the spill site. If additional cleanup is needed, the cleanup crew will
continue as before, removi"ng more material or cleaning surfaces more thoroughly.
Remedial action will be followed by additional sampling and analysis to ver-
ify the adequacy of the cleanup.
9. Site Restoration
This is not addressed under TSCA and is a matter to be settled be-
tween the company responsible for the PCB spill and the property owner.
10. Records
Although there are no TSCA requirements for records of PCB cleanup
activities except for documentation of PCBs stored or transported for disposal
[40 CFR 761.80(a)], the PCB owner should keep records of the spill cleanup
in case of future questions or concern. Relevant information may include
dates, a description of the activities, records of shipment and disposal of
PCB-contaminated materials, and a report of collected samples and results of
analysis.
11. Miscellaneous Considerations
a .. Exceditious and effective action are desired throughout tne
cleanup process to minimize the concern of the public, especially residents
near the site or individuals with a s~ecial interest in the site. Likewise,
speed and effectiveness in the cleanup may prevent any future concern or action
related to the PCB spill.
b. Education and training of the spill response crews and re-
sponsible staff members is a constant concern. The employees need sufficient
training to make proper judgements and to know when additional assistance or
guidance is needed.
8
IV. GUIDELINES ON SAMPLING AND ANALYSIS
Reliable analytical measurements of ~nvironmental samples are an
essential ingredient of sound decisions for safeguarding public health and
improving the quality of the environment. Effective enforcement monitoring
should follow the general operational model for conducting analytical mea-
surements of environmental samples, including: planning, quality assurance/
quality control, verification and validation, precision and accuracy, sam-
pling, measurements, documentation, and reporting. Although many options are
available when analyzing environmental samples, differing degrees of reli-
ability, dictated by the objectives, time, and resources available, influence
the protocol chosen for enforcement monitoring. The following section out-
lines the factors critically influencing the outcome and reliability of en-
forcement monitoring of PCB spill cleanup.
A. Samolina Desian
This section presents a sampling scheme, for use by EPA enforce-
ment staff, for detecting residual PCB contamination above a limit designated
by EPA-OPTS after the site has been cleaned up. Two types of error traceable
to sampling and analysis are possible. The first is false positive, i.e.,
concluding that PCBs are present at levels above the allowable limit when, in
fact, they are not. The false positive rate for the present situation should
be low, because an enforcement finding of noncompliance must be legally de-
fensible; that is, a violator must not be able to claim that the sampling re-
sults could easily have been obtained by chance alone. Moreover, all sampling
designs used must be documented or referenced.
The second type of error possJble is a false neaative, i.e.,. failure
to detect the presence of PCB levels above the allowable limit. The false
negative rati will depend on the size of the contaminated area and on the
level of contamination. For 1arge areas contaminated at levels well above
the allowable limit, the false negative rate must, of course, be low to en-
sure that the site is brought into compliance. The false negative rate can
increase as the area or level of contamination decrease.
1. Proposed Samoling Desian
In practice, the contaminated area from a spill will be irregular
in shape. In order to standardize sample design and layout in the field, and
to protect against underestimation of the spill area by the cleanup crew, sam-
pling within a circular area surrounding the contaminated area 1s proposed.
Guidance on choosing the center and radius of the circle, as well as the number
of sample points to be used is provided in Section 2 below.
, ,
The detection problem was modeled as follows: try to detect a
circular area of uniform residual contcmination whose center is randomly
placed within the sampling circle. Figure 1 illustrates the model. The
figure depicts a sampling circle of 10 ft centered on a utility pole (site of
the spill). After cleanup, a residually contaminated circle remains. How-
ever, in choosing locations at which to sample, the sampler has no knowledge
of either the location of the circle or the level of contamination. This
9
r !
______ _.,. Utility Pole
r = 10 ft
Randomly Located
Area of Residual
Contamination
Sampling Circle
Fiqure 1. Randomly located area of residual contamination
within the samolinq circle.·
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1ack of knowledge was mode1ed by treating the sampling locations as fixed and
the center of the contaminated circle as a randomly located point in the circle
of radius 10 ·ft. The implicit assumption that-residual contamination is equally
likely to be present anywhere within the sampling area is reasonable, at 1east
as a first approximation (Lingle 1985). This is because more effort is likely
to have been expended in c1eaning up the areas which were obviously highly
contaminated.
Two general types of design are possible for this detection problem:
grid designs and random designs. Random designs have two disadvantages com-
pared to grid designs for this application. First, -random designs are more
difficu1t to implement in the field, since the sampling crew must .be trained
to generate random 1ocations onsite, and since the resulting pattern is ir-
regular. Second, grid designs are more efficient for this type of problem
than random designs. A grid design is certain to detect a sufficiently large
contaminated area while some random designs are not. For example, the sug-
gested design with a sample size of 19 has a 100~ chance to detect a contam-
inated area of radius 2.8 ft within a sampling circ1e of radius 10 ft. By
contrast, a design based on a simp1e random sample of 19 points has only a
79% chance of detecting such an area.
Therefore, a grid design is proposed. A hexagonal grid based on
equilateral triangles has two advantages for this problem. First, such a grid
minimizes the circular area certain to be detected (among all grids with the
same number of points covering the same area). Second, some previous experi-
ence (Mason 1982; Matern 1960) suggests that the hexagonal grid performs well
for certain soil sampling problems. The hexagonal grid may, at first sight,
appear to be compl ·icated to lay out in the field. Guidance is provided in
Section 2 below and shows that the hexagonal grid is quite practical in the
field and is not significantly more difficult to deploy than other types of
grid.
The smallest hexagonal grid has 7 points, the next 19 points, the
third 37 points as shown in Figures 2 through 4. In general, the grid has
3n2 + 3n + 1 points. To completely specify a hexagonal grid, the distance
between adjacent points, s, must be determined. The distances was chosen
to minimize, as far as possible, the size of the residual contaminated circle
which is certain to be sampled. Values of s so chosen, together with number
of sampling points and radius of smallest circle certain to be sampled are
shown in Table 2. For example, the grid spacing for a circ1e of radius 20 ft
for the 7-point design is s = (0.87)(20) = 17.4 ft. For a given size circle,
the more points on the grid, the smaller the residual contamination area which
can be detected with a given probability.
11
No. of
points
7 ·'
19
.37
Table 2. Parameters of ~exagonal Sampling Designs for a
Sampling Circle of Radius r Feet
Distance between adjacent
points, s (ft)
I
0. 87r -
0. 48r -
0.3r
12
Radius of smallest circle
certain to be sampled
0. 5r
0.28r
0.19r
4
3
2
1
y 0
1
2
3
4
0
\ \ I \ \
□-. -■c . ----··~ --
0 0
' 4 3 2 0 2 .. --.. -·
X
The outer boundary of the contaminated area
is ·;ssumed to be 4 feet from the ce_nter· ( C)
of the spi 11 site. ·
Fi gure 2. Location ~f sampling points in
a 7-point grid.
13
0
3 4
1--I
1·•.
f--
~
I
!·:.
r·-·
y
.,+
10
8 0 0 0
6
4 0 0 0 0
2
0 0 0 ■C □ □
2
4 0 □ 0 0
6
8 0 0 □
10.___.__. _ _.____.__._ ___ _.._ ____ _._____._......__.___.._.......__,__...._ _____ _..___.____.
10 8 6 4
-
2 0
X
2 4 6
The outer boundary -of the contcminated area is assumed to be
10 feet from th~ center (C) of the spill site.
8
Figure 3. Location of sampling points in a 19-point ~rid.
14
10
i
i
r
20
,---16 D D D D I .,
12
□ D D □ □
8
□ D D D D □ 4
y 0 D □ D ■C □ □ 0
4
0 D D D 0 0
8
0 0 D 0 D
12
16 0 D D □
20 I I
20 16 12 8 4 0 4 8 12 16 20
X
The outer boundary of the contami noted area is cssumed to be
20 feet from the center {C) of the spill site.
Figure 4. Location of sampling points in a 37-point grid.
15
The first three hexagonal designs are shown in Figures 2 to 4, for a sampling circle radius of r = 10 ft. The choice of sample size depends on the cost of analyzing each sample and the reliability of detection desired for various-residually contaminated areas. ·subsection 2 below provides some suggested sample sizes for different spill areas, based on the distribution of spill areas provided by the Utility Solid Waste Activities Group (USWAG 1984; Lingle 1985).
2. Sample Size and Desian Lavout in the Field
a. Sample Size
The distribution of cleanup areas for PCB capacitor spill sites, based on data collected by USWAG (1984; Lingle 1985) is shown in Table 3. The smallest spill recorded in the USWAG database is 5 ft2 , the largest 1,700 ft2 . The median cleanup area is 100 ft, the mean 249 ft2 ; the wide dis-crepancy between the mean and the median reflects the presence of a small per-centage of relatively large spills in the database.
Recommended sample sizes are giv.en in Table 4. Several con-siderations were involved in arriving at these recommendations. First, the maximum number of samples recommended for the largest spills is 37, in recog-nition of practical constraints on the number of samples that can be taken. Even so, it is important to note that not all samples collected will need to be analyzed. The calculations in Section 5 below show that, even for the 37 sample case, no more than 8 analyses will usually be required to reach a de-cision. Since the cost of chemical analyses is a substantial component of sampiing and analysis costs, even the 37-sample case should not, therefore, be prohibitively expensive. Second, the typical spill will require 19 sam-ples. Small spills, with sampling radius no greater than 4 ft, will have 7 samples, while the largest spills, with sampling radius 11.3 ft and up, will require 37 samples. It should be noted that only capacitor spills are repre-sented in Table 3. Transformer spills, however, would be expected to be generally smaller than capacitor spills because energetic releases are less likely from transformers. Thus, one would expect the smaller sample sizes to be relatively more likely for transformer spills than capacitor spills.
16
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Sampl1n~ area . ( ft )
~ 50
51-400
> 400
Table 3. Distribution of PCB Capacitor Spill
Cleanup Areas Based on ~0 Cases
Cleanup area (ft2)
~ 50
51-100
101-200
201-300
301-400
401-700
701-1,300
~ 1,300
Source: Lingle 1985.
Table 4. Recommended
Radius of samol1na
c·; rel e (ft) -
~ 4
4-11.3
> 11. 3
17
Percent of cases
32.5
18.8
15.0
12.5
Sample
.3.8
7.5
8.8
1.3
Sizes
Percent of PCB
capacitor spills
32.5
50.0
17.5
Sample size
7
19 ✓
37
i F-"
! i
I ..
\--
' .
The final consideration in recommending sample sizes was to
achieve roughly comparable detection capability for different size spills.
The radius of the smallest contaminated circle,.certain to be sampled at least
once by the sampling scheme is used for comparative purposes (see Table 2).
Table 5 presents some calculations of this quantity. The absolute detection.
capability of the sampling scheme is seen to be relatively constant for dif-
ferent spill sizes. This means that a given area of residual contamination I
is about as likely to be detected in any sized spill.
Table 5. Detection Capability of the Recommended Sampling Schemes
Sampling area Radius Sample Radius of smallest circle to
(ft2 ) (ft) size be sampled (ft)
50 4.0 7 ... 2.0
150 6.9 19 l. 9
. 400 11. 3 19 3.2
875 16.7 37 3.2
b. Design Lavout in the Field
Figure 5 presents a typical illustration of design layout·in
the field. The first step is to determine the boundaries of the original
cleanup area (from records of the cleanup). Next, find the center and radius
of the sampling circle which is to be drawn surrounding the cleanup area.
The following approach is recommended: ·
(a) Draw the 1ongest dimension, L1 , of the spill area.
(b) Determine the midpoint, P, of L1 •
(c) Draw a second dimension, L2 , through P perpendicular to
L1.
(d) The midpoint, C, of L2 is the required center.
(e) The distance from C to the extremes of L1 is the requi~~d
radius, r.
Figure 5 shows an example of the procedure; Figure 6 demonstrates how the center
is determined for several spill shapes. Even if the center determined is
slightly off, the sampling design will not be adversely affected.
18
~-
I f-.
[
LJ
0 □
0 □
(!
12 11
7
:: ~
1
0
---.
r,
-~
Fi~ure 5
19
(c) Original cleanup crea
(b) Locating the center of the
sampling circle
( c) Centering the hexogonc I grid
(d) Staking out the grid points
Once the sampling radius, r, has been found, the sample size
can be selected based on Table 4.
Examcle: Suppose r = 5 ft. From Table 4, a sample size of 19
should be used.
Having selected the sample size, the grid spacing can be calculated from Table
2.
Examcle (continued): For a 19-point design with radius r = 5,
the grid spacing is s = 0.48r = (0.48)(5) = 2.4 ft.
The procedure for laying out a 19 point design is as ·follows.
The first sampling location is the center C of the sampling circle, as shown
in Figure 5. Next, draw a diameter through C and stake out locations 2
through 5 on it as shown; adjacent locations are a distances apart. The
orientation of the diameter (for example east-west) used is not important; it
may be chosen at random or for the convenience of the samplers. The next 4
locations, Nos. 6-9, are laid out parallel to the first row, again a distance
s apart. The only difficulty is in locating the starting point, No. 6, for
this row. To accomplish this the sampler needs two pieces of rope (or sur-
veyor's chain, or equivalent measuring device) of lengths. Attach one piece
of rope to the stake at each location 4 and 5. Draw the ropes taut horizontally
until they touch at location 6. Once the second row is laid out, the third
and final row of 3 locations in the top half of the design is found similarly,
starting with number 10. In the same way, the bottom half of the design is
staked out. The 7-point or 37-point designs are laid out in an analogous
fashion.
Once the sampling locations are staked out the actu~l samples
can be collected. In the example in Figure 5, three of the sampling locations
fall outside the original cleanup area. Samples should be taken at these
points, to detect contamination beyond the original cleanup boundaries. This
verifies that the original spill boundaries were accurately assessed.
In practice, various obstacles may be encountered in laying
out the sampling grid. Mar,y 11 obstacles11 can be handled by taking a different
type of sample, e.g., if a fire hydrant is located at a point in a sampling
grid otherwise consisting of soil samples, then a wi~e sample should be taken
at the hydrant, rather than taking a sample of nearby soil. The obstacle most
likely to be encountered is a vertical surface such as a wall. To determine
the sampling location on such a surface, draw taut the ropes (chains) of
lengths attached to two nearby stakes and find the point on the vertical
surface where their common ends touch. See Figure 7 for an illustration of
the procedure. If more samples from the vertical surface are called for, the
same principle may be applied, always using tne last two points located to .,
find the next one.
3. Judaemental Samoling
The inspector or sampling crew may use best judgement to collect
samples wherever residual PCB contamination is suspected. These samples ·are
20
l
r
I r
[
I .
I '
Figure 6. Locating the center and sampling circle radius of an
irregularly shaped spill area.
21
in addition to those collected from the sampling grid. Examples of extra sam-
pling points include suspicious stains outside the designated spill area,
cracks or crevices, ·and any other area where the inspector suspects inade-
quate cleanup.
4. Compositing Strateav for Analysis of Samoles
Once the samples have been collected at a site, the goal of the
analysis effort is to determine whether at least one sample has a PCB concen-
tration above the allowable limit. This sampling plan assumes the entire spiil
area will be recleaned if a single sample contaminated above the limit is
found. Thus, it is not important to determine precisely which samples are
contaminated or even exactly how many . This means that the cost of analysis
can be substantially reduced by employing comoositina strategies, in which
groups of samples are thoroughly mixed and evaluated in a single analysis .
If the PCB level in the composite is sufficiently .b..:i.9..b., one ·can conclude that
a contaminated sample is present; if the level is low enough, all individual
samples are clean. For intermediate levels, the samples from which the com-
posite was constructed must be analyzed individually to make a determination.
Thus, the number of analyses needed is greatly reduced in the presence of
very high levels of contamination in a few samples or in the presence of very
low levels in most samples.
For purposes of this discussion, assume that the maximum allowable
PCB concentration in a single soil sample is 10 ppm. The calculations can
easily be adapted for a different level or for different types of samples.
Based on review of t he available precision and accuracy data (Erickson 1985),
method performance of 80% accuracy and 30% relative standard deviation should
be attainable for soil concentrations above 1 ppm.
To protect against false positive findings due to analytical error,
the measured PCB level in a single sample must exceed some cutoff greater than
10 ppm for a finding of contamination. Assume that a 0.5% false positive rate
for a single sample is desired. As will be shown later, this single sample
false positive rate controls the overall false positive rate of the sampling
schemes to acceptable levels . Then, using standard statistical techniques,
the cutoff level for a single sample is
(0.8)(10) + (2.576)(0.3)(0.8)(10) = 14.2 ppm,
where 0.8(80%) represents the accuracy of the analytical method, 10 ppm is
the allowable limit for a single sample, 2.576 is a coefficient from the stan-
dard normal distribution, and 0.3(30~) is the relative standard deviation of
the analytical method. Thus, if the measured level in a single sample is
14.2 ppm or greater, one can be 99.5% sure that the true level is 10 ppm or =~
greater. --
Now suppose that a composite of, say, 7 samples is analyzed. The
true PCB level in the composite (assuming perfect mixing) is simply the aver-
age of the 7 levels of the individual samples. Let X ppm be the measured PCB
level in the composite. If X ~ (14.2/7) = 2.0, then all 7 individual samples
23
r=
j
F
I I-
1-
I -
: -.
are rated clean. If X > 14.2, then at least one individual sample must be above the 10 ppm limit. If 2.~ < X ~ 14.2~ no conclusion is possible based on analysis of the composite arod the 7 samples~must be analyzed individually to reach a decision. These res~lts may be ~eneralized to a composite of any arbitrary number of samples, subject to the limitations noted below.
The applicability of compositing is potentially limited by the size of the individual specimens and by the performance of the analytical method at low PCB levels. First, the individual specimens must be large enouah so that the composite can be formed while leaving enough material for individual analyses if needed. For verification of PCB spill ~leanup, adequacy of speci-men sizes should not be a prob1em. The second limiting factor is the analyt-ical method. Down to about 1 ppm, the performance of the stipulated analytical methods should not degrade markedly. Therefore, since the assumed permissible level is 10 ppm, no more than about 10 specimens should be composited at a time.
In compositing specimens, the location of the sampling points to be grouped should be taken into account. If a substantial residual area of con-tamination is present, then contaminated samples will be found close together. Thus, contiguous specimens should be composited, if feasible, in order to maximize the potential reduction in the number of analyses produced by the compositing _ strategy. Rather than describe a (very complicated) algorithm for choosing specimens to composite, we have graphically indicated some possi-ble compositing strategies in Figures 8 Through 11. Based on the error proba-bility calculations presented in Section 4 below, we recommend the compositing strategies -indicated in Table 6. The recommended strategy for the 7-point design requires no explanation. The strategies for the 19-and 37-point cases are shown in Figures 9 and 11, respectively. The strategie.s shown in Figures 8 and 10 are used in Section 5 for comparison purposes. For details on the reduction in number of analyses expected to result (as compared to individual analyses), see the next Section, 5.
5. Calculations of Averaae Number of Analyses, and Error Probabil-ities
Estimates of exoected number of analyses and probabilities of false positives (incorrectly deciding the site is contaminated above the limit), and false neaatives (failure to detect residual contamination) were obtained for various scenarios. The calculations were performed by Monte Carlo simula-tion using 5,000 trials for each combination of sample size, compositing strategy, level, and extent of residual contamination. The computations were based on the following assumptions:
a. Only soil samples are involved. In practice other types of samples will often be obtained and analyzed. Although the results· of th'is section are not directly applicable to. such cases, they do indicate in gen-eral terms the type of accuracy obtainable and the potential cost savings from compositing.
24
I L
[
'-..
.A 2 GROUP COMPOSITING PLAN FOR 7 SAMPLE POINTS
T
so
SI e
7 e
·~
.c
:5
. 2
1
0
-1
-2
-J
--4
~
-e
-7 -e
~ -10 ....... __.___..__,_...,__.......____._ ........ _._.....__..__.._._. ................................. ____.
~r~~P~7~~~Q~~~~~~~~~~
I
X
Figure 8
A 2 GROUP COMPOSITING PLAN FOR 19 SAMPLE POINTS
y
0
0 0
-e
-9 -1c ..__.__,___,___._ ____ -'----'-..:...-i..._..:,__......__~..__.-..:..__,___._...._...J.-..J
X
Figure 9
25
A 6 GROUP COMPOSITING PLA.N FOR 19 SAMPLE POINTS
T
-~
~
~
-7
~
-i -10 .__.,......_.....__.__ ......... --..i..__,_.....,_.,L-.'---1,---'-.-........J......i.......:.-... ......... -,,..J
~~~~~~~~~~o~~~~~c~~~~ I .
X
Figure 10. Location of sample ooints in a 19 sample point plan,
with detail of a 2 group compositing design.
26
·,-.
I
' ~
i \-
' \ \.
.,.
A 4 GROUP COMPOSITING PLAN FOR 37 SAMPLE POINTS
10
9
8
7
6
5
~
3
2
1
B
-1
-2
-3
-4
-5
-6
-7
-8
-9
□
□ □
D □
D □ D
D
D D □
D
-10 ......... ~~•...___•.....__,_•.....__,_•__..__,•__..__,•_.___•......_.:_.._~._._~• ..........,,........._,..........i............J.~_.__J_.__J_._J
FiGure 11. Location of samole ooints in 17 sample noint nlan,
with detail of a 4 crouo cornnositino desian.
27
Table 6. Recommended Compositing Strategies
-~ No. of samples collected ~compositing strategy
7
19
37
One group of 7
One group of 10, one of 9
Three groups of 9, one of 10
b. If the true PCB level in a sample is C, then the measured
value is a normally distributed random variable with mean 0.8C and standard
deviation (0.3)(0.8C) = 0.24C. Thus, it is assumed that the analytical method
is 80% accurate, with 30% relative standard deviation.
c. The maximum allowable level in a single sample is 10 ppm.
However, the measured level for a single sample must exceed 14.2 ppm for a
finding of noncompliance. As previously discussed, this corresponds to a
single-sample false positive rate of 0.5%.
d. The residual contamination present is modeled as a randomly
placed circle of variable radius and contamination level. The PCB level is
assumed to be uniform within the randomly-placed circle and zero outside it.
e. Analysis of samples is terminated as soon as a positive
result is obtained on a singli analysis. If a composite does not give a de-
finitive result (positive or negative), the individual specimens from which
the composite was formed are analyzed in sequence before any other composite.
f. The compositing strategies · used are shown in Figures 8 and
11.
28
r C
The results of the computations are shown in Tables 7 through 20.
Tables 7 through 12 show the performance of the compositing strategies recom-
mended in Section 3. For each strategy, there,,.is a pair of tables. The first
table shows the probability of reporting a violation of a 10 ppm cleanup stan-
dard, for different levels of residual contamination and percent of cleanup ·
area contaminated. When the contamination level is 10 ppm or less, the number
in the table is the probability of a false positive, i.e., a false finding of
noncompliance. These probabilities are all very low, as they should be. When
the level is above 10 ppm, the number in the table is the probability that a
violation will be detected by the sampling design. For levels close to 10
ppm, and for small percentages of cleanup area residually contaminated, the
detection probability is low . When the level is high and the percent of area
contaminated is large, however, detection probability approaches 100%. For
small areas with high contamination, detection capability is modest. This is
because there is only a small chance that the contaminated area will be sam-
pled. Similarly, detection capability is also modest for large areas contam-
inated near the 10 ppm limit. The reason for this is that, even though a
number of contaminated samples will be found in such cases, the analytical
method is not likely to give positive identification of levels near the 10
ppm cutoff. This is the price paid for reducing the single-sample false pos-
itive rate to 0.5%.
The second table for each compositing strategy shows the expected
(average) number of analyses needed to reach a decision. For a fixed percent
of area contaminated, the smallest number of analyses is needed if the level
of contamination is very high or very low. For intermediate levels, more
analyses are needed. The largest number of analyses are required with a
large area contaminated at close to 10 ppm . In such a situation, the levels
of the composite(s) will mostly lie in the intermediate range for which no
conclusion is possible based on analysis of the composite. Thus, individual
analyses will almost always be required, so that the advantage of compositing
is lost.
Tables 13 through 20 compare the recommended compositing strategies
for the 7-point and 19-point designs to alternative compositing strategies
for these designs, for 4 different contaminated percentages (1%, 9%, 25%, and
49%). The comparison is based on the expected number of analyses required.
Overall detection capabilities are comparable for the different strategies.
The tables show that the recommended strategies are best, except for larger
areas contaminated close to the 10 ppm level .
29
i .•
Table 7. Probability of Declaring a Violation of a 10 gpm
Cleanup Standard, for the 7 Point, 1 Composite Design
·"'
Level of residual
PCB contamination Percent of cleanup area with residual PCB contamination
(ppm) 1 4 9 16 25 49
Compliant 8 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001
10 < 0.001 < 0.001 < 0.001 < 0.001 0.002 0.007
Noncompliant 11 < 0.001 < 0.001 < 0.001 < 0.001 0.009 0.032
12 < 0.001 0.001 0.001 0.002 0.017 0.092
13 0.001 0.005 0.005 0.009 0.045 0.184
14 0.003 0.010 0.019 0.028 0.085 0.298
15 0. 006 -0.016 0.039 0.065 0.134 0.396
16 0.009 0.029 0.064 0.102 0.202 0.517
18 0.019 0.074 0.137 0.218 0.344 0.655
20 0.030 0.110 0.199 0.335 0.479 0.787
25 0.048 0.186 0.342 0.554 0.736 0.905
50 0.070 · 0. 245 0.487 0.767 0.977 0.989
75 0.071 0.245 0.496 0.787 0.992 0. 995 .
100 0.068 0.255 0.499 0.800 0.995 0.997
150 0.070 0.246 0.481 0.796 0.998 0.999
200 0.073 0.254 0.489 0.806 > 0.999 > 0.999
300 0.069 0.257 0.494 0.792 > 0.999 > 0.999
500 0.070 0.242 0.492 0.811 > 0.999 > 0.999
/ ~
aSeven samples an·a ly:z.ed first as a composite, then indivi dually if necessary
to reach a decision.
30
,----Table 8. Expected Number of Analyses to Decide Compliance or
Violation, for a 10 ppm Clean~p~tandijrd, for the
7-Point, 1-Composite Oesign°
Level of residual
PCB contamination
(ppm)
Percent of cleanuo area with residual PCB contamination
Compliant 4
6
8
10
Noncompliant 11
12
13
14
15
16
18
20
25
50
75
100
150
200
300
500
1 4 9 16 25 49
1.00
1.00
1.00
1.00
1.01
1.04
1.04
1.10
1.13
1.15
1.19
1. 24
1. 26
1. 28
1. 28
1. 21
1. 09
1. 03
1.01
1.00
1.00
1.00
1.00
1.01
1.04
1.08
1.18
1. 32
1. 45
1. 52
1. 69
1.85
1. 98
1. 96
1. 94
1. 79
1. 28
1.11
1.01
1.00
1.00
1.00
1.00
1.02
1.05
1.17
1. 40
l. 63
1.85
2.03
2.41
2.57
2.85
2.93
2.93
2.53
l. 52
1. 15
l. 04
1. 01
1.00
1.00
1.00
1.03
1.11
1. 32
1. 59
2.02
2.35
2.67
3.18
3.59
3.84
3.99
3.98
3.45
l. 86
1. 34
1.09 ·
1. 02
1.00
1. 06
1. 44
1. 75
2.01
2.21
2.56
2.86
3.22
3.50
3.95
4.19
4.47
11 £l.,. .. 'J
4.23
3.54
1. 89
1. 33
1.06
1. 02
1.11
2.31
3. 96
11 a-.. Jo
5. 3 l
C:. 1C ...J • ..J..-
5.3S
5.18
4.S0
11 --'. I l
ll 1'" .. -0
4.04
1 ,---.Ol
2.%
2.26
7 c-_.u/
l. 30
1.13
1.03
l. 01
a Seven samples analyzed first as a composite, then individually if necessary
to reach a decision.
31
l r-
Table 9. Probability of Declaring a Violation of a 10 p~m Cleanup_
Standard, for the 19 Point, 2 Composite Design --
Level of residual
PCB contamination
(ppm)
Percent of cleanup area with residual PCB contamination
1 4 9 16 25 49
Compliant 8 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001
10 < 0.001 < 0.001 0.002 0.007 · 0. 015 0.028
Noncompliant 11 < 0.001 < 0.001 0.007 0.034 0.058 0.017
12 0.001 0.002 0.029 0.084 0.153 0.281
13 0.003 0.007 0.062 0.179 0.304 0.497
14 0.005 0.021 0.114 0.304 0.455 0.693
15 0.012 ----GA)S-2--·· ··0.178 0.407 0.606 0.832
16 0.025 0.083 0.264 0.518 0.744 0.908
18 0.046 0.167 0.421 0.698 0.883 0.978
20 0.077 0.263 0.556 0.812 0.945 0.993
25 0.125 0.461 0.784 0.923 0.990 0.999
50 0.161 0.631 0.978 0.992 0.999 > 0.999
75 0.171 0.651 0.993 0.997 > 0.999 > 0. 999 .
100 0.168 0.642 0.994 0.999 > 0.999 > 0.999
150 0.166 0.657 0.998 0.999 > 0.999 > 0.999
200 0.175 0.648 0.999 0.999 > 0.999 > 0.999
300 0.168 0.654 0.999 > 0.999 > 0.999 > 0.999
500 0.180 0.661 0.999 > 0.999 > 0.999 > 0.999
aN" 1neteen samples analyzed first as two composites, then individually if
necessary to reach a decision.
-·· --·.
32
' l---
Table 10. Expected Number of Analyses to Decide Compliance or
Violation, for a 10 ppm Clea~up~Standa~d, for the
19-Point, 2-Composite Design
-Level of residual
PCB contamination ... -. (ppm) Percent of cleanup area with residual PCB contamination
Compliant
Noncompliant
4
6
8
10
11
12
13
14
15
16
18
20
25
50
75
100
150
200
300
500
1 4 9 16 25 49
2.00
2.00
2.00
2.01
2.03
2.10
2.21
2.25
2.37
2.49
2.60
2.68
2.82
2.80
2.80
2. 77
2.53
2.21
1. 99
1. 92
2.00
2.00
2.00
2.03
2.14
2.32
2.74
3.02
3.40
3.84
4.36
4.65
5.02
5.03
5.05
4.95
3.94
2.67
1. 89
1. 69
2.00
2.00
3.01
3.72
4.07
4.57
4.84
5.16
5.50
5.89
6.11
6.26
6.20
5. 96
5.69
5.37
3.99
2.61
1. 70
·1.48
2.18
3.79
6.15
7.46
7.90
8.08
7 :94
7.90
7.65
7.30
6.57
6.18
5.45
4.70
3.68
3.46
2.59
1. 91
1.50
1. 39
3.30
6.70
9.20
10.55
10.74
10.67
9.95
9.31
8.42
7.59
6.29
5.48
4.57
3.48
2.63
2.26
1.80
1. 55
1. 34
1. 30
7.49
11.22
13.18
14.02
13. 81
12. 78
11. 00
9.27
7.80
6.63
5.02
4.25
3.36
2.28
1. 84
1. 69
1.46
1.33
1.19
1.15
aNineteen samples analyzed first as two composites, then individually if
necessary to reach a decision.
33
r -r--
,. Table 11. Probability of Declaring a Violation of a 10 ~pm Cleanup I ~ Standard, for the 37 Point, 4 Composite Design I I
Level of residual
I-PCB contamination Percent of cleanuo area with residual PCB contamination
(ppm) 1 4 9 16 25 49
Compliant · 8 < 0.001 < 0.001 < 0.001 < 0.001 . < 0. 001 < 0.001
10 < 0.001 0.002 0.010 0.022 0.031 0.060
Noncompliant 11 0.001 0.008 0.041 0.084 0.124 0.225
12 0.001 0.024 0.103 0.217 0.305 0.488
13 0.005 0.053 0.224 0.388 0.536 0.751
14 0.012 0.094 0.360 0.575 0.726 0.908
15 0.023 0.159 0.501 0.740 0.859 0.950
16 0.039 0.242 0.621 0.831 0.936 0.991
18 0.091 0.390 0.785 0.940 0.985 > 0.999
20 0.147 0.542 0.884 0.981 0.996 > 0.999
25 0.249 0.771 0.958 0.995 0.999 > 0.999
50 0. 340 · 0.976 0.997 0.999 0.999 > 0.999
75 0.343 0.991 0.999 0.999 > 0.999 > 0.999 '
100 0.353 0.993 0.999 > 0.999 > 0.999 > 0.999
150 0.339 0.997 > 0.999 > 0.999 > 0.999 > 0.999
200 0.357 0. 996 > 0.999 > 0.999 > 0.999 > 0.999
300 0.344 0.997 > 0.999 > 0.999 > 0.999 > 0.999
500 0.348 0.999 > 0.999 > 0.999 > 0.999 > 0.999
aThirty-seven samples analyzed first as four composites, then individually if
necessary to reach a decision.
-. . .. -
34
!
!
Table. 12. Expected Number of Analyses to Decide Compliance or
Violation, for a 10 ppm Clean~p ~tanda,d, for the
_ 37-Point, 4-Composite Design
Level of residual
PCB contamination
(ppm)
Percent of cleanuo area with residual PCB contamination
Compliant
Noncompliant
4
6
8
10
11
12
13
14
15
16
18
20 25 .
50
75
100
150
200
300 ·
500 .
1 4 9 16 25 49
4.00
4.00
4.00
4.02
4.07
4.18
4.35
4.57
4.73
4.90
5.09
5.26
5.34
5.27
5.23
5.22
4.55
3. 95 ·.
3. 59 ·
3.49
4. 01
4.15
4.77
5.36
5.69
5.97
6.28
6.78
7.04
7.33
7.59
7.74
7.55
7.14
6.84
6.43
4.89
3.57
2.67
2.48
4.41
6.66
9.01
10.56
10.87
10.94
10.56
10.21
9.60
9.08
8.02
7.28
6.53
5.39
4.31
3.73
3.02
2.53
2.28
2.22
6. 72 .
10.22
12.76
14.29
14.29
13. 74
12.74
11. 21
9.71
8.77
7.05
6.26
5.28
3.78
3.04
2.64
2.37
2.15
2.04
1. 99
9.85
13.48
15.98
17 .18
16.93
15.68
13.44
11.13
9.33
7.83
6.16
5.30
4.37
3.06
2.55
2.32
2.07
1. 90
1. 81
1. 79
15.69
19 .36
22.08
23 .04
21. 28
17.84
13. 54
10.10
7.78
6.12
A -7 .• I -
3. 96
3.08
2.16
1.90
7 ----· ,~
1. 57
1. 52
1.44
1.44
aThirty-seven samples analyzed first as four composites, then individually if
necessary to reach a decision .
. . ·----·-·-.. -
35
r -
-·-
...
Level
Table 13. Comparison of Expected Number of Analyses for Different
Compositing Strategies for the 7-Point_Design, When an Area 1%
of the Size of the Cleanup Site Remains Contaminated
of residual PCB
contamination (ppm) 1 Composite 2 Composites Individually
Compliant 4 1.00 2.00 7.00
8 LOO 2.00 7.00
10 1.00 2.00 7.00
Noncompliant 12 1.04 2.02 6.98
14 1.10 2.05 6.96
16 1.15 2.07 6.92
20 1.24 2.10 6.88
25 1.26 2.11 6.84
50 1.28 2.09 6.80
100 1.21 1. 98 6.78
200 1.03 1.96 6.80
500 1.00 1.96 6.81
Table 14. Comparison of Expected Number of Analyses for Different
Compositing S~rategies for the 7-Point Desi.gn r When an Area 9:
of the Size of the Cleanup Site Remains Contaminated
· Level of residual PCB
contamination (ppm) 1 Composite 2 Composites Individually
Compliant 4
8
10
Noncompliant 12
14
16
20
25
50
100
200
500
1.00
1.00
l.02
1.17
1. 63
2.03
2.57
2.85
2.93
2.53
1.15
1.01
36
2.00 7.00
2.00 7.00
2.01 6.99
2.09 6.91
2.32 6.69
2.50 6.49
2.77 6.06
2.79 5.65
2.60 5.45
1.85 5.46 :-~
1. 72 5.45
1.17 5.45
L-
'
----
Table 15. Comparison of Expected Number of Analyses for Different
Compo~iting Strategies for the 7-Point~esign, When an Area 25%
of the Size of the Cleanup Site Remains Contaminated
Level of residual PCB
contamination (ppm) 1 Composite 2 Composites Individually
Compliant 4 1.00 2.00 7.00
8 1.44 2.13 7.00
10 1.71 2.24 6.98
Noncompliant 12 2.21 2.44 6.81
14 2.86 2.84 6.29
16 3.50 3.23 5.64
20 4.19 3.54 4.68
25 4.47 3.56 4.12
50 4.45 2.97 3.58
100 3.54 1. 61 3.51
200 1. 33 1. 38 3.50
500 1.02 1. 37 3.50
Table 16 . Comparison of Expected Number of Analyses for Different
Compositing Strategies for the 7-Point Design, When an Area 49%
of the Size of the Cleanup Site Remains Contaminated
Level of residual PCB
contamination (ppm)
Compliant 4
8
10
Noncompliant 12
14
16
20
25
50
100
200
500
1 Composite 2
1.11
3. 96
4. 96
5.39
5.18
4.71
4.04
3.61
2.96
1. 87
1.13
1.01
37
Composites Individually
2.02 7.00
2.99 7.00
3.50 6.96
3 .. 81 6.61
3.94 5.79
3.86 4.82
3.49 3.53
3.03 2.87
2.22 2.40
1. 36 2.40
1. 23 2.39
1. 20 2.39
• I
Table 19. Comparison of Expected Number of Analyses for Different
Compositing Strategies for the 19-Pojnt•Design, When an Area 25%
of the Size of the Cleanup Site Remains Contaminated
Level of residual PCB
contamination (ppm)
Compliant 4
8
10
Noncompliant 12
14
16
20
25
50
100
200
500
2 Composites 6
3.30
9.20
10.55
10.67
9.31
7.59
5.48
4.57
3.48
2.26
1. 55
1. 30
Composites Individually
6.·07 19.00
7.73 19.00
8.44 18.83
8.47 17.31
7.67 13.72
6.57 10.58
5.09 6.25
4.24 4.35
3.22 3.34
2.51 3.29
2.41 3.26
2.43 3.23
Table 20. Comparison of Expected Number of Analyses for Different
Compositing Strategies for the 19-Point Design, when an Are= 49%
of the Size of the Cleanup Site Remains Contaminated
Level of residual PCB
contamination (ppm)
Compliant 4
8
10
Noncompliant 12
14
16
20
25
50
100
200
500
2 Composites 6
7.49
13.18
14.02
12.78
9.27
6.63
4.25
3.36
2.28
1. 69
1.33
1.16
39
Composites Individually
6.28 19.00
9.85 19.00
10.84 18.73
10.10 16.15
7.78 11 .34
5.87 7.14
3.92 3.74
3.23 2.61
2.46 2.10
1.85 2.06
1. 79 2.04
1. 78 2.02
. ,
. i
' I
The major conclusions that can be drawn from these results are as
follows. First, the proposed cutoff on the measured PCB level for a finding
of noncompliance for a single sample, 14.2 ppm, is successful in controlling
the overall false positive rate of the sampling scheme. For example, when an
area half the size of the entire site remains contaminated just at the allow~
able limit of 10 ppm, the false positive rate is 1.% for the 7-point design,
3% for the 19-point design, and 6% for the 37-point design. Note, that the
overall false-positive rate is highest for cont~mination just at the allow-
able limit. Second,. the detection capabilities of the design appear satis-
factory, bearing in mind the difficulty of detecting randomly-located contam-
ination by any sampling scheme without exhaustive sampling. As an example,
the proposed 19-point design can detect 50 ppm contamination present in 9% of
the cleanup area with 98% probability. Similarly, the 19-point design can
detect 20 ppm contamination present in 25% of the area with 95% probability.
Third, the proposed compositing strategies are quite effective in reducing
the number of analyses needed to reach a decision in all cases except those
involving large areas contaminated near the cutoff of 10 ppm. For example,
for contaminated levels of 25 ppm or greater, the expected number of analyses
to reach a decision never exceeds 5 for the 7-point design, or 7 for the 19-
point design, or 8 for the 37-point design. Larger number of analyses are
needed in cases of contamination close to the allowable limit of 10 ppm, up
to 23 for the 37-point design when 45% of the area is contaminated at 10 ppm.
8. Sampling Techniques
The types of media to be sampled will include soil, water, vegeta-
tion and solid surfaces (concrete, asphalt, wood, etc.): General sampling
methods are described below. Additional sampling guidance documents are avail-
able (Mason 1982, USWAG 1984).
1. Solids Samoling
When soil, sand, or sediment samples are to be taken, a surface
scrape samples should be collected. Using a 10 cm x 10 cm (100 cm2 ) template
to mark the area to be sampled, the surface should be scraped to a depth of
1 cm with a stainless steel trowel or similar implement. This should yield
at least 100 g soil. If more sample is required, expand the area but do not
sample deeper. Use a disposable template or thoroughly clean the template
between samples to prevent contamination of subsequent samples. The sample
should be scraped directly into a precleaned glass bottle. If it is free-
flowing, the sample should be thoroughly homogenized by tumbling. If not,
successive subdivision in a stainless steel bowl should be used to create a
representative subsample.
. ,
In some cases, such as sod, scrape samples may not be appropriate.
For these cases, core samples, not more than 5 cm deep, should be taken using
a soil coring device. These core samples should be well-homogenized in a
stainless steel bowl by successive subdivision. A portion of each sample
should then be removed, weighed and analyzed.
Samples should be stored in the dark at 4°C in precleaned glass
bottles. If samples are to be analyzed quickly, the storage requirements may
be relaxed as long as sample integrity is maintained. Before collection of
40
verification samples, this equipment must be used to generate a field blank
as described in Section IV.E.
2. Water Samolina
a. Surface Samolina
If PCBs dissolved in a hydrocarbon oil were spilled, they will
most likely be dispersed on the surface. Therefore, a surface water collec-
tion technique should be used. Surface water samples should be collected by
grab techniques. Where appropriate, the precleaned glass sample bottle may
be dipped directly into the body of water at the designated sample collection
point. A sample is collected from the water surface by gently lowering a
precleaned sample bottle horizontally into the water until water begins to
run into it. The bottle is then slowly turned upright keeping the lip just
under the surface so that the entire sample is collected from the surface.
b. Subsurface Samol ina
If the PCBs were in an Askarel or other heavier-than-water
matrix, the PCBs will sihk. In these cases water near the bottom should be
collected. To collect subsurface water, the bottle should be lowered to the
specified depth with the cap on. The cap is then removed, the bottle allowed
to fill, and the bottle brought to the surface.
c. Other Samoling Aooroaches
When the above approaches are not feasible, other dippers,
tubes, siphons, pumps, etc., may be used to transfer the water to the sample
bottle. The sampling system .should be of stainless steel, Teflon, or other
inert, impervious, and noncontaminating material. Before collection of sam-
ples, this equipment must be used to generate a field blank as described in
Section IV.E.
d. Sample Preservation
The bottle is then lifted out of the water, capped with a PTFE-
or foil-lined lid, identified with a sample number, and stored at approximately
4°C (USEPA 1984a) until analysis to retard bacterial growth. If samples are
to be analyzed quickly, the storage requirements may be relaxed as long as
sample integrity is maintained.
3. Surface Samo 1 i ng
a. Wi pe Samoles
·If the surface to be sampled is smooth and impervious (e.g.,
rain gutters, aluminum house siding), a wipe sample should indicate whether
the cleanup has sufficiently removed the PCBs. These surfaces should be sam-
pled by first applying an appropriate solvent (e.g., hexane) to a piece of
11 cm filter paper (e.g., Whatman 40 ashless, Whatman 11 50 11 smear tabs, or
equivalent) or gauze pad. This moistened filter paper or gauze pad is held
with a pair of stainless steel forceps and used to thoroughly swab a 100-cm2
area as measured by a sampling template.
41
I .
Care must be taken to assure proper use of a sampling template.
Different templates may be used for the variously shaped areas which must be
sampled. A 100 cm2 area may be a 10 cm x 10 cm square, a rectangle (e.~.,
1 cm x 100 cm or 5 cm x 20 cm), or any other s·hape. The use of a template
assists the sampler in the collection of a 100 cm 2 sample and in the selec-
tion of representative sampling sites. When a template is used it must be
thoroughly cleaned between samples to prevent contamination of subsequent
samples by the template.
The wipe samples should be stored in precleaned glass jars at
4°C. Before collection of verification samples, the selected filter paper or
gauze pad and solvent should be used to generate a field blank as described
in Section IV.E.
b. Samolina Porous Surfaces
Wipe sampling is inappropriate for surfaces which are porous
and would absorb PCBs. These include wood and asphalt. Where possible, a
discrete object (e.g., a paving brick) may be removed. Otherwise, chisels,
-drills, saws, etc., may be used to remove a sufficient sample for analysis.
Samples less than 1 cm deep on the surface most likely to be contaminated with
PCBs should be collected.
4. Veaetation Samolinq
The sample design or visual inspection may indicate that samples of
vegetation (such as leaves, bushes, and flowers) are required. In this case,
samples may be taken with pruning shears, a saw, or other suitable tool and
placed in a precleaned glass bottle.
C. Analytical Techniques
A number of analytical techniques have been used for analysis of
PCBs in the types of samples which may be associated with PCB spills. Some
of the candidate analytical methods are listed in Table 21. The analysis
method(s) most appropriate for a given spill will depend upon a number of
factors. These include sensitivity required, precision and accuracy required,
potential interferents, ultimate use of the data, experience of the analyst,
availability of laboratory equipment, and number of samples to be analyzed.
As shown in Table 21, many analytical methods are available. The
general analytical techniques are discussed and then compared below.
1. Gas Chromatograohy (GC)
As can be seen in Table 21, analysis of PCBs by gas chromatography
is frequently the method of choice. PCBs are chromatographed using either
packed or capillary columns and may be detected using either specific detec-
to!s ·or mass spectrometry. A comprehensive method for analysis of PCBs in
transformer fluid and waste oils was developed by Bellar and Lichtenberg
(1982). This method describes six different cleanup techniques, recommends
three GC detectors, and suggests procedures for GC calibration and for mea-
surement of precision and accuracy. This method also discusses several cal-
culation methods.
42
IAlolr ;'I. St.111,1.1rrl l'rnu•il11rr\ ul /111.,ly\ I\ ltu-f't:11~ ---·-· -----··---····-··---···· ---· -------···------•·• ....... -. •·• ... -··-----· ..... --· . -· ....... ... I. . .... -... --------·••····-···-····--·------·· f't·ocrtlurP llrlrrml11,1lio11 1)11a I I I ,ii I vr Q11.111l ii al inn Qr. ties I !Jll,l l I un fl,1 l r I• l'xlrAcllon C lt>,lllllp C n,rlluul ,,~ !.«!\ ~ni,-nt n,rlhn,I I 1111 tll~CIIHPII R,•lt!nncP. ---------------·-· ·--··----. ··-. ---------------···-· --.... ---· ·-....... ·-··---·-·--·--... -. -... ·-·· . -.... ·-. . ...... ------.. --. ···-____ ., --·-····----. --· 1nr,J1-no \.la l r·r '!-llex.anp/(112C 12 (I lurl s 11) l'ta:/!Clltl llo lolAI ,,rr,1 111· fl. I 1•!1/I llu /IS 111, l'HII a ( S 11 ILa 1;p I) 11,.1,1, ttcf..111 filtO \.la l rr Cll2Cl2 (flnrlsll) 1•1:C/1 Cll 1111 llrr,1 1i.111•1l. l!j l'!t/l y,,~ f P/1, l'JM,1; . ! (S l'l'IROVJI l l.u11!tlool luon atul l lr.hlr11hrqJ, l'JOZ 625 \la l r r tit, CI 2 llone .. 1•1;ur11,~ Yr~ /\rea 111· 11i 1'!1/l Yes £1'/\, l'lMh; 11:1:i:1 I Oll!tloullom ~1111 L llhl f!llhl'l'!J, l'Jn7 JIMh \.l,1t rr llrxano•/ florls 11/ rc:urrn Yrs S11m~1r,I ~reas II~ VI'S r I'll, 1'110 Ctl2Cl2 silica !JPI 01 tlf(I) 01· \J,•hh·tlcCd 11 (ll~/IS) ( CJJ3(.JJ) (S rrm11val) £PA (by-\1,1 t er Sl'vl'ral Sevl'ral I lllfif./f HI~ Y~s 11111. pl'aks II\ Yes rrlckson el al., proclucls) 1907, 198),t; r 1•11. 1901, ~ w /\IJSI \.ldlrr lll'xane (112 SO,) 1•,;f.!( fl) lln Sit1!1le prak or 7 ppm YPS /\llSI, 1914 (Sapo11I f lc.,11011) \ttn1ni('fl JW,11ii S Al11mi11,1 Honsanto \.l,llH llrxane /ll11ml11.1 l'lir/lCO tin l111llvltl11al or z """ lln Hnrln, 1'116 t11la I pe,,k t11-lc11tts -i, ltK·OOf \la I er llrxane Sil Ir.a or.I PC:C/rr.n lln llS 1116 1111/I. tin llK·Oll[, l!J1'J; 1lr.,·e11 I sh an,I llarl l11wnowen, 19011 03104-74 /\Ir 01 r•,:ctrrn llo lolal area IIS VI'S /\S 111, I 'JO 111 \.laler llfxa11e (lli SO t) Sol 1, ll20/C113CN (Sapu11I I lr,1t Inn) $Pd lnie11l (AI 11nii na) [PA (humolog) Sol It.ls anti Severa I SPvera 1 llllf.C/f IMS Yes )tut, flP,lkS llS Yrs frld~on el al., 111111 I tis l'tOSa · £Pl\ 625-S Sluct!Jl' t111Cl2 Florlsll, unr.r./flHS or Yes /\rpa IIS VI'S ll,1 I le a11tl Silica !tel, l'1:uc1m lopr1·/\vl la, or (il'C l'JtM
~ ·r; ·-,. ! ! ---11 l~ltle 21 ( (onll 1111e11) -·-----. ----------------·--·-·---------•·• .. ····-•·••···---·--·-·-------·--------·----·------------------------v rrurr,lurr lletrrminat Inn Qua! lt,1! Ive Quant Ital Inn QC \\ rlrs l11nat ln11 lhl rlx r•tr11cllun Clr,1n11p r inl'lhnrl assessment mPthn,l 1011 discus std Reltrence ' ··---·----·-------· -··-... ·--.................... ---··--·-·----·-------·----------··--·-·--······--·--·--·--·----------·---------( l'I\ . . · S l11rl11~ llexane/ ere, rGC/[Cll YPS r,ak area c,r IIS YPS R111lrl!J11~, (IIAlncarhon) Cll1Cl1/ S ru,,,v,1 I pPak hel11hl rl al., l'JOO acelonl! 1 • I ,· 1.·. (Ol/l!i/2) rrlorlty ; , S 111,lql' Cll1Cl1 : f.l'C rc;ctr lltS Yes HS IIS Yrs r1•1\, l'll'}c rul l11t1111l :!', (hJse/ .·1•1••· nP.111 ra I I' Jlltl acid lrJrllnns) RIOO Sl111l!IP. Cll1Cl1 r.1·c ltRf.C/LIHS \'p s IIS HS Y,, 8,1ll l11!Jer, 1918 (J lrarllnns) S 11 lc a 111• I or NiC/l IHS nruio Sul 1,1 w.HIP Cll1Cl1 (llorlsll) rr.c/Hll Ho fll'P,l I l•!J/!J Yrs rrA, l'l82e A2r,o Solid wHlf' rn1c11 llune rr.ctr IHS Hn 11S I 11!Jl!J Yes £1'1\, l!l02e A2111 Sol ltl waslP me 11 lln11P. Cf.Cl( IHS llo HS I f,!J/g Yu Cl'I\, l'JB?t .I l'fl ( srl I ls l llM11r.r:llltrl lleunr/ (Cll3CII) rr.r.tr r:n llo lnl11I aru or IIS Ho Beard and .p. 11crl1111e (rlorlsll) ~Phb-HlCall Sch,111m, 1918 .p. ( S 11 lca !JP. I) (llrrcury) ( l'fl · :·.·Sol I 111tl flctln11e/ rlorlsll rr.C/CCll 11,, Com1111ler HS Yes Crl\, ICJBM Sr,llmrnl lle•ane SI I lea ue I (S n,mnvdl) -) H1111<a11lo SP11l11r11l Cll_1CH Saponl I lral Inn rr.ctrrn Hu ·1 nd Iv I 1t11a I n r 2 l'rll llu tt11el11, 1')16 111S0 total pe,,k fl I umln~ liPlghls 1\11~ I Sr1llmPnl, Cll3f.ll SAponl I lcal lc,11 rr.ctcrn llo SlnglP peak or '1 ppm Yo.s ,,,,~,. 1914 so II 111 S01 s11.,,,,e,I ped s . Al111nl11,1 rr" Ctiv-I'd,· col ltel<'rf llexa11e (111 so, l 11nr.uc 111s YH 11111. pPaks 11S YPS [rlcks,:,11 el al., pr-n,luc ls) 011 llnrlsll 111· (florlsl I) l'J02, l'JOld; XI\U·l (rlrkson, l'lfl4b (l'fl (11n,hlrnl. Air nPar h,11-llexane/ I\ 1111n I n,1 rr.urrn Ho lul~I area nr 10·50 ll!J/ml lln I cwls, 1902 · a Ir) 11nln11~ waste e 11,er pe,tk hcl!1hl sllrs col· I ec l rrl nn l'lff
r' .p. Ul ; ,\. ·. ;,, .. :; ' -., •. ,. ji,,: !'-. 1-· ; I ·.'.f\,.1 'I : ' /• :-•: rrocP.1l11re·'. 1l~s l!lnall"n tl,,trl• i;:•. ,·· £•tract Inn . C Cl~••111f1 l.1hlt ?I (C:1,111 inur.11) --·--· ---····-··-·--·-llrl Prml11.,lion ()ual 11.,t lvt ••r llu••I ,\S srssm1•nl l)uanl I tat Ion mrlh111I 1011 QC 1IIH11ssetl ·---7 Relerr.nce -··---·-·-----·-·------···· ····-------------·-·-·-.... ·------·----------······---· .... ···---··--·--·-·--------. --•·••· ·----·-·---------·--·-···---------U, ,.,., £1'A ('slai:i< )' Inc fntr~I nr I' ll~lian, ··•· • •!(lf1S01)-•·'·· rerchlorlna-lln llrra Ill ll!f llo Ila I IP. anti enolss Ions I inn rGC/[ f.O o., I a,li, 1911; a111I ~mh I rnl llraril •ml Sch~um, f!i ,t, air, till lccl1•1I ';1 1•1,n on rlorldl ,: .,.·,. I' 11'11 Cc,mh11stln11 renl a'np or (lloolsl 1/ l'f.C/t1S Yr< llre,,/hc,mn I 011 II 1 1111/ I nJ 1111 levlns el al., sourcrs ; Cll2Cl2 · s 111 c ,1 !I'' I) 1 'l /'l col ltclP.11 onrlnrlsll 1r11 ( lncln· Slack !J•H r,nlanr/ 1•1;r.111s Yes Sln!Jle flt•k IIS Yu o,arr1 anti r.ralnrs) mr. l11a110 I ~chaum, 1918 IIIISI Air (112 ~01) rr:C/CCII tlo Sln!1le r,eak l flr>h Yt.s AIISI, 1974 (tnlurne (Sapnni I ir.al 11111) l1np ln!Jr.r) (AI umi n,,) IIIOSII Air col l1•cle1I llewanP llnne 1·1:c;rrn fin rea~.• he l9hl or II.DI "'!1/m1 llo IIIOSII, 1911a (l'MAII ?H) on llnrl~il area lru"' stan· 1lar1I curve or \lt'hb·llcCal I tllOSII /\Ir col lcct,.,I llrwan" tlonP. rr.urco fin reak 1,~l!Jhl or o. 01 m11/m1 llo IIIOSII, 1'111h,c (rl,CAH 7!il) 011 rlodsll l'erchlnl'lna· a,·«'a lrom slan· l Ion. danl curve [l'A (!J,H) llalural -!las Ur.wane 111So1 1•r.c1rco lolal area, reak 0. 1·7 p!J/"'' llo llarrls el a}., umpletl wl th hel9hl or \/~Ith· J'JOI llnrls II HcCall (Perchlorlnat Ion) [r,\ (!i,A,(l)) Blond llewane (r lo.-1s11) rr.urco 1111 IIS IIS llo \/alls, l!lOO rrA 1s,A,Ct>I AtllroH l'el. ether/ rrodsll l'f.C/HO 1111 IIS IIS Yes \Jalls, 1900 Cll3Ctl [Pl\ (9,0) Acllfln<e rel. ether/ Saronlllcallon II C llo Seml1111anl, 10 fl('ffl llo \Jal.Is, l!lOO Cll_,r.H rlorlsll [l"l'I (9,0) 1111 k Acetone/ Cll~CII r1:uc en Yrs Jud. r,eaks ~O 1•11h Yes \Jall s, 1900 l•P•an~ rlorlsll Sh.rm•, I 'lll I Slllca .,cl1I :-·--7-
-l==-°' J.1h Ir 11 ( Cont I 1111r1f) ---·---------------·----·----rrocr,lure ,1P.sl911oltlo11 AUAC C?'J) Japan rAH i\Oi\C (29) OJ ]OJ· 14 MIIS'l·Rl rrA (oll) [Pi\ (by· protfucts) OCl!i\ 0011 (rA-(lsomer 9rn11ps) HJI rl • footf ron,t fnn,I ra[IH a111f ·, I 11,111r1 hn,11·1! Ca(•.\c I I or As~.1, rls Hlnr,·,,1 nl I lroln,forMrr flui,h or wHI ,, nl Is Products or wasles l pigment types Chlorlnat,tf be111enes tfnsrec If I ed lwtractlnn C113Cll/ret, f'lhtr rr.t. 0ether/ C:UlCII rel. rlhcr/ Cll.,rn Sapnnl I lc,t• l 11111 111" Ill lute wl th hP•ant or lsooclanf' Ill Sevnal A. llewan,/ 112501 o. rn,c11 01 C l""""l'c f0lori°\.I I ll,10/ Celllt Sapnnlflcal ln11 Sil lea qr.I Saronlllcalin11 (florhll) Slllclc acl,1 (SAponl I ir.al Ion) (O• lfl,tl Ion) (rtorlsl I) florlsll 11,,11/ Crlllt \,1p1111I I icoll ln11 llnnr r lnrls 11 s luriy ( 111~011 (I lorld I cnlu.,n) (111501) (florlsll) ( i\ I um Ind) ( S 111 ca !JC I) (C.rC), (CIIJCII) Sr.veral llnn, florlsll llnne lint atf,lrts sr1I llol acl,fres sr.,I llrtennlnat Ion Qua I Ital Iv, mrl hn,I assessment r,:urrn rr.C/HD rGC/[CO 1 rr.r:11,r en> (Ill'· II C} ( Rf'· II C) rr:ctr(ll ~ro1 11nr.ur rn rt:C/LW ( l'l;C/111 lll) rr.f./11( Cll or /LUI or /I IHS 111111:c l 11n1:C/[ IHS rr.urcn rGUCIHS IIRf.C/[ IHS tin Yes tin llu tin Yrs tin Yes llo Yr.s Yes f)11J11l 11,,t Ion mi?lhnff lnl.\l arr.\ 01 11111. pra~s Summed olrP~S prrchlor 111.,t Ion Arel lolal area or 11111. pulr.s lolal HU Ind. peah or llehb·ltcCa 11 lotal area or llcbh·ltc(d 11 Ind. peaks 10 Isomers lntat peak he I rJhl /ho.,n I n!I 1111I. peaks Source:-H:-·b-:-rrlc'I~ lie 1iialyilc'iT11ittil st ry or Hfil;"fiiin er.;.-;rir.s;-liosTtt11;-"ll,\ ~-l~ii~·.-·111 prr•\ s. 1 Ho sp,clflc detollls. b Olrtct lnJ,ctlon or rlllut, and lnj,ct. c lrchnlquu In rarrnlheas arae clescrlhe,I .is optlu11,,I 111 lhr fll'OCr1hore. d Or l'f.C with ,wlcrornnlometrh: or 1elHlrnlyllc. c11111h11:l lvlty. ---------------I Oil 11~" II~ IIS us" 2.0 • 10·• mol/l SO ppm I mg/k9 IIS , I r•11m/ho110 I og IIS IIS QC diHIISSetl lfu Ito lln Ito llo Ito Yes Yrs Yes YH Yrs Referrnce i\Or.C, 1900a lanahe, 19/li ror., 1911 AOi\C, 1980h ASHI, 1900a ASIH, l9Rl fl'A, l'181 • Otllar ,11d l lchltnh...-9! 1qo1 · [rlckson tl ,t., 1902, l'lOld; [rldson, 1901a OCHA, 1902 !low, 1901 rr•A, 1904,1 -7 I
a. Gas Chromatograph/Electron Caoture Detection
. Packed column gas chromatography with electron capture detec-
tion (GC/ECD) is generally the method of choice for analysis of spill site
samples, transformer oils, and other similar matrices which must be analyzed .
for PCB content prior to disposal (Copland and Gohmann 1982). GC/ECO is very
sensitive, highly selective against hydrocarbon background, and relatively
inexpensive to operate. The technique is most appropriate when the PCB resi-
due resembles an Aroclor~ (Aroclora is a registered trademark of Monsanto
Company; the trademark designation is not used throughout this report) stan-
dard and other halogenated compounds do not interfere.
While it is considered a selective detector, ECO also detects
non-PCB compounds such as halogenated pesticides, polychlorinated naphthal-
enes, chloroaromatics, phthalate and adipate esters, and other compounds.
These compounds may be differentiated from PCBs only by chromatographic re-
tention time. Elemental sulfur can interfere with PCB analysis in sediment
and other samples which have been subjected to anaerobic degradation condi-
tions. There are also common interferences which do not give discrete peaks.
An example of a nonspecific.interference is mineral oil (ASTM 1983). Mineral
oil, a complex mixture of hydrocarbons, can cause a general suppression of
ECO response. Mineral oils from transformers often contain PCBs as a result
of cross-contamination of transformer oils.
A major disadvantage of ECO is the range of response factors
whic b,_ different PCB congeners exhibit. Zitko et al. (1971) and Hattori et al.
(19ft .; published response factors ranges of about 540 and 9000, respectively.
Boe and Egaas (1979), Onsuka et al. (1983) and Singer et al. (1983) have also
published ECO response factors. The range of response factors seriously in-
hibits reliable quantitation of individual _ PCB congeners or non-Aroclor PCBs
unless the composition of the sample and standard are the same.
When PCBs are analyzed by packed column gas chromatography,
the PCBs are usually quantitated by total areas or individual peaks. In the
total areas method, the areas of all peaks in a retention window are summed
and this total compared with the corresponding response of an Aroclor stan-
dard. With the individual peak quantitation method, response factors are
calculated for each peak in the packed column chromatogram. The most prom-
inent individual peak quantitation method was originated by Webb and McCall
(1973). These results may be reported as an Aroclor concentration or as
total PCB. Packed column GC techniques are generally useful for quantitation
of samples which resemble pure Aroclors but are prone to errors from inter-
fering compounds or from PCB mixtures that do not resemble pure Aroclors
(Albro 1979). For this reason analysts have been using capillary gas chro-,,
matography for the analysis of PCBs. Capillary gas chromatography offers the_
analyst the ability to ·separate most of the individual PCB isomers. Bush
et a1. (1982) has proposed a method of_ obtaining 11 total PCB 11 values by inte-
gration of all PCB peaks, using response factors generated from an Aroclor
mixture. Zell and Ballschmiter (1980) have developed a simplified approach
where only a selected few 11 diagnostic peaks" are quantitated. In a similar
approach Tuinstra et al. (1983) have quantitated six specific, diagnostic
congeners which appear to be useful for regulatory cutoff anclyses.
47
b. GC/Hall Electrolytic Conductivity Detector
Electrolytic conductivity dete~tors have also been used with
packed colu~n gas chromatography to selectively detect PCBs (Webb and McCall
1973, Sawyer 1978). The Hall electrolytic conductivity detector (HECD) mea-.
sures the change in conductivity of a solution containing HCl or HBr which is
formed by pyrolysis of halogenated organic GC effluents. The HECD exhibits
105-10 6 selectivity for halogenated compounds over other compounds. It also
gives a linear response over at least a 103 range. HECO and ECO were com-
pared for their use in detecting PCBs in waste oil, hydraulic fluid, capacitor
fluid, and transformer oil (Sonchik et al. 1984). They found both detectors
acceptable, but noted that .the HECD gave higher results with less precision
than the ECO. The method detection limits ranged from 3-12 ppm for HECD and
2-4 ppm for ECO. Greater than 100% recovery of spikes analyzed by HECO indi-
cated a nonspecific response to non-PCB components, since extraneous peaks
were not observed. Another comparison of HECO and ECO for the analysis of
PCBs in oils at the--3&-5-60 ·ppm levels found that the type of detector made no
significant difference in the results (Levine et al. 1983). The authors noted
that they had expected higher accuracy from the more specific HECO. They
postulated that the cleanup procedures (Florisil, alumina, and sulfuric acid)
all had effectively removed the no~-PCB species which would have caused
interferences in the ECO and reduced its accuracy.
c. GC/Mass Spectrometry
Highly specific identification of PCBs is performed by GC with
mass spectrometric (GC/MS) detection. High resolution gas chromatography is
generally used with mass spectrometry, so individual PCB isomers may be
separated and identified. A GC/MS produces a chromatogram consisting of data
points at about 1 second intervals, which are actually full mass spectra. The
data are stored by a computer and may be retrieved in a variety of ways. The
data file contains information on the amount of compound (signal intensity),
molecular weight (parent ion), and chemical composition (fragmentation pat-
terns and isotopic clusters). ·
· GC/MS is particularly suited to detection of PCBs because of
its intense molecular ion and the characteristic chlorine cluster. Chlorine
has two naturally occurring isotopes, 35 Cl and 37 Cl, which occur in a ratio
of 100:33. Thus, a molecule with one chlorine atom will have a parent ion,
M, and an M+2 peak at 33% relative intensity. With two chlorine atoms, M+2
has an intensity of 66~~ and M+4, 113~.
Because of its expense, complexity of data, and lack of sensi-
tivity, GC/MS has not been used as extensively as other GC methods (particu-
larly GC/ECD), despite its inherently higher information content. As the .,
above factors have been improved, GC/MS has become much more popular for
analysis of PCBs, and will probably continue to increase in importance. Sev-
eral factors including the introductio·n of routine instruments without costly
accessories, decreasing data system costs, and mass-marketing, have combined
to keep the costs of GC/MS down while prices of other instruments have risen
stead~ly. With larger data systems and more versatile and 11 user-friendl/1
48
software, the large amount of data is more easily handled. However, data re-
duction of a GC/MS chromatogram still requires substantially more time than
for a GC/ECO chromatogram. In addition, the ..sensitivity of GC/MS has im-
proved.
d. Field-Portable Gas Chromatoaraohv Instrumentation
Gas chromatography may be used for analysis of samples in the
field. Gas chromatography is a well-established laboratory technique, and
.portable instruments with electron capture detectors are available (Spittler
1983, Colby et al. 1983, Picker and Colby 1984). A field-portable GC/ECD
was used to obtain rapid measurements of PCBs in sediment and soil (Spittler
1983). The sample preparation consisted of a single solvent extraction. The
PCBs were eluted from the GC within 9 min. In a 6-h period, 40 soils and
10 QC samples were analyzed, with concentrations ranging from 0.2 to 24,000
ppm. The use of field analysis permits real-time decisions in a cleanup op-
eration and reduces the need for either return visits to a site.
Mobile mass spectrometers are also available. An atmospheric
pressure chemical ionization mass spectrom·eter, marketed by SCIEX, has been
mounted in a van and used for in situ analyses of soil and clay (Lovett et al.
1983). The instrument has apparent1y been used for field determination of
PCBs in a variety of emergency response situations, including hazardous waste
site cleanups. Ot her, more conventional mass spectrometers, should also be
amenable to use in the field.
2. Thin-Laver Chromatoaraohv (TLC)
Thin-layer chromatography is a well-established analytical tech-
nique which has been used for the determination of PCBs for many years.
Since the publication of a TLC method for PCBs by Mulhern (Mulhern 1968,
Mulhern et al. 1971), several researchers have used TLC to measure PCBs in
various matrices. Methods have been reported by Willis and Addison (1972)
for the analysis of Aroclor mixtures, by Piechalak (1984) for the analysis of
soils, and by Stahr (1984) for the inalysis of PCB containing oils. Even with
a densitometer to measure the intensity of the spots, TLC is not generally
considered quantitative. Order-of-magnitude estimates of the concentration
are certainly obtainable, but the precision and accuracy probably do not
approach that of the gas chromatographic methods.
A spill site sample extract will probably need to be cleaned up
before TLC analysis. Levine et al. (1983) have published a comparison of
various cleanup procedures. Stahr (1984) has compared the Levine sulfuric
acid cleanup to a SepPak® C16 cleanup method.
Different TLC techniques have been used to improve the sensitivity
and selectivitv of the method. Several researchers have reoorted that the
use of reverse:phase TLC (C 18-bonded phase) achieves a better separation
of PCBs from interferences (DeVos and Peet 1971, DeVos 1972, Stalling and
Huckins 1973, Brinkman et al. 1976). Koch (1979) has reported an order of
magnitude improvement in the PCB limit of detection through use of circular
49
TLC . The two most common methods of visualization are fluorescence (Kan et al.
1973, Ueta et al. 1974) and reaction with AgN0 3 followed by UV irradiation
(DeVos and Peet 1971, OeVos 1972, Kawabata 1914, Stahr 1984).
No direct comparison of the performance of TLC with other techniques
for analysis of samples from spill sites has been made. Two studies (Bush et
al. 1975, Collins et al. 1972) compared TLC and GC/ECD. In both studies, the
PCB values obtained were comparable. However, the study by Bush et al. indi-
cated that the TLC results were generally lower than GC/ECD.
3. Total Oraanic Halide Analyses
Total organic halide analysis can be used to estimate PCB concen-
trations for guiding field work, but is not appropriate for verification or
enforcement analyses. A total organic halide analysis indicates the presence
of chlorine and sometimes the other halogens. Many of the techniques also
detect inorganic chlorides such as--sodi-t!m ~hioride. The reduction of organo-
chlorine to free chloride ion with metallic sodium can be used for PCB analy-
sis. The free chloride ions can be then detected colorimetrically (Chlor-N-
Oil®) or by a chloride ion-specific electrode (McGraw-Edison). The perfor-
mance of these kits has not been tested with any matrix other than mineral
oil. X-ray fluorescence (XRF) has also been studied as a PCB screening tech-
nique (McQuade 1982 , Schwalb and Marquez 1982).
D. Selection of Aoprooriate Methods
1. Criteria for Selection
The primary criterion for an enforcement method is that the data be
highly reliable (i.e., they are leg2lly defensible), This does not necessarily
_imply that the most exotic, state-of-the-art methods be employed; rather that
:the methods have a sound scientific basis and v2lidation data to support their
use. Many other criteria also enter into selection of a method, including
accuracy, precision, reproducibility, comparability, consistency across ma-
trices, availability, and cost.
For PCB sp i lls, it is assumed that the spills will be relatively
fresh and therefore that PCB mixtures will generally resemble those in com-
mercial products (i.e., Aroclors). It is further assumed that, for most of
the matrices likely to be encountered, the levels of interferences will be
relatively low .
. 2. Selection of Instrumental Techniaues : ,
Based upon the above criteria and assumptions, either GC/ECD or
GC/MS should provide suitable data. Since GC/ECD is included in more stan-
dard methods and since the technique ts more widely used, it appears to be
the technique of choice . The primary methods recommended below are all based
on GC/ECD instrumental analysis. Some of the secondary and confirmatory tech-
niques are based on GC/EIMS.
50
!
i -
3. Selection of Methods
Ideally, a standard method would be~vailable for each matrix likely
to be encountered in a PCB spill. The matrices of concern include solids (soil,
sand, sediment, bricks, asphalt, wood, etc.), water, oil, surface wipes, and.
vegetation. The methods for these matrices are summarized in Table 22 and
discussed in detail below. A primary recommended method is given and should
be used in most spill instances. The secondary method may be useful for con-
firmatory analyses, or where the situation (e.g., high level of interferences)
indicates that the primary method is not applicable. The methods used must
be documented or referenced.
a. Solids (Soil, Sand, Sediment, Bricks. Asohalt, Wood. Etc.)
EPA Method 8080 from SW-846 (USEPA 1982e) is the primary recom-
mended method. The secondary methods, Method 8250 and Method 8270, are GC/MS
analogs. Method 8080 entails an acetone/hexane (1:1) extraction, a Florisil
column chromatographic cleanup, and a GC/ECD instrumental determination. A
total area quantitation versus Aroclor standards is specified. No qualitative
criteria are supplied. A detection limit of 1 µg/g is prescribed. No valida-
tion data are available.
Bulk samples (bricks, asphalt, wood, etc.) should be re~dily
extractable using a Soxhlet extractor according to EPA Method 8080 (USEPA
1982e). The sample must be crushed and subsampled to ensure proper solvent
contact.
b. Water
EPA Method 608 (USEPA 1984e) is recommended as the primary ·
method. This is one of the 11 pri ori ty po 11 utant11 methods and i nvo 1 ves extrac-
tion of water samples with dichloromethane. An optional Florisil column
chromatographic cleanup and also an optional sulfur removal are given. Sam-
ples are analyzed by GC/ECO and quantitaied against the total area of Aroclor
standards. No qualitative criteria are given. This method has been exten-
sively validated and complex recovery and precision equations are given in
the method for seven Aroclor mixtures . The average recovery is about 86% and
average overall precision about± 26%. The average recovery and precision
for the more common Aroclors (1242, 1254, and 1260) are about 78% and± 25%,
respectively. Detection limits are not given in the current version (USEPA
1984a), although they were listed as between 0.04 and 0.15 µg/L for the seven
Aroclor mixtures listed as priority pollutants in the method validation study
(Millar et al. 1984).
c. Oils
Spilled oil samples shquld be analyzed according to an EPA
method (Bellar and Lichtenberg 1981). The method is written for transformer
fluids and waste oils, but should also be applicable to other similar oils
such as capacitor fluids. In this method, samples are diluted by an appro-
priate factor (e.g., 1:1000). Six optional cleanup techniques are given.
51
r -\· Table 22. , Summary of Recommended Analytical Methods Primar~ method (GC/ECO) Secondar~ method Matrix . Designation Reference Designation GC detector Reference Solids· 8080 USEPA 1982e 8250, 8270 MS USEPA 1982e Water GOO USEPA 1904a 625 MS USEPA 19Mb Oil 110 i l 11 USEPA 1901a; 110 i l" MS USEP/\ 1981a; llel lar and nellar and Ul . Lichlenherg, Lichtenberg, N 1981 1981 Surface llexane extrac-None Hexane extrac-MS None wipes tion/608 tion/625 -i, Vegetation AO/\C (29) AOAC 1980a None None None .
The sample may be analyzed by GC/ECD as the primary method. Secondary instru-
mental choices, also presented in the method, are GC/HECD, GC/MS, and capil-
lary GC/MS. PCBs are quantitated by either tgtal areas or the Webb-McCall
(1973) method. No qualitative criteria are given. QC criteria are given. A
detection limit of 1 mg/kg is stated, although it is highly dependent on the_
amount of dilution required. An interlaboratory validation study (Sonchik
and Ronan 1984) indicated 81 to 126% recoveries for different PCB mixtures,
with an average of 97% for Aroclors 1242, 1254, and 1260, as measured by ECO.
The overall method precision ranged from± 11 to± 55%, with an average of
± l~~ for Aroclors 1242, 1254, and 1260. The method validation statistics
were presented in more detail as regression equations.
d. Surface Wipes
No standard method is available for analysis of PCBs collected
on surface wipes. However, since this matrix should be relatively clean and
easily extractable, a simple hexane extraction should be sufficient. Samples
should be analyzed according to EPA Method 608 (USEPA 1984a), except for
Section 10.1 through 10.3. In lieu of these sections, the sample shou1d be
extracted three times with 25 to 50 ml of hexane . The sample can be extracted
by shaking for at least 1 min per extraction in the wide-mouthed jar used for
sample storage. Note that the rinses should be with hexane so that solvent
exchange from methylene chloride to hexane (Section 10. 7) is not necessary.
e. Veaetation
The AOAC (1980a) procedure for food is recommended for analysis
of vegetation (leaves, vegetables, etc.). This method involves extraction of
a macerated sample with acetonitrile. The acetonitrile is diluted with water
and the PCBs extracted into petroleum ether. The concentrated extract is
cleaned up by Florisil column chromatography by elution with a mixture of ethyl
ether and petroleum ether. The sample is analyzed by GC/ECO with quantitation
by total areas or individual peak heights as compared to Aroclor standafds.
No qualitative criteria are given. Validation studies with chicken fat and
fish (Sawyer 1973) are not relevant to the types of matrices to be encountered
in PCB spills .
4. Imolementation of Methods
Each laboratory is responsible for generating reliable data. The
first step is preparation of an in-house protocol. This detailed 11 cookbook 11
is based on methods cited above, but specifies which options must be followed
and provides more detail in the conduct of the techniques. It is essential
that a written protocol be prepared for auditing purposes.
: ,
53
Each laboratory is responsible for generating validation data to
demonstrate the performance of the method in the laboratory. This can be
done before processing of samples; however, it is often impractical. Valida-
tion of meth6d performance (replicates, spikei, QC samples, etc.) while ana-
lyzing field samples is acceptable.
Changes in the above methods are acceptable, provided the changes
are documented and also provided that they do not affect performance. Some
minor changes (e.g., substitution of hexane for petroleum ether) do not
generally require validation. More significant changes (e.g., substitution
of a HECD for ECO) will require documentation of equivalent performance.
E. Quality Assurance
Quality assurance must be applied throughout the entire monitoring
program including the sample planning and collection phase, the laboratory
analysis phase, and the data processing and interpretation phase.
Each participating EPA or EPA contract laboratory must develop a
quality assurance plan (QAP) according to EPA guidelines (USEPA 1980). Ad-
ditional guidance is also available (USEPA 1983). The quality assurance plan
must be submitted to the regional QA officer or other appropriate QA official
for approval prior to analysis of samples.
1. Quality Assurance Plan
The elements of a QAP (U.S. EPA, 1980) include:
Title page
Table of contents
Project description
Project organization and responsibility
QA objectives for measurement data in terms of precision, ac-
curacy, completeness, representativeness, and comparability
Sampling procedures .
Sample tracking and traceability
Calibration procedures and frequency
Analytical procedures
Data reduction, validation and reporting
Internal quality control checks
Performance and system audits
Preventive maintenance
Specific routine procedures used to assess data precision,
accuracy and completeness
Corrective action
Quality assurance reports to management
54
: ,
2. Quality Control
Each laboratory that uses this method must operate a formal quality
control (QC) program. The minimum requirements of this program consist of an
initial and continuing demonstration of acceptable laboratory performance by.
the analysis of check samples, spiked blanks, and field blanks. The labora-
tory must maintain performance records which define the quality of data that
are generated.
The exact quality control measures will depend on the laboratory,
type and number of samples, and client requirements. The QC measures should
be stipulated in the QA Plan. The QC. measures discussed below are given for
example only. Laboratories must decide on which of the measures below, or
additional measures, will be required for each situation.
a. Protocols
Virtually all of the available PCB methods contain numerous
options and general instructions. Effective implementation by a laboratory
requires the preparation of a detailed analysis protocol which may be followed
unambiguously in the laboratory. This document should contain working instruc-
tions for all steps of the analysis. This document also forms the basis for
conducting an audit.
b. Certification and Performance Checks
Prior to the analysis of samples, the laboratory must define
its routine performance. At a minimum, this must include demonstration of
acceptable response factor precision with at _least three replicate analyses
of a calibration solution; and analysis of a blind QC check sample (e.g., the
response factor calibration solution at unknown concentration submitted by an
independent QA officer). Acceptable criteria for the precision and the ac-
curacy of the QC check sample analysis must be presented in the QA plan.
Ongoing performance checks should include
of the initial demonstration or more elaborate measures.
sures may include control charts and analysis of QA check
unknown PCBs, and possibly with matrix interferences.
c. Procedural QC
periodic repetition
More elaborate mea-
samp1es containing
The various steps of the analytical procedure should have qual-
ity control measures. These include, but are not limited to, the following:
Instrumental Performance: Instrumental performance crt~
teria and a system for routineiy monitoring the performance should be set out
in the QA Plan. Corrective action fo~ when performance does not meet the
criteria should also be stipulated.
55
Qualitative Identification: Any questionable results should be confirmed by a second analytical method. A least 10% of the ;__ identifications, as well as any questionable r..esults, should be confirmed by a second analyst.
Ouantitation: At least 10% of all calculations must be checked. The results should be manually checked after any changes in computer quantitation routines.
d. Samole QC
Each sample and each sample set must have QC measures applied to it to establish the data quality for each analysis res·ult. The following should be considered when preparing the QA plan:
Field Blanks: Field blanks are analyzed to demonstrate that the sample collection equipment has not been contaminated. A field blank may be generated by using the sampling equipment to collect a blank sample (e.g., using the water sampling equipment to sample laboratory reagent grade water) or by extracting the sampling equipment (e.g., extracting a sheet of filter paper from the lot used to collect wipe samples or rinsing the soil sampling apparatus into the sample jar). A field blank must be collected and . analyzed for each type of sample collected.
Laboratory Reaaent Blanks: These blanks are generated in the laboratory and are analyzed to assess contamination of glassware, reagents, etc., in the laboratory. Generally, a reagent blank is processed through the entire analysis process. Although in special circumstances, additional reagent blanks may be generated which are processed through only part of the procedure to isolate sources of contamination. At least one laboratory reagent blank must be generated and analyzed for each type of sample analyzed.
Check Samoles: These samples contain known concentrations of PCBs in the sample matrix. They are analyzed along with field samples to demonstrate the method performance. The PCB concentrations may be known to the analyst.
Blind Check Samoles: These samples are the same as the check samples discussed above, except the PCB concentration is not known to the analyst.
Reolicate Samoles: One sample from each batch of 20 or fewer will be analyzed in triplicate. The sample is divided into three rep-licate subsamples and all these subsamples carried through the analytical pro-cedure, blind to the analyst. The results of these analyses must be compar-a-ble within the limits required for spiked samples.
Soiked Samoles: The sensitivity and reproducibility must be demonstrated for any method used to report verification data. -This can be done by analyzing spiked blanks near the required detection limit. To demon-strate the ability of the method to reproducibly detect the spiked sample, one or more spiked samples should be analyzed in at least triplicate for each group of 20 or fewer samples within each sample type collected. Samples will
56
r-:
l i be spiked with a PCB mixture similar to that spilled (e.g., Aroclor 1260).
Example concentrations are:
Matrix
Soil, etc.
Water
Wipes
Soike Level
10 µg/g (10 ppm)
100 µg/L (100 ppb))
100 µg/wipe (100 µg/100 cm~)
Quantitative techniques must detect the spike level within ±30% for all spiked
samples.
e. Samole Custodv
As part of the Quality Assurance Plan, the chain-of-custody
protocol must be described. A chain-of-custody provides defensible proof of
the sample and data integrity. The less rigorous sample traceability docu-
mentation merely .provides a record of when operations were performed and by
whom. Sample traceability is not acceptable for enforcement activities.
Chain-of-custody is required for analyses which may result in
legal proceedings and where the data may be subject to legal scrutiny.
Chain-of-custody provi9es conclusive written proof that samples are taken,
transferred, prepared, and analyzed in an unbroken line as a means to maintain
sample integrity. A sample is in custody if:
It is in the possession _of an authorized individual;
It is in the field of vision of an authorized
individual;
It is in a designated secure area; or
It has been placed in a locked container by an
authorized individual.
A typical chain-of-custody protocol contains the following elements:
1. Unique sample identification numbers.
2. Records of sample container preparation and integrity ·•
· prior to sampling .
· 3. Records of the sample collection such as:
Specific location of sampling.
57
Date of collection.
Exact time of collect;on.
Type of sample taken (e.g., air, water, soil).
Initialing each entry.
Entering pertinent information on chain-of-
custody record.
Maintaining the ~amples in one's possession or
under lock and key.
Transporting or shipping the samples to the
analysis laboratory.
Filling out the chain-of-custody records.
The chain-of-custody records must accompany the
samples.
4. Unbroken custody during shipping. Complete shipping
records must be retained; samples must be shipped in
locked or sealed (evidence tape) containers.
5. -Laboratory chain-of-custody procedures consist of:
Receiving the samples.
Checking each sample for tampering.
Checking each sample against the chain-of-custody
records.
Checking each sample and noting its condition.
Assigning a sample custodian who will be responsible
for maintaining chain-of-custody.
Maintaining the sign-offs for every transfer of each
sample on the chain-of-custody record.
Ensuring that~ manipulations of the sample _ are .,
duly recorded in a laboratory notebook along with
sample number and date. These manipulations will
be verified ~y the program manager or a designee.
F. Documentation and Records
Each laboratory is responsible for maintaining complete records of
the analysis. A detailed documentation plan should be prepared as part of
58
---1
I
the QAP. Laboratory notebooks should be used for handwritten records. Digi-
tal or other GC/MS data must be archived on magnetic tape, disk, or a similar
device. Hard copy printouts may also be kept.,.if desired. Hard copy analog
data from strip chart recorders must be archived. QA records should also be
retained.
The documentation must completely describe how the analysis was
performed. Any variances from a standard protocol must be noted and fully
described. Where a procedure lists options (e.g., sample cleanup), the op-
tion used and specifics (solvent volumes, digestion times, etc.) must be
stated.
The rema1n1ng samples and extracts should be archived for at least
2 months or until the analysis report is approved by the client organization
(whichever is longer) and then disposed unless other arrangements are made.
The magnetic disks or tapes, hard copy chromatograms, hard copy spectra, quan-
titation reports, work sheets, etc., must be archived for at least 3 years.
All calculations used to determine final concentrations must be documented.
An example of each type of calculation should be submitted with each verifi-
cation spot.
G. Reporting Results
Results of analysis will normally be reported as follows:
Matrix
Soil, etc.
Water
Surfaces (wipes)
Reoortina Units
µg PCB/g of sample (ppm)
mg PCB/L of sample (ppm)
µg PCB/wipe (µg PCB/100 cm2 )
In some cases, the results are to be reported by homolog. In this
case, 11 values are reported per sample: one each for the 10 homologs and
one for the total. Some TSCA analyses require reporting the results in terms
of resolvable gas chromatographic peak (U.S. EPA, 1982c, 1984e). In these
cases, _the number of results reported equals the number of peaks observed on
the chromatogram. These analyses are generally associated with a regulatory
cutoff (e.g., 2 µg/g per resolvable chromatographic peak (U.S. EPA, 1982c,
1984). In these cases it may be sufficient, depending on the client organi-
zation's request, to report only those peaks which are above the regulatory
cutoff.
Even if an Aroclor is used as the quantitation standard, the re-
sults are never to be reported as 11 µg Aroclor@/g sample.11 TSCA regulates all
PCBs, not merely a specific commercia) mixture.
59
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63
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65
t --
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66
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67
-
TECHNICAL REPORT DATA
(Pleau read Jnsrrucnons on the "verse before complaing/
1. RE?ORT NO. 12. 13. RECIPIENT"S ACCESSION NC.
560/5-85-026
4'. TITLE ANO SUBTITLE ,=. 5. REPORT DATE
Verification of PCB Spill Cleanup by Sampling August 1985
6 . PERFORMING ORGANIZATION COO: and Analysis 8501-A(37)
7. AUTHOR(Sl Bruce A. Boomer, Hi tchell D. Erickson, 8 . PERFORMING ORGANIZATION RE?OR7 NC
Stephen E. S1.·anson, Gary L. Kelso, David C. Cox, * Interim Report. No. 2
Bradlev D. Sch111t7*
9. PERFORMING ORGANIZATION NAME ANO ADDRESS 10. PROGRAM ELEMENT ~O.
Midwest Research Insticuce * Washington Consulting Work Assignment No. 37
425 Volker Boulevard Group 11. CONTRAC7/GRANT NO. -Kansas City, Missouri 64110 1625 I Street, N.W. EPA Contract No. 68-02-3938
Washington, DC 20006 I& EPA Contract No. 68-01-6721 I
12. S?ONSORING AGENCY NA,'-'1E ANO ADDRESS 13. TYPE CF RE?OR7 ANO PERIOD c:::,v=c;:;=c::
Exposure Evaluacion Division, TS 798
Office of Toxic Substances, U.S. EPA 14. S?ONSORING AG:NCY CCCE
401 M Street, Sw
washington, DC 20460
15. SUPPLEMENTARY NOTES
The EPA work assignment r:ianagers are Daniel T. Eeggem and Richard A. Levy -The EPA project offi cers Joseph J. Breen and Jose'Jh s. Carr2 are
16. ABSTRACT This report., intended primarily for EPA enforcement personnel, l . out_1nes spe-
cific sampling and analysis methods to determine compliance •,;i th EPA policy on the '
cleanup of PCB spills . The sampling and analysis methods can be used to deter:nine the
residual levels of PCBs at a spill site following the completion of cleanup activities .
~ Although the methodologies outlined in this document are applicable to PCB spills in
\. general, specific incidents may require special efforts beyond the scope of this report.
A sampling design lS proposed for use by EPA enforcement staff in detecting
residual PCB contamination above a designated limit after a spill site has been cle::ne•.:.
The proposed design involves sampling on a hexagonal grid which is centered on the
cleanup area and extends just beyond its boundaries. Guidance is provided for cente::--
ing the design on the spill site, for staking out the sampling locations, and for tak-
1ng possible obstacles into account. Compositing strategies, in .,,,·hich several samples
a re pooled and analyzed together, are recommended for e~ch of the three proposed de-
signs. Sampling and analysis techniques are described for PCB-contaminated so lids
(soil, sediment, etc.), water, oils, surface wipes, and vegetation. Quality assurance
(QA) must be applied throughout the entire monitoring program. Quality control (QC)
measures, including protocols, certification and performance checks, procedural QC,
sample QC, and sample custody as appropriate, should be stipulated in a QA plan.
17. K!:Y WOROS .>.NO DOCUMENT ANALYSIS
~ ··----·-----·-
J . DESCRIPTORS ,b.lOENTIFIERS;OP!:N ENDED TERMS ~-COS.>. Tl 1-ich-!/S;ruup -·--------
PCBs, polychlorinated biphenyl spills, spil
cleanup, sampling, analysis
-...
... '~8. DISTRIBUTION ST.>.TEMENT 19. SECURITY CLASS (This RtporcJ Unclas s if :.ed 121. NO. OF PAGES ,4
20. SECURITY C~ASS (ThiJ pagt/ 122. PRICE
Unlimited Unclassifieri
EPA Fo,m 2:.20-1 (Rn. 4-77) P .. e;v,ous E:::llTION IS OflSOI..ETE:
I
I .
Zell M, Ballschmiter K. 1980. Baseline study of the global pollution. III.
Trace analysis of polychlorinated biphenyls (PCB) by ECO glass capillary gas
chromatography in environmental samples of different trophic levels.
Fresenius' i Anal Chem 304:337-349. -
Zitko V, Hutzinger 0, Safe S. 1971. Retention times and electron-capture
detector responses of some individual chlorobiphenyls. Bull Environ Contam
Toxicol 6(2):160-163.
68
' ,
CHAPTER1
OSHA Instruction CPL 2-2.20B CH-1
NOV 1 3 1990
Directorate of Technical Support
PERSONAL SAMPLING FOR AIR
CONTAMINANTS
A. GENERAL
1. Unnecessary air sampling can tie up
laboratory resources and produce delays in
reporting results of necessary sampling.
Evaluate the potentiai for employee
overexposure through observation and
screening samples before any partial or
full-shift air sampling is conducted Do not
overe xpose the employee to gather a
sample.
2. Screening with portable monitors,
gravimetric sampling, or detector tubes can
be used to evaluate the following:
a. Processes, such as electronic soldering.
b. Exposures to substances with
exceptionally high PELs (Permissible
Exposure Limits) in relatively dust-free
atmospheres, e.g., ferric oxide and
aluminum oxide.
c. Intermittent processes with substances
without STELs (Short Term Exposure
Limits)
d. Engineering controls, work practices, or
isolation of process.
e. The need for CSHO protection
3. Take a sufficient number of samples to
obtain a representative estimate of
exposure. Contaminant concentrations vary
seasonally, with weather, with production
levels, and in a single location or job class.
4. The number of samples taken depends on
tt1e error of measurement and differences in
results. Consult the NIOSH Occupational
Exposure Sampling Strategy Manual for
further information.
5. If the employer has conducted air sampling
and monitoring in the past, review the
records .
6. Bulk Samples are often required to assist the
Salt Lake City Lab in the proper analysis of
field samples. (See the Sample Shipping
and Handling Chapter.) Some contaminants
which tali into these categories include:
-silica,
-portland cement,
-asbestos
-mineral oil and oil mist,
-chlorodiphenyl,
-hydrogenated terphenyls, and
-chlorinated camphene
-fugitive grain dust
-explosibility testing.
B. GENERAL SAMPLING
PROCEDURES
1. Screen the sampling area using detector
tubes, if appropriate. Determine the
appropriate sampling technique (see
Section C and the Chemical Information
Manual). Prepare and calibrate the
equipment and prepare the filter media
(Section F).
2. Select the employee to be sampled and
discuss the purpose of the sampling. Inform
the employee when and where the
equipment will be removed . Stress the
1 -1
OSHA Instruction CPL 2-2.208 CH-1
NOV 1 3 1990
Directorate of Technical Support
importance of not removing or tampering
with the sampling equipment. Turn off or
remove sampling pumps before an
employee leaves a potentially contaminated
area (such as when he/she goes to lunch or
on a break).
3. Instruct the employee to notify the
supervisor or the CSHO if the sampler
requires temporary removal.
4. Place the sampling equipment on the
employee so that it does not interfere with
work performance.
5. Attach the collection device (filter cassette,
charcoal tube, etc.) to the shirt collar or as
close as practical to the nose and mouth of
the employee, i.e., in a hemisphere forward
of the shoulders with a_ra~i~~ . .-R!
approximately 6 to 9 inches. ~~
The inlet should always be in a downward
vertical position to avoid gross
contamination. Position the excess tubing
so as not to interfere with the work of the
employee.
6. Turn on the pump and record the starting
time.
7. Observe the pump operation for a short time
after starting to mal<e sure it is operating
correctly.
8. Record the information required by the Air
Sampling Data Form (OSHA-91A).
9. Check pump status every two hours. More
frequent checks may be necessary with
heavy filter loading. Ensure that the sampler
is still assembled properly and that the hose
has not become pinched or detached from
the cassette or the pump. For filters, observe
for symmetrical deposition, finger prints, or
large particles, etc. Record the flow rate.
10. Periodicali y monitor the employee
throughout the 'Nork day to ensure that
1 -2
Figure 1-1a. Improperly sealed
cassette allows access to inlet and
outlet ports after sample has been
taken.
Figure 1-1 b. Properly sealed
cassette covering inlet and outlet ports
provides for sample security.
sample integrit, is maintained and cyclical
activities and work practices are identified.
11. Take photographs, as appropriate, and
detailed notes concerning visible airborne
contaminants, worl< practices, potential
interferences, movnnents, and other
conditions to assist in determining
appropriate engineering controls.
12. Prepare a blank(s) during the sample period
for each type of sample collected. See the
Sample Shipping and Handling Chapter. For
any given analysis, one blank will suffice for
up to 20 samples collected, except for
asbe$tos which requires a minimum of two
field blanks.. These blanks may include
opened but unused charcoal tubes, and so
forth.
13 Before removing the pump at the end of the
sample period, check the flow rate to ensure
that the rotameter ball is still at the calibrated
mark (if there is a pump rota meter). If the ball
is no longer at the mark, record the pump
rotameter reading.
14. Turn off the pump and record tho ending
time.
15. Remove the collection device from the pump
and seal it with an OSHA-21 as soon as
possible. The seal should be attached
across sample inlet and outlet so that
tampering is not possible. (See Figures 1-1 a
and1-1b.)
16. Prepare the samples for mailing to the Salt
Lake City Analytical Laboratory (SLCAL) for
analysis. (See Chapter 9.)
17. Recalibrate pumps after each day of
sampling (before charging).
18. For unusual sampling conditions, such as
wide temperature and pressure differences
from the calibration conditions, call the
regional technical support section.
OSHA Instruction CPL 2-2.20B CH-1
NOV 1 3 1990
Directorate of Technical Support
C.SAMPUNG
TECHNIQUES
1. Detector Tubes
a. Each pump should be leak-tested before
use.
b. Calibrate the detector tube pump for
proper volume at least quarterly or after
100 tubes. (See Appendix 1-A.)
2. Total Dust and Metal Fume
a. Collect total dust on a pre-weighed,
!ow-ash polyvinyl chloride filter at a flow
rate of about 2 liters per minute (1pm),
depending on the rate required to prever,t
overloading.
b. Collect metal fumes on a 0.8 micron mixed '
cellulose ester filter at a flow rate of
approximately 1.5 1pm, not to exceed
2.0 1pm. When the gravimetric weight
needs to be determined for welding fumes,
collect these fumes on a low-ash polyvinyl
chloride filter.
c. Take care to avoid any overloading of the
filter, as evidenced by any loose
particulate.
d. Calibrate personal sampling pumps
before and after each day of sampling,
using a bubble meter method (electronic
or mechanical) or the precision rotameter
method (that has been calibrated against
a bubble meter), as described in
Section E.
e. Weigh PVC filters before and after taking
the sample. See Section F.
3. Respirable Dust
a. Collect respirable dust using a clean
cyclone equipped with a pre-weighed
low-ash polyvinyl chloride filter at a flow
+ rate of 1.7 -=-0.2 Lpm.
1 -3
OSHA Instruction CPL 2-2.208 CH-1
NOV 1 3 1990
Directorate of Technical Support
b. Collect silica only as a respirable dust. A
bulk sample should be submitted to the
Salt Lake City Analytical Laboratory.
c. All filters used shall be pre-weighed and
post-weighed.
d. Calibration Procedures
1) Do the calibration at the pressure and
temperature where the sampling is to
be conducted .
2) For respirable dust sampling using a
cyclone or for total dust sampling using
an open face filter cassette, set up the
calibration apparatus as shown in
Figure 1-10.
3) Place the open face filter cassette or
cyclone assembly in a 1-liter jar. The
jar is provided with a special cover.
4) Connect the tubing from the electronic
bubble meter to the inlet of the jar.
5) Connect the tubing from the outlet of
the cyclone holder assembly or from
the filter cassette to the outlet of the jar
and then to the sampling pump.
6) Calibrate the pump. The calibration
readings must be within 5% of each
other.
e. Cyclone cleaning
1) Unscrew the grit pot from the cyclone.
Empty the grit pot by turning it upside
down and tapping it gently on a solid
surface.
2) Clean the cyclone thoroughly and
gently after each use in warm soapy
water or, preferably, wash in an
ultrasonic bath. Rinse thoroughly in
clean water, shake off excess water,
and set aside to dry before
reassembly. Never insert anything
into the cyclone during clea ning. See
Figure 1-2.
3) Inspect the cyclone parts for signs of
wear or damage, such as scoring,
rifling, or a loose coupler. Replace the
units or parts if they appear damaged.
1 -4
HOLDER
ASSEMBLY
----FLOW CONNECTOR
ASSEMBLY
c,, cQLOCKING NUT
~~:!)
Figure 1-2. The cyclone (chamber) of
the cyclone assembly is sensitive to
scratches.
Figure 1-3. A charcoal or "C"-tube
with glass-sealed ends and
NIOSH-approved caps is shown
before taking a sample.
4) Leak test the cyclone at least o~ce a
month with regular usage.
5) Detailed instructions on leak testing are
available from the Directorate of
Technical Support.
4. Organic Vapors and Gases
a. Organic vapors and gases may be
collected on activated charcoal, silica gel,
or other adsorption tubes using low flow
pumps.
b. Immediately before sampling, break off the
ends of the charcoal tube so as to provide
an opening approximately one-half the
internal diameter of the tube. Wear eye
protection when breaking ends. Use tube
hoiders, if available, to minimize the
hazards of broken glass. Do not use the
charging inlet or the exhaust outlet of the
pump to break the ends of the charcoal
tubes. See Figure 1-3, charcoal tube.
c. Use the smaller section of the charcoal
tube as a back-up and position it near the
sampling pump. The charcoal tube shall
be held or attached in an approximately
vertical position with the inlet either up or
down during sampling.
Figure 1-4a. Correctly, sealed 1
"C"-Tube. Sample is completely
enclosed in the seal and no tampering ·
is possible.
1 --5
OSHA Instruction CPL 2-2.20B CH-1
NOV 1 3 1990
Directorate of Technical Support
d. Draw the air to be sampled directly into
the inlet of the charcoal tube. This air is
not to be passed through any hosE! or
tubing before entering the charcoal tube.
e. Cap the charcoal tube with the supplied
plastic caps immediately after sampling
and seal with an OSHA-21 as soon as
possible. (See Figures 1-4a and 1 ·-4b,
C-tube seal.) Do not ship with bulk
material.
f. For other adsorption tubes, follow the
same procedures as those for the charcoal
tube, with the following exceptions:
1) Tubes may be furnished by SLCAL with
either caps or flame-sealed glass ends.
If using the capped version, simply
uncap during the sampling period and
recap at the end of the sampling period.
2) The ends of the flame-sealed glass
tubes are broken at the beginning e,f the
sampling period and capped at the end
of the sampling period.
g. For organic vapors and gases, low flow
pumps are required. Refer to the
Chemical Information Manual to .
Figure 1-4b. Incorrectly, sealecl
"C"-Tube. End caps can be removed
and sample integrity jeopardized
without disturbing the seal.
OSHA Instruction CPL 2-2.20B CH-1
NOV 1 3 1990
Directorate of Technical Support
determine the appropriate flow rates
recommended for specific chemicals.
h. With sorbent tubes, flow rates may have to
be lowered or smaller air volumes (1/2 the
maximum ) used when there is high
humidity (above 90%) in the sampling area
or relatively high concentrations of other
organic vapors.
i. Calibration Procedures
1) Set up the calibration apparatus as
shown In Figure 1-9 replacing the
cassette with the solid sorbent tube to
be used in the sampling (e.g., charcoal,
silica gel, etc.). If a sampling protocol
requires the use of two charcoal tubes,
then the calibration train must include
two charcoal tubes. The air flow must
be in the direction of the arrow on the
tube.
2) Calibrate the pump.
5. Midget lmpingers/Bubblers
a. Method
1) Take care in preparing bubblers and
impingers to see that frits or tips are not
Figure 1-5. A typical glass bubbler is
illustrated.
1 -6
damaged and that joints can be
securely tightened.
2} Rinse the impinger/bubbler, Figure 1-5,
with the appropriate reagent (see the
Chemical Information Manual and
Appendix 1-D). Then, add the
specified amount of this reagent to the
impinger flask either in the office or at
the sampling location. If flasks
containing the reagent are transported,
caps must be placed on the impinger
stem and side arm. To prevent
overflowing, do not add over 10
milliliters of liquid to the midget
impingers.
3) Collect contaminants in an impinger at
a maximum flow rate of 1.0 1pm.
Contact the SLCAL prior to collecting
samples for dust counting.
4) The impi11ger may either be hand-held
by the industrial hygienist or attached
to the employee's clothing using an
impinger holster. In either case, it is
very important that the impinger does
not tilt, causing the reagent to flow
down the side arm to the hose and into
the pump.
NOTE: Attach a trap in line to the pump, if
possible.
5) In some instances, it will be necessary
to add additional reagent during the
sampling period to prevent the amount
of reagent from dropping below
one-half of the original amount.
6) After sampling, remove the glass
stopper and stem from the impinger
flask.
7) Rinse the absorbing solution adhering
to the outside and inside of the stem
directly into the impinger flask with a
small amount (1 or 2 ml.) of the
sampling reagent. Stopper the flask
tightly with the plastic cap provided or
pour the contents of the flask into a
20 cc. glass bottle. Rinse the flask with
a small amount (1 or 2 ml.) of the
reagent and pour the rinse solution into
the bottle. Tape the cap shut to prevent
it from coming loose due to vibration. If
electrical tape is used, do not "stretch"
tape since it will contract and loosen
cap.
b. Calibration Procedure
1) Set up the calibration apparatus as
shown in Figure 1-9, replacing the
cassette with the impinger/bubbler
filled with the amount of liquid reagent
specified in the sampling method.
(Refer to Chemical Information
Manual.)
2) Connect the tubing from the electronic
bubble meter to the inlet of the
impinger/bubbler.
3) Connect the outlet of the
impinger/bubbler to the tubing to the
pump.
4) Calibrate the pump at a maximum flow
rate of 1.0 1pm.
Figure 1-6. Vapor badge shown has
a clothing clip.
OSHA Instruction CPL 2-2.20B CH -1
NOV 1 3 1990
Directorate of Technical Support
6. Mailing
Mail bulks and air samples separately to
avoid cross-contamination. Pack the
samples securely to avoid any rattle or
shock damage (do not use expanded
polystyrene-"packing"). Use bubble
sheeting as packing. Put identifying
paperwork in every package. Do not send
samples in plastic bags or in envelopes.
Use OSHA Form 91A. PRINT LEGIBLY
ON ALL FORMS. See Chapter 9.
7. Vapor Badges
a. Passive diffusion sorbent badges,
Figure 1-6, are useful for screening and
monitoring certain chemical exposures,
especially vapors and gases. Few badges
have been validated for use in compliance.
b. Badges are available from the SLCAL to
detect mercury, nitrous oxides, ethylene
oxide, formaldehyde, etc.
c. Interfering substances should be noted.
D. SPECIAL SAMPLING
PROCEDURES
1 -7
1.Asbestos
a. Collect asbestos on a special
0.8 micrometer pore size, 25 mm diameter
mixed cellulose ester filter, using a
back-up pad .
b. Use fully conductive cassette with
conductive extension cowl, Figure 1-7.
c. Sample open face in worker's breathing
zone.
d. Assure that the bottom joint (between the
extension and the conical black piece) of
the cassette is sealed tightly with a shrink
band or electrical tape. Point the open end
of the cassette down to minimize
contamination.
e. Use a flow rate in the range of 0.5 to
2.5 liters per minute. One liter per minute
is suggested for general sampling. Office
OSHA Instruction CPL 2-2.20B CH -1
NOV 1 3 1990
Directorate of Technical Support
environments allow flow rates of up to
2.5 1pm. Calibrate pump before and after
sampling. Calibration may be done either
as in figure 1-9 or 1-10. Do not use nylon
or stainless steel adaptors if in-line
(Figure 1-9) calibration is done.
f. Sample for as long a time as possible
without overloading (obscuring) the filter.
g. Submit 10% blanks, with a minimum in all
cases of 2 blanks.
h. Where possible, collect and submit to the
SLCAL a bulk sample of the material
suspected to be in the air.
i. Mail bulks and air samples separately to
avoid cross-contamination. Pack the
samples securely to avoid any rattle or
Clear tape is placed
circumferentially to
keep the seal on
and intact.
Ends taped together
(seal is not long
enough to go clear
around )
Figure 1-7. A standard asbestos
cassette (25mm.) sealed properly with
an OSHA 21 form.
shock damage (do not use expanded
polystyrene-"packing"). Use bubble
sheeting as packing. Put identifying
paperwork in every package. Do not send
samples in plastic bags or in envelopes.
Use OSHA Form 91A. PRINT LEGIBLY
ON ALL FORMS.
j. Instruct the employee to avoid knocking
the cassette and to avoid using a
compressed air source that might
dislodge the sample.
k. This procedure has been revised as of
May, 1989. For exceptional sampling
conditions or high flow rates, contact the
SLCAL. More detailed instructions can be
obtained from SLCAL.
2. Sampling for welding fumes
a. When sampling for welding fumes, the
filter cassette must be placed inside the
welding helmet to achieve an accurate
characterization of the employee"s
exposure.
b. Welding fume samples are normally taken
using 37-mm filters and cassettes;
however, if these cassettes will not fit
inside the helmet, 25-mm filters and
cassettes can be used. Care must be
taken not to overload the 25-mm. cassette
when sampling.
c. The Assistant Regional Administrator for
Technical Support should be consulted in
the case of any technical difficulties.
E. EQUIPMENT
PREPARATION AND
CALIBRATION
1. Replace alkaline batteries frequently (once
a month). Al so carry fresh replacement
batteries with the equipment
1 -8
E. EQUIPMENT
PREPARATION AND
CALIBRATION
1. Replace alkaline batteries frequently (once
a month). Also cany fresh replacement 4.
batteries with the equipment.
2. Check the rechargeable NI-Cad batteries In
· older pumps under load (e.g., tum pump on
and check voltage at charging jack) before
use.
3. Calibrate personal sampllng pumps before
and after each day of sampling, using either
the electronic bubble meter method or the
precision rotameter method (that has been
calibrated against a bubble meter).
4. Electronic Flow Callbrator1
a. These units are high accuracy electronic
bubble flowmeters that provide
Instantaneous air flow readings and a
cumuatlve averaging of mutlple samples.
OSHA Instruction CPL 2-2.20B CH-1
OCT I 8 199! Directorate of T echnlcal Support
These calibrators measure the flow rate of
gases and present the results as volume
per unit of time.
b. These calibrators should be used to
calibrate all air s,rpltng pumps.
c. See Appendix 1 ~or more detaDs on this
piece of equipment.
When a sampling train requires an unusual
combination cl sampling media (e.g., glass
fiber filter preceding lmplnger), the ~me
medla/d~ should be In line during
calibration. ,
a. Electronic Bubble Meter Method
1) A11a-11 the pump to run 5 minutes prior
to voltage check and caJlbratlon.
2) Assemble the polystyrene cassette filter
holder, using the appropriate filter for
the sampling method. Compress
cassette by using a mechanical press
or other means cl applying pressure.
Use shrink tape around cassette to
cover joints and prevent leakage. If a
cassette adaptor Is used, care shoud
be taken to ensure that l does not come
In contad with the back-up pad.
Tubint ........... -:.-:.-:.-:..-:..-:..-:..-:..-:.-:.-:.=====:::l lll~===-=-::.-:.-:..-:..-:..-:..-:..-:..-:..~---=----_-_.-
Electronic
Bubble
Meter
F i1ter Cassette
E Personal
Sampling
Pump
Figure 1-9. For calibration, the cassette Is attached to an electronic bubble meter as
shown In the ltustratlon.
1-9
OSHA Instruction CPL 2-2.208 CH-1 ncT I ~ 1c-,-.,
\,.: '---· Directorate of Technical Support
Electronic Cyclone in
Bubble Holder
Meter Assembly E ,.1,pm
~ -
1 liter Bottle Sampling Pump
Rgure 1-10. The cyclone Is calibrated by placing th.:. :yd00v ;., a 1 liter vessel attached
to an electronlc bubble meter as Dlustrated above.
NOTE: When calibrating with a bubble
meter, the use d cassette adaptors
can cause moderate to severe
pressure drop at high flow rates In
the sampling train. which wDI affect
the calibration resut. If adaptors are
used for sampling, then they should
be used when calibrating.
CAUTION: Nylon adapters can restrict air flow
due to plugging over time. Stainless
steel adapters are preferred.
3) Connect the collection device, tubing,
pump and calibration apparatus as
shown In Figures 1-9 and 1-10,
cassette and cyclone samplers,
respectively.
4) A visual Inspection should be made of
all Tygon tubing connections.
5) Wet the Inside d the electronic flow cell
with the supplied soap solution by
pushing on the button several times.
6) Tum on the pump and adjust the pump
rotameter, If available, to the
appropriate flow rate setting.
bubble and electronlcally time the
bubble. The accompanying printer will
automatically record the calibration
reading In liters per minute.
8) Repeat step 7 untl two readings are
wlthJn 5%.
9) Whle the pump ls stDI running, adjust
the pump, I necessary.
Figure 1-11. A single column
precision rotameter can be used a
secondary calibration device. 7) Press the button on the electronic
bubble meter. Visually capture a single
b. Precision Rotameter Method. The
1 _ 10 .Jv precision rotameter, Figure 1-11 Is a
-11"-secondary calibration device. If It Is to be
used in place of a primary device such as
a bubble meter, care must be taken to
ensure that any introduced error will be
minimal and noted.
1) Replacing the Bubble Meter. The
precision rotameter may be used for
calibrating the personal sampling pump
In lieu of a bubble meter provided it Is:
a) Calibrated with an electronic bubble
meter or a bubble meter, as described
In Appendix 1-C, on a regular basis
(at least monthly).
b) Disassembled, cleaned as necessary,
and recalibrated. It should be used
with care to avoid dirt and dust
contamination which may affect the
flow.
c) Not used at substantially different
temperature and/or pressure from
those conditions present when the
rotameter was calibrated against the
primary source.
d) Used such that pressure drop across
it is minimal.
2) Unusual conditions. If altitude or
temperature at the sampling site are
substantially different from the
calibration site, it is necessary to
calibrate the precision rotameter at the
sampling site where the same
conditions are present.
c. Manual Buret Bubble meter method. See
Appendix 1-C.
F. FILTER WEIGHING
PROCEDURE
The step-by-step procedure for weighing filters
depends on the make and model of the balance.
Consult the manufacturer's instruction book for
directions. In addition, follow these guidelines:
OSHA Instruction CPL 2-2.20B CH-1
NOV 1 ;i 1990
Directorate of Technical Support
Ring piece
Figure 1-12. Exploded view of three
piece cassette shows placement of
backup pad.
1. There shall be no smoking or eating in the
weighing area. All filters will be handled with
tongs or tweezers. Do not handle the filters
with bare hands.
2. Desiccate all filters at least 24 hours before
weighing and sampling. Change desiccant
before it completely changes color (e.g.,
before blue desiccant turns all pink).
Evacuate desiccator with a sampling or
vacuum pump.
3. Zero the balance prior to use.
4. Calibrate the balance prior to use and after
every 1 o samples.
5. Immediately prior to placement on the
balance, pass all filters over an ionization unit
to remove static charges. (Return the unit
after 12 months of use to the distributor for
disposal.)
6. Weigh all filters at least twice.
a. If there is more than 0.005 milligram
difference in the two weighings, repeat the
zero and calibration and reweigh the filter.
1 -11
OSHA Instruction CPL 2-2.208 CH-1
NOV 1 3 1990
Dimctorate of Technical Support
b. If there is less than 0.005 milligram
difference in the two weighings, average
the weights for the final weight.
7. Record all the appropriate weighing
information (in ink) in the Weighing Log
(OSHA-96).
8. In reassembling the cassette assembly,
remember to add the unweighed backup
pad (Figure 1-12).
9. When weighing the filter after sampling,
dessicate first and include any loose material
from an overtoaded filter and cassette.
NOTE: At all times take care not to exert
downward pressure on the weighing pan(s).
Such action may damage the weighing
mechanism.
EUBUOGRAPHY
American Industrial Hygiene Association (AIHA).
1 B87. Fundamentals of Analytical Procedures
in Industrial Hygiene. AIHA: Akron, OH.
Hesketh, H. E. 1986. Fine Particles in Gaseous
Media. Lewis Publishers, lnc.:Chelsea, MA.
Lioy, P.J. 1989. Air Sampling Instruments for
Evaluation of Atmospheric Contaminants .
.A.merican Conference of Governmental
Industrial Hygienists: Cincinnati.
Lodge, J.P. Jr., Ed. 1988. Methods of Air
~iampling and Analysis. Lewis Publishers, Inc.:
Chelsea, MA.
Occupational Safety and Health Administration,
IJ.S. Dept. of Labor. Chemical Information
Manual. 1987. U.S. Government Printing Office:
Washington, D.C.
1 -12
Principle/Description
APPENDIX 1-A
OSHA Instruction CPL 2-2.208 CH-1
Directorate of Technical Support
DETECTOR TUBES/PUMPS
1. Detector tube pumps are portable equipment which, when used with a variety of commercially
available detector tubes, are capable of measuring the concentrations of a wide variety of
compounds In Industrial atmospheres.
2. Operation consists of using the pump to draw a known volume of air through a detector tube
designed to measure the concentration of the substance of Interest The concentration Is
determined by a colorimetric change of an Indicator which is present in the tube contents.
3. Some of the more frequently used detector tubes are available from the OSHA Cincinnati Lab
(OCL). Most tubes can be obtained locally.
Applications/Limitations
1. Detector tubes/pumps are screening Instruments which may be used to measure over 200
organic and Inorganic gases and vapors or for leak detection. Some aerosols can also be
determined.
2. Detector tubes of a given brand are to be used only with a pump of the same brand. The tubes
are calibrated specifically for the same brand of pump and may give erroneous results if used
with a pump of another brand.
3. A limitation of many detector tubes Is the lack of specificity. Many Indicators are not highly
selective and can cross-react with other compounds. Manufacturer's' manuals describe the
effects of interfering contaminants.
4. Another important consideration is sampling time. Detector tubes give only an instantaneous
interpretation of environmental hazards. This may be beneficial in potentially dangerous
situations or when ceiling exposure determinations are sufficient. When long-term
assessment of occupational environments Is necessary, short-term detector tube
measurements may not reflect time-weighted average levels of the hazardous substances
present.
5. Detector tubes normally have a shelf-life at 25 °C of 1 to 2 years. Refrigeration during storage
lengthens the shelf-life. Outdated detector tubes (i.e., beyond the printed expiration date)
should never be used. The OSHA Training Institute can sometimes use these outdated tubes
for training purposes.
Performance Data
1. Specific manufacturers' models of detector tubes are listed in the Chemical Information
Manual. The specific tubes listed are designed to cover a concentration range that is near the
PEL. Concentration ranges are tube-dependent and can be anywhere from one-hundredth
to several thousand ppm. The limits of detection depend on the particular detector tube.
2. Accuracy ranges vary with each detector tube.
1-13
OSHA Instruction CPL 2-2 .20B CH-1
Directorate of Technical Support
3. The pump may be handheld during operation (weighing from 8 to 11 ounces), or it may be an
automatic type (weighing about 4 pounds) which collects a sample using a preset number of
pump strokes. A full pump stroke for either type of short-term pump has a volume of about
100 cc.
4. In most cases where only one pump stroke Is required, sampling time is about one minute.
Determinations for which more pump strokes.are required take proportionately longer.
Maintenance
Contact the OSHA Calibration laboratory in Cincinnati, Ohio for long-term maintenance.
Leakage Test
1. Each day prior to use, perform a pump leakage test ~y inserting an unopened detector tube
into the pump and attempt to draw In 100 ml of air. After a few minutes, check for pump leakage
by examining pump compression for bellows-type pumps or return to resting position for
piston-type pumps. Automatic pumps should be tested according to the manufacturer's
instructions.
2. In the event of leakage which cannot be repaired in the field, send the pump to the OSHA
Cincinnati laboratory for repair.
3. Record that the leakage test was made on the Direct-Reading Data Form (OSHA-93).
Calibration Test
1. Calibrate the detector tube pump for proper volume measurement at least quarterly.
2. Simply connect the pump directly to the bubble meter with a detector tube in-Une. Use a
detector tube and pump from the same manufacturer.
3. Wet the inside of the 100 cc bubble meter with soap solution.
4. For volume calibration, experiment to get the soap bubble even with the zero ml mark of the
buret.
a. For piston-type pumps, pull the pump handle all the way out (full pump stroke) and
note where the soap bubble stops; for bellows-type pumps, compress the bellows
fully; for automatic pumps, program the pump to take a full pump stroke. For either
type pump, the bubble should stop between the 95 cc and 105 cc marks. Allow
4 minutes for the pump to draw the full amount of air (fhis time interval varies with
the type of detector tube being used in-line with the calibration setup).
b. Also check the volume for 50 cc (\/2 pump stroke) and 25 cc (V4 pump stroke) if
pertinent. As in Section 1 above, a ±5 percent error is permissible. If error is greater
than ±5 percent, send the pump to OCL for repair and recalibration.
5. Record the calibration information required on the Calibration log (OSHA-93).
6. It may be necessary to clean or replace the rubber bung or tube holder if a large number of
tubes have been taken with the pump.
1-14
Additional Information.
1. Draeger, Model 31 (bellows)
QSHA Instruction CPL 2-2.20B CH-1
NOV 1 3 1990
Directorate of Technical Support
When checking the pump for leaks with an unopened tube, the bellows should not be
completely expanded after 10 minutes.
2. Draeger, Quantimeter 1000, Model 1 (automatic)
A battery pack is an integral part of this pump. The pack must be charged prior to initial use.
One charge Is good for 1000 pump strokes. During heavy use, it should be recharged daily.
If a "U" (undervoltage) message Is continuously displayed in the readout window of this pump,
the battery pack should be immediately recharged.
3. Matheson-Kitagawa, Model 8014-400A (piston)
When checking the pump for leaks with an unopened tube, the pump handle should be pulled
back to the 100-ml mark and locked. After 2 minutes, the handle should be released carefully.
It should return to a point < 6 mm from zer~ or resting position. After taking 100 to 200 samples,
the pump should be cleaned and relubricated. This involves removing the piston from the
cylinder, removing the inlet and pressure-relief valve from the front end of the pump, cleaning,
and relubricating.
4. Mine Safety Appliances, Samplair Pump_. Model A, Part No. 463998 (piston)
The pump contains a flow-rate control orifice protected by a plastic filter which periodically
needs to be cleaned or replaced. To check the flow rate, the pump is connected to a buret
and the piston is withdrawn to the 100-ml position with no tube in the tube holder. After
24-26 seconds, 80 ml of air should be admitted to the pump. Every 6 months the piston should
be relubricated with the oil provided.
5. Sensidyne--Gastec, Model 800, Part No. 7010657-1 (piston)
This pump can be checked for leaks as mentioned for the Kitagawa pump; however, the handle
should be released after 1 minute. Periodic relubrication of the pump head, the piston gasket,
and the piston check valve is needed and is use-dependent.
Special considerations
1. Detector tubes should be refrigerated when not in use to prolong shelf life.
2. Detector tubes should not be used when cold. They should be kept at room temperature or
in a shirt pocket for one hour prior to use.
3. Lubrication of the piston pump may be required if volume error is greater than 5 percent.
1-15
OSHA lnstru~ti~n CPL 2-2.20B CH-1 NOV 1 3 1~
Directorate of Technical Support
THIS PAGE IS BLANK
r
1-16
O~a◊ 11swufl>1 CPL 2-2.20B CH-1
Directorate of Technical Support
APPENDIX 1-8 S } ) .. S<·C" :C.
ELECTRONIC FLOW CALIBRATORS I IJA --
Description
1. These units are high accuracy electronic bubble flowmeters that provide instantaneous air flow
readings and a cumulative averaging of multiple samples. These calibrators measure the flow
rate of gases and report volume per unit of time.
2. The timer is capable of detecting a soap film at 80 microsecond intervals. This speed allows
under steady flow conditions an accuracy of + or-0.5% of any display reading. Repeatability
is + or -0.5% of any display.
3. The range with different cells Is from 1 cc/min to 30 Lpm.
4. Battery power will last 8 hours with continuous use. Charge for 16 hours. Can be operated
from NC charger.
Maintenance of Calibrator
1. aeaning before use:
Remove the flow cell and gently flush with tap water. The acrylic flow cell can be easily
scratched. Wipe with cloth "only." Do not allow center tube, where sensors detect soap film
to be scratched or get dirty. NEVER clean with ACETONE. Use only soap and warm water.
When cleaning prior to storage, allow flow cell to air dry. If stubborn residue persists, it is
possible to remove the bottom plate. Squirt a few drops of soap into the slot between base
and flow cell to ease removal.
2. Leak Testing:
The system should be leak checked at 6" H2O by connecting a manometer to the outlet boss
and evacuate the inlet to 6" H2O. No leakage should be observed.
3. Verification of Calibration:
The calibrator is factory calibrated using a standard traceable to National Institute of Standards
and Technology, formerty called the National Bureau of Standards, (NBS). Attempts to verify
calibrator against a glass one liter burette should be conducted at 1 ooo cc/min. for maximum
accuracy. The calibrator is linear throughout the entire range.
Shipping/Handling
1. When transporting, especially by air, it is important that one side of the seal tube which
connects the inlet and outlet boss, be removed for equalizing internal pressure within the
calibrator.
2. Do not transport unit with soap solution or storage tubing in place.
1-17
'Wo1f r~tr~ir CPL 2-2.20B CH-1
Directorate of Technical Support
Precautions/Warnings
1. Avoid the use of chemical solvents on flow cell, calibrator case and faceplate. Generally, soap
and water will remove any dirt.
2. Never pressurize the flow cell at any time with more than 25 inches of water pressure.
3. Do not charge batteries for longer than 16 hours.
4. Do not leave NC adapter plugged into calibrator when not in use as this could damage the
battery supply.
5. Black close fitting covers help to reduce evaporation of soap in the flow cell when not is use.
6. Do not store flow cell for a period of one week or longer with soap. Clean and store dry.
7. The Calibrator Soap is a precisely concentrated and sterilized solution formulated to provide
a clean, frictionless soap film bubble over the wide, dynamic range of the calibrator. The sterile
nature of the soap is important in the prevention of residue build-up in the flow cell center tube,
which could cause inaccurate readings. The use of any other soap is not recommended.
1-18
APPENDIX 1-C
OSHA Instruction CPL 2-2.20B CH-1
NOV 13 1900
Directorate of Technical Support
MANUAL BURET BUBBLE METER TECHNIQUE
When a sampling train requires an unusual combination of sampling media (e.g., glass fiber filter
preceeding impinger), the same media/devices should be In line during calibration. Calibrate
personal sampling pumps before and after each day of sampling.
Bubble Meter Method
1. Allow the pump to run 5 minutes prior to voltage check and calibration.
2. Assemble the polystyrene cassette filter holder using the appropriate filter for
the sampling method. If a cassette adaptor is used, care should be taken to
ensure that it does not come in contact with the back-up pad.
NOTE: When calibrating with a bubble meter, the use of cassette adaptors can cause
moderate to severe pressure drop in the sampling train, which will affect the
calibration result. If adaptors are used for sampling, then they should be used
when calibrating.
3. Connect the collection device, tubing, pump and calibration apparatus as shown
in Figures 1-13 and 1-14.
4. A visual inspection should be made of all Tygon tubing connections.
5. Wet the inside of a 1~iter buret with a soap solution.
6. Turn on the pump and adjust the pump rotameter to the appropriate flow rate
setting.
7. Momentarily submerge the opening of the buret in order to capture a film of
soap.
8. Draw two or three bubbles up the buret in order to ensure that the bubbles will
complete their run.
9. Visually capture a single bubble and time the bubble from o to 1000 ml for high
flow pumps or O to 100 ml for low flow pumps.
10. The timing accuracy must be within + 1 second of the time corresponding to
the desired flow rate.
11 . If the time is not within the range of accuracy, adjust the flow rate and repeat
steps 9 and 10 until the correct flow rate is achieved. Perform steps 9 and 10 at
least twice, in any event.
12. While the pump is still running, mark the pump or record on the OSHA-91 the
position of the center of the float in the pump rotameter as a reference.
13. Repeat the procedures described above for all pumps to be used for sampling.
The same cassette and filter may be used for all calibrations involving the same
sampling method.
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OSHA Instruction CPL 2-2.20B CH-1 NOV 1 3 1990
Directorate of Technical Support
filler~
eu.i. nn
lW
Soapbubble ~
0 Meter -
(1-edbutel) -----
500 -------
l!!!!!!I
Buker -Soap
Solution
,T ....
"' -~ Personal
Sampling Pump
Figure 1-13. Calibration setup for personal sampling with filter cassette.
1000 ml buret -
T
250 ml Beaker
Cyclone In
Holder
AsMrnbly
Tubing
1 Liter bottle
Tubing -
Sampling
Pump
Figure 1-14. Calibration of cyclone respirable dusf_sampler using a bubble meter.
1-20
OSHA Instruction CPL 2-2.20B CH-1
NOV 1 3 1990
Directorate of Technical Support
APPENDIX 1-D
SHELF-LIFE OF SAMPLING MEDIA PROVIDED BY SLCAL
Sampling Medium
Sodium hydroxide (all normalities)
Hydrochloric acid
Sulfuric acid
Methanol In water
All organic solvents in pure state
Bis-chloromethyl ether (BCME) and
Chloromethyl methyl ether (CMME)
collecting solution
Hydroxylammonium chloride solutions
(for acetic anhydride, ketene)
Hydroxylammonium chloride-Sodium
hydroxide mixed solutions (for acetic
anhydride, ketene collection)
Hydrogen peroxide (0.3N) for sulfur
dioxide collection
Girard T Reagent
Folin's Reagent
Passive Monitors
Nitrogen oxides collection tubes
1-21
Shelf-Life
6 months
one year
4 years
2 months
2weeks
Stable only
2 hours
6 months
2weeks
5 days
Comments
Same for all concentrations
of all solutions.
Must be stored in a dark
bottle in a refrigerator.
Should be stored In a
refrigerator in a
light-protected container.
Must be prepared fresh just
prior to use.
Stable If it is protected from
light and refrigerated.
Store in glassware in the
dark.
Must be stored in a
refrigerator.
Must be used before the expiration date
(if given) printed on the monitor package.
Should be stored in a
refrigerator.
OSHA Instruction CPL 2-2.208 CH-1 NOV 1 3 1990
Directorate of Technical Support
APPENDIX 1-E
SAMPLING FOR SPECIAL ANALYSES
Silica Samples Analyzed by X-Ray Diffraction (XRD).
1. Air Samples. Respirable dust samples are analyzed for quartz and cristobalite by X-ray
diffraction (XRD). XRD is the preferred analytical method due to its sensitivity, minimum
requirements for sample preparation and ability to identify polymorphs (different crystalline
forms) of free silica.
a. The analysis of free silica by XRD requires that the particle size distribution of the samples
be matched as closely as possible to the standards. This is best accomplished by
collecting a respirable sample.
1) Respirable dust samples are collected on a tared low ash PVC filter using a 10mm
nylon cyclone at a flow rate of 1. 7 1pm.
2) A sample not collected in this manner is considered a total dust
(or nonrespirable) sample. CSHOs are discouraged from submitting total dust
samples since an accurate analysis cannot be provided by XRD for such
samples.
3) If the sample collected is nonrespirable, the laboratory must be advised in Item
37 on the OSHA-91 Form.
b. Quartz and cristobalite are the only two polymorphs of free silica which are presently
being analyzed by the laboratory. Tridymite is not currently being analyzed. Samples
are analyzed for cristobalite only upon request.
c. Quartz (or cristobalite) is identified by its major (primary) X-ray diffraction peak. Because
other substances also have peaks at the same position, it is necessary to confirm quartz
(or cristobalite) principally by the presence of secondary and/or tertiary peaks.
d. If they are considered to be present in the work environment, the following major
chemicals which.can interfere with an analysis should be noted:
Aluminum phosphate
Feldspars (microcline, orthoclase, plagioclase)
Graphite
Iron carbide
Lead sulfate
Micas (biotite, muscovite)
Montmorillonite
Potash
Sillimanite
Silver chloride
Talc
Zircon (Zirconium silicate)
NOTE: Specific additional chemicals should be listed in Item 37 of the OSHA-91 Form only if they
are suspected to be present.
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OSHA Instruction CPL 2-2.208 CH-1
Directorate of Technical Support
e. A sample weight and total air volume shall accompany all filter samples. Sample weights
of 0.5 to 3.0 milligrams are preferred.
1) Do not submit a sample(s) unless its weight or the combined weights of all filters
representing an Individual exposure exceed 0.05 milligram.
2) If heavy sample loading Is noted during the sampling period, It Is recommended
that the filter cassette be changed to avoid collecting a sample with a weight
greater than 5.0 milligrams.
3) If a sample weight exceeds 5.0 mg, another sample of a smaller air volume,
whenever possible, should be collected to obtain a sample weight of less than
5.0mg.
f. Laboratory results for air samples are usually reported under one of four categories:
1) Percent Quartz (or Crlstobalite). Applicable for a respirable sample In which the
amount of quartz (or cristobalite) In the sample was confirmed.
2) •Less Than or Equal To· Value in Units of Percent Less than or equal to values
are used when the adjusted 8-hour exposure Is found to be less than the PEL,
based on the sample's primary diffraction peak. The value reported represents
the maximum amount of quartz (or cristobalite) which could be present
However, the presence of quartz (or cristobalite) was not confirmed using
secondary and/or tertiary peaks in the sample since the sample could not be In
violation of the PEL
3) Approximate Values in Units of Percent The particle size distribution In a total
dust sample Is unknown and error in the XRD analysis may be greater than for
respirable samples. Therefore, for total dust samples, an approximate result Is
given.
4) Nondetected. A sample reported as nondetected Indicates that the quantity of
quartz (or cristobalite) present In the sample Is not greater than the detection
limit of the instrument The detection limit is usually 10 micrograms for quartz
and 30 micrograms for cristobalite.
• If less than a full-shift sample was collected, the CSHO should evaluate
a nondetected result to determine whether adequate sampling was
performed.
• If the presence of quartz (or cristobalite) is suspected in this case, the
Industrial Hygienist may want to sample for a longer period of time to
increase the sample weights.
2. Bulk Samples. Bulk samples must be submitted for all silica analyses.
a. They have two purposes:
1) For laboratory use only, to confirm the presence of quartz or cristoblite in
respirable samples, or to assess the presence of other substances that may
interfer in the analysis of respirable samples.
2) To determine the approximate percentage of quartz (or cristobalite) in the bulk
sample.
b. A bulk sample submitted "for laboratory use only" must be representative of the airborne
free silica content of the work environment sampled; otherwise it will be of no value.
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OSHA Instruction CPL 2-2.208 CH-1
NOV 1 3 1990
Directorate of Technical Support
c. The laboratory's order of preference for bulk samples for an evaluation of personal
exposure is:
1) A high volume respirable area sample.
2) A high volume area sample.
3) A representative settled dust (rafter) sample.
4) A bulk sample of the raw material used in the manufacturing process.
• This is the last choice and the least desirable.
• It should be submitted "for laboratory use only" if there Is a possibility
of contamination by other materials during the manufacturing process.
d. The type of bulk sample submitted to the laboratory should be stated on the OSHA-91
Form and cross-referenced to the appropriate air samples.
e. A bulk sample analysis for percent quartz (or cristobalite) will be reported only upon
specific request by the CSHO in Item 36 of the OSHA-91 Form.
f. A reported bulk sample analysis for quartz (or cristobalite) will be semi-quantitative In
nature because:
1) The XRD analysis procedure requires a thin layer deposition for an accurate
analysis.
2) The error for bulk samples analyzed by XRD Is unknown because the particle
size of nonrespirable bulk samples varies from sample to sample.
Samples Analyzed by Inductively Coupled Plasma (ICP).
1. Metals. Where two or more of the following analytes are requested on the same filter, an ICP
analysis may be conducted. However, the Industrial Hygienist should specify the metals of
interest in the event samples cannot be analyzed by the ICP method. A computer print-out of
the following 13 analytes may be reported:
Antimony
Beryllium
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Molybdenum
Nickel
Vanadium
Zinc
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OSHA Instruction CPL 2-2.20B CH-1
NOV l 3 1990
Directorate of Technical Support
2. Arsenic. Samples analyzed for the 13 analytes mentioned above can also be analyzed for
arsenic by request. The arsenic analysis is performed by a different technique and results are
reported separate from ICP results.
3. If requested, the laboratory can analyze for "solder-type" elements, such as:
Antimony
Beryllium
Cadmium
Copper
Lead
SUver
Tin
Zinc
Samples Analyzed by X-Ray Fluorescence (XRF).
1. Filter, wipe and bulk samples can be qualitatively analyzed by XRF.
2. Requests for XRF analyses should be preceded by a phone call to SLCAL to determine the
extent and value of the analysis.
3. Packaging and shipping of such samples should be done in a manner consistent with directions
previously given In this chapter.
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OSHA Instruction CPL 2-2.20B CH-1
,~av 1 3 1990
Directorate of Technical Support
APPENDIX 1 - F
Sampling and Analytical Errors (SAE's).
1. Definition of SAE's. WheA an employee is sampled and the results analyzed, the measured
exposure will rarely be the same as the true exposure. This variation is due to sampling and
analytical errors (SAE's). The total error is dependent upon the combined effects of the
contributing errors inherent in sampling, analysis, and pump flow.
2. Definition of Confidence Limits. Error factors determined by statistical methods shall be
incorporated into the sample results to obtain the lowest value that the true exposure could
be (with a given degree of confidence) and also the highest value the true exposure could be
(also with some degree of confidence).
a. The lower value is termed the lower cor.fidence limit (LCL) and the upper value is termed
the upper confidence limit (UCL).
b. These confidence limits are termed "one-sided" since the only concern is with being
confident that the true exposure is on one side of the PEL.
3. Determining SAE's. SAE's which provide a 95 percent confidence limit have been developed
and are listed on each OSHA 91 B report form (most current SAEs) and are also presented in
the Chemical Information Manual. If there is no SAE listed in the manual for a specific
substance, apply the manufacturer's recommended error.
4. Environmental Variables. Environmental variables generally far exceed sampling and
analytical errors. Samples taken on a given day are used by OSHA to determine compliance
with PEL's. However, where samples are taken over a period of time (as is the practice of
some employers) the CSHO should review the long term pattern and compare it with the results
he/she obtains. Where OSHA's samples fit the long term pattern this helps to support the
compliance determination. Where OSHA's results differ substantially from the historical
pattern, the CSHO should investigate the cause of this difference and perhaps conduct
additional sampling.
5. Confidence Limits. One-sided confidence limits can be used to classify the measured
exposure into one of three categories.
a. If the measured results do not exceed the standard and the UCL also does not exceed
the standard, we can be 95 percent confident that the employer is in compliance.
(See equation 1 F-6.)
b. If the measured exposure exceeds the PEL and the LCL of that exposure also exceeds
the PEL, we can be 95 per-cent confident that the employer is in noncompliance, and a
violation is established. (See equation 1 F-7.)
c. If the measured exposure does not exceed the PEL, but the UCL of that exposure does
exceed the PEL, we cannot be 95 percent confident that the employer is in compliance.
(See equation 1 F-6.) Likewise, if the measured exposure exceeds the PEL, but the LCL
of that exposure is below the PEL, we cannot be 95 percent confident that the employer
is in noncompliance. (See equation 1F-7.) In both of these cases, our measured
exposure falls into a region which is termed "possible over-exposure."
1) A violation is not established if the measured exposure falls into the "possible
overexposure" region. It should be noted that the closer the LCL comes to
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OSHA Instruction CPL 2-2.20B CH-1
NOV 13 1~
Directorate otTechnical Support
exceeding the PEL, the more probable it becomes that the employer is in
noncompliance.
2) If measured results are in this region, the CSHO should consider further sam-
pling, taking into consideration the seriousness of the hazard, pending citations,
and how close the LCL is to exceeding the PEL
3) If further sampling is not conducted, or if additional measured exposures still fall
into the "possible overexposure" region, the CSHO should carefully explain to
the employer and employee representative in the closing conference that the
exposed employee(s) may be overexposed but that there was insufficient data
to document noncompliance. The employer should be encouraged to volun-
tarily reduce the exposure and/or to conduct further sampling to assure that
exposures are not in excess of the standard.
6. Sampling Methods. The LCL and UCL are calculated differently depending upon the type of
sampling method used. Sampling methods can be classified into one of three categories:
a. Full-period, Continuous Single Sampling. Full-period, continuous single sampling is
defined as sampling over the entire sample period with only one sample. The sampling
may be for a full-shift sample or for a short period ceiling determination.
b. Full-period, Consecutive Sampling. Full-period, consecutive sampling is defined as
sampling using multiple consecutive samples of equal or unequal time duration which,
if combined, equal the total duration of the sample period. An example would be taking
four 2-hour charcoal tube samples. There are several advantages to this type of
sampling.
1) If a single sample is lost during the sampling period due to pump failure, gross
contamination, etc., at least some data will have been collected to evaluate the
exposure.
2) The use of multiple samples will result in slightly lower sampling and analytical
errors.
3) Collection of several samples allows conclusions to be reached concerning the
manner in which differing segments of the workday affect overall exposure.
c. Grab Sampling. Grab sampling is defined as collecting a number of short-term samples
at various times during the sample period which, when combined, provide an estimate
of exposure over the total period. Common examples include the use of detector tubes
or direct-reading instrumentation (with intermittent readings).
7. Calculations.
a. If the initial and final calibration flow rates are different, a volume calculated using the
highest flow rate should be reported to the laboratory. If compliance is not established
using the lowest flow rate, further sampling should be considered.
b. Generally, sampling is conducted at approximately the same temperature and pressure
as calibration, in which case no correction for temperature and pressure is required and
the sample volume reported to the laboratory is the volume actually measured. Where
sampling is conducted at a substantially different temperature or pressure than
calibration, an adjustment to the measured air volume may be required depending on
sampling pump used, in order to obtain the actual air volume sampled.
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OSHA Instruction CPL 2-2.20B CH-1
NOV 1 3 1990
Directorate of Technical Support
c. The actual volume of air sampled at the sampling site is reported, and used in all
calculations.
1) For particulates. the laboratory reports mg/m3 of contaminant using the actual
volume of air collected at the sampling site. The value in mg/m3 can be
compared directly to OSHA Toxic and Hazardous Substances Standards
(e.g. 29 CFR 1910.1000).
2) The laboratory does not measure concentrations of gases and vapors directly
in parts per million (ppm). Rather, the analytical techniques determine the total
weight of contaminant in collection medium. Using the air volume provided by
the CSHO, the lab calculates concentration in mg/m3 and converts this to ppm
at 25°C and 760mm Hg using Equation 1 F-1 . This result is to be compared with
the PEL without adjustment for temperature and pressure at the sampling site.
ppm(NTP) = mg/m3 (24.45)/(Mwt) Equation 1 F-1
where: 24.45 = molar volume at 25°C {298°1<) and 760mm Hg
Mwt = molecular weight
NTP = Normal Temperature and Pressure, 25°C and 760mm Hg.
3) If an occasion arises where it is necessary to know the actual concentration in
ppm at the sampling site, it can be derived from the laboratory results reported
in ppm at NTP by using the following equation:
ppm(PT) = ppm(NTP) (760)/(P) (T)/(298) Equation 1 F-2
where: P = sampling site pressure (mm of Hg)
T = sampling site temperature (°K)
298 = temperature in degrees Kelvin {273°K + 25°)
since ppm(NTP) = mg/m3 (24.45)/(Mwt)
ppm(PT) = mg/m3 X 24.45/Mwt X 760/P X T /298 Equation 1 F-3
NOTE: When a laboratory result is reported as mg/m3 contaminant, concentrations expressed
as ppm(PT) cannot be compared directly to the standards table without converting to NTP.
NOTE: Barometric pressure can be obtained by calling the local weather station or airport,
request the unadjusted barometric pressure. If these sources are not available then a rule of
thumb is For every 1 ooo feet of elevation, the barometric pressure decreases by 1 inch of Hg.
8. Calculation Method for a Full-period, Continuous Single Sample.
a. Obtain the full-period sampling result (value X), the PEL and the SAE. The SAE can be
obtained from the Chemical lnfonnation Manual.
b. Divide X by the PEL to determine Y, the standardized concentration. That is:
Y = X / PEL (Equation 1 F-5)
c. Compute the UCL (95%) as follows:
UCL (95%) = Y + SAE (Equation 1 F-6)
d. Compute the LCL (95%) as follows:
LCL (95%) = Y -SAE (Equation 1F-7)
1-28
OSHA Instruction CPL 2-2.20B CH-1
Directorate of Technical Support
e. aassify the exposure according to the following classification system:
1) If the UCL ~ 1, a violation does not exist.
2) If LCL~ 1 and the UCL> 1, classify as possible overexposure.
3) If LCL > 1, a violation exists.
9. Calculation Method for Full-period Consecutive Sampling. The use of multiple
consecutive samples will result in slightly lower sampling and analytical errors than the use of
one continuous samp(e since the Inherent errors tend to partially cancel each other. The
mathematical calculations, however, are somewhat more complicated. If preferred, the CSHO
may first determine if compliance or noncompliance can be established using the calculation
method noted for a full-period, continuous, single sample measurement If results fall into the
"possible overexposure· region using this method, a more exact calculation should be
performed using equation 1 F-8.
a. Obtain X1, X2 ... , Xn, the n consecutive concentrations on one workshift and their time
durations, T1, T2, ... , Tn. Also obtain the SAE in the Chemical Information Manual.
b. Compute the TWA exposure.
c. Divide the TWA exposure by the PEL to find Y, the standardized average (TWNPEL).
d. Compute the UCL {95%) as follows:
UCL(95%) = Y + SAE (Equation 1 F-6)
e. Compute the LCL {95%) as follows:
LCL(95%) = Y -SAE (Equation 1F-7)
f. aassify the exposure according to the following classification system:
1) If UCL~1. a violation does not exist
2) If LCL~ 1, and the UCL> 1, classify as possible overexposure.
3) If LCL > 1, a violation exists.
g. When the LCL~ 1.0 and UCL> 1.0, the results are in the "possible overexposure" region,
and the CSHO must analyze the data using the more exact calculation for full-period
consecutive sampling as follows:
LCL = Y-[SAE (v.--r-1_2_X_1_2_+_T2_2_X_2_2 _____ -_ T_n_2_X_n_2_]] Equation 1F-8
PEL T1+T2+ ... Tn
10. Grab Sampling. If a series of grab samples (e.g ., detector tubes) are used to determine
compliance with either an 8-hourTWA limit or a ceiling limit, consult with the ARA for Technical
Support regarding sampling strategy and the necessary statistical treatment of the results
obtained.
11. SAEs for Exposure to Chemical Mixtures. Often an employee is simultaneously exposed
to a variety of chemical substances in the workplace. Synergistic toxic effects on a target
1-29
OSHA Instruction CPL 2-2.20B CH-1
Directorate of Technical Support
organ is common for such exposures in many construction and manufacturing processes.
This type of exposure can also occur when impurities are present in single chemical operations.
New permissible exposure limits for mixtures, such as the recent welding fume standard
(5 mg!m3}, address the complex problem of synergistic exposures and their health effects. In
addition, 29 CFR 1910.1000 contains a computational approach to assess exposure to a
mixture. This calculation should be used when components In the mixture pose a synergistic
threat to worker health.
Whether using a single standard or the mixture calculation, the sampling and analytical error
(SAE) of the Individual constituents must be considered before arriving at a final compliance
decision. These SAEs can be pooled and weighted to give a control limit for the synergistic
mixture. To illustrate this control limit, the following example using the mixture calculation is
shown:
The mixture calculation is expressed as:
Em = (C1/L 1 + C2/L2 + ... ~) Equation 1 F-9
Where: Em = equivalent exposure for a mixture (Em should be :::; 1 for compliance)
C = concentration of a particular substance
L = PEL
As an Example, an exposure to three different but synergistic substances:
Material 8-hr Exposure (ppm) 8-hr TWA PEL (ppm) SAE
Substance 1 500 1000 0.089
Substance 2 80 200 0.11
Substance 3 70 200 0.18
Using Equation 1 F9: Em = 500/1000 + 80/200 + 70/200 = 1.25
Since Em> 1, an overexposure appears to have occurred; however, the SAE for each
substance also needs to be considered:
Exposure ratio (for each substance) Y n = ~
Ratio to toal exposure R1 = Y1/Em, .... Rn = Yn/Em
The SAEs {95% confidence) of the substance comprising the mixture can be pooled by:
RSt = [((R1)2 X (SAE1)2) + (R2)2 X (SAE2)2) + .... (Rn)2 X (SAEn)2))] 112
The mixture Control Limit (CL) is equivalent to: 1 + RSt
If Em~CL, then an overexposure has not been established at the 95% confidence level; futher
sampling may be necessary.
1-30
OSHA Instruction CPL 2-2.20B CH-1
Directorate of Technical Support
If Em> 1 and Em>Cl, then an overexposure has occurred (95% confidence).
Using the mixture data above:
Y1 = 500/1000
Y1 = _5
R1 = Y1/Em = 0.4
Y2 = 80/200
Y2 = .4
R2 = 0.32
Ya= 70/200
Ya= .35
Ra= 0.28
RSt2 = (0.4)2 (0.089)2 + (0.32)2(0.11 )2 + (0.28)2(0.18)2
RSt = (RSd1/2 = 0·011
CL = 1 + RSt = 1.071
Em= 1.25
Therefore Em > CL and an overexposure ~s occured within 95% confidence limits.
This calculation is also used when considering a standard such as the one for total welding fumes.
A computer program is available for personal computers which will calculate a control limit for
any synergistic mixture. The program will run on any IBM compatible computer.
Sample Calculation for Full-period, Continous Single Sample
A single fiberglass filter and personal pump were used to sample for carbaryt for a 7-hour period ..
The CSHO was able to document that the exposure during the remaining unsampled one-half
hour of the 8-hour shift would equal the exposure measured during the 7-hour period. The
laboratory reported 6.07 mg/rn3. The SAE for this method is 0.23. The PEL is 5.0 mg/rn3.
(See Chemical Information Manual.)
Step 1. Calculate the standardized concentration.
Y = 6.07/5.0 = 1.21
Step 2. Calculate confidence limits.
LCL = 1.21 -0.23 = 0.98
Since the LCL does not exceed 1.0 noncompliance is not established. The UCL
is calculated:
UCL= 1.21 + 0.23 = 1.44
Step 3. Classify the exposure.
Since the LCL::S 1.0 and the UCL> 1.0, classify as possible overexposure.
1-31
OSHA Instruction CPL 2-2.208 CH-1
Directorate of Technical Support
Sample Calculation for Full-period, Consecutive Sampling
If two consecutive samples had been taken for carbaryl instead of one continuous sample, and
the following results were obtained:
Sample
Sampling Rate Qpm)
Time (Min)
Volume (L)
Weight (mg)
Concentration (mg/m3)
The SAE for carbaryl is 0.23.
A
2.0
240
480
3.005
6.26
B
2.0
210
420
2.457
5.85
Step 1. Calculate the UCL and the LCL from the sampling and analytical results:
Step 2.
LCL = 1.21 -
TWA = (6.26 mg/m3) 240 min + (5.85 mg/m3) 210 min
450 min = 6.07 mg/m3
Y = 6.07 mg/m3/PEL = 6.07/5.0 = 1.21
Assuming a continuous sample:
LCL = 1.21 -0.23 = 0.98
UCL= 1.21 + 0.23 = 1.44
Since the LCL < 1.0 and UCL> 1.0, the results are in the possible overexposure
region, and the CSHO must analyze the data using the more exact calculation
for full-period consecutive sampling as follows:
= 1.21 -0.20
= 1.01
Since the LCL > 1.0, a violation is established.
1-32