EPA/540/R-95/528

August 1995

FIELD ANALYTICAL SCREENING PROGRAM: PCP

METHOD

INNOVATIVE TECHNOLOGY EVALUATION REPORT

NATIONAL RISK MANAGEMENT RESEARCH LABORATORY

OFFICE OF RESEARCH AND DEVELOPMENT

U.S. ENVIRONMENTAL PROTECTION AGENCY

CINCINNATI, OHIO 45268

NATIONAL EXPOSURE RESEARCH LABORATORY

OFFICE OF RESEARCH AND DEVELOPMENT

U.S. ENVIRONMENTAL PROTECTION AGENCY

LAS VEGAS, NEVADA 89193
Notice

The information in this document has been funded wholly or in part by the U.S. Environmental

Protection Agency (EPA) in partial fulfillment of Contract No. 68-C0-0047, Work Assignment

No. 0-40, to PRC Environmental Management, Inc. It has been subject to the Agency’s peer and

administrative review, and it has been approved for publication as an EPA document. The

opinions, findings, and conclusions expressed herein are those of the contractor and not

necessarily those of the EPA or other cooperating agencies. Mention of company or product

names is not to be construed as an endorsement by the agency.

ii
Foreword

The U.S. Environmental Protection Agency is charged by Congress with protecting the Nation’s land,

air, and water resources. Under a mandate of national environmental laws, the Agency strives to formulate and

implement actions leading to a compatible balance between human activities and the ability of natural systems

to support and nurture life. To meet this mandate, EPA’s research program is providing data and technical’

support for solving environmental problems today and building a science knowledge base necessary to manage

our ecological resources wisely, understand how pollutants affect our health, and prevent or reduce environmental

risks in the future.

The National Risk Management Research Laboratory is the Agency’s center for investigation of

technological and management approaches for reducing risks from threats to human health and the environment.

The focus of the Laboratory’s research program is on methods for the prevention and control of pollution to air,

land, water and subsurface resources; protection of water quality in public water systems ‘; remediation of

contaminated sites and ground water; and prevention and control of indoor air pollution. The goal of this research

effort is to catalyze development and implementation of innovative, cost-effective environmental technologies;

develop scientific and engineering information needed by EPA to support regulatory and policy decisions; and

provide technical support and information transfer to ensure effective implementation of environmental

regulations and strategies.

This publication has been produced as part of the Laboratory’s strategic long-term research plan. It is

published and made available by EPA’s Office of Research and Development to assist the user community and

to link researchers with their clients.

E. Timothy Oppelt, Director

National Risk Management Research Laboratory
Abstract

This innovative technology evaluation report (ITER) presents information on the demonstration of the U.S.

Environmental Protection Agency (EPA) Region 7 Superfund Field Analytical Screening Program (FASP) method

for determining pentachlorophenol (PCP) contamination in soil and water. This method was demonstrated in

Morrisville, North Carolina, in August 1993.

The FASP PCP Method was developed by the EPA Superfund Branch for use at Superfund sites. The method uses

a gas chromatograph (GC) equipped with a megabore capillary column and either a flame ionization detector (FID)

or an electron capture detector (ECD). Gas chromatography is an EPA-approved method for determining PCP

concentrations in soil, water, and waste samples. The FASP PCP Method is an abbreviated, modified version of

approved methods. Soil and water samples require extraction before GC analysis. To remove interferences caused

by petroleum hydrocarbons, an acid-base partition cleanup step is used during the FASP PCP Method.

The FASP PCP Method was found to be field-portable only in a mobile laboratory, must be done in a temperaturecontrolled environment, and requires a skilled chemist for operation. The detection limit reported by this method for

is 0.8 part per million for soil samples and 1 .O part per billion for water samples. PRC used linear regression and

inferential statistics to compare the method’s data to that from the confirmatory laboratory. When the data sets were

evaluated as a whole, the FASP PCP Method did not perform well. However, the demonstration’s samples were

collected from two different sites, and the method was found to have performed well on samples from the site where

petroleum hydrocarbons had not been used as a carrier solvent. This indicates that the problems with the method may

have been due to the petroleum hydrocarbons in the soil. The water analysis portion of this demonstration produced

similar results.

PRC evaluated field duplicate samples to determine the technology’s precision relative to the confirmatory

laboratory’s. PRC found no significant difference between the precision of the FASP PCP Method and that of the

confirmatory laboratory’s for soil and water analysis. In addition, no PCP carrier effect on precision was observed.

This report was submitted in partial fulfilment of contract 68-CO-0047 by PRC Environmental Management, Inc.,

under the sponsorship of the U.S. Environmental Protection Agency. This report covers a period from July 1, 1993,

to August 31, 1993, and work was completed as of February 1, 1994.

iv
Table of Contents

Notice.. ...............................................................................ii

Foreword ..............................................................................iii

Abstract .............................................................................. iv

List of Figures.................................................................................. vii 

ListofTables .........................................................................vii

List of Abbreviations and Acronyms ..................................................... VIII

Acknowledgments ...................................................................... ix

ExecutiveSummary ................................................................ 1

Introduction ....................................................................... 3

EPA’s Site Program and MMTP: an Overview ....................................... 3

The Role of Monitoring and Measurement Technologies ......................... 3

Defining the Process .................................................... 4

Components of a Demonstration .........................; :. ............... 4

Rationale for this Demonstration .................................................. 4

Demonstration Purpose, Goals, and Objectives ...................................... 5

Predemonstration Activities ......................................................... 6

Identifying Developers .......................................................... 6

The Sites and Their Principal Contaminants ......................................... 6

Selecting the Confirmatory Laboratory and Analytical Methods .......................... 7

Training Technology Operators ................................................... 7

Predemonstration Sampling and Analysis ........................................... 7

Demonstration Design and Description ................................................ 8

Demonstration Design .......................................................... 8

Implementation of the Demonstration Plan .......................................... 8

Field Modifications to the Demonstration Plan ....................................... 9

Data Collection ............................................................... 9

Statistical Analysis of Results .................................................... 10

Confirmatory Analysis Results ...................................................... 12

Confirmatory Laboratory Procedures ............................................. 12

Sample Holding Times.. ................................................ 12

Sample Extraction ..................................................... 12

Detection Limits and Initial and Continuing Calibrations ........................ 13

Sample Analysis ....................................................... 13

Quality Control Procedures .............................................. 13

Quality Control ProceduresmmmmmmDDDDDDDDDDDDD............ Data Reporting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

V
Table of Contents (Continued)

Section

Data Quality Assessment ...................................................... 15

Confirmatory Laboratory Costs and Turnaround Times ............................... 16

6 EPA Region 7 Super-fund Program: FASP PCP Method ................................. 17

Operational Characteristics .................................................... 17

Performance Factors .......................................................... 20

Specificity .................................................................. 21

Intramethod Assessment ....................................................... 22

Comparison of Results to Confirmatory Laboratory Results ............................ 26

Soil Samples: Intermethod Accuracy ...................................... 26

Soil Samples: Intermethod Precision ...................................... 31

Water Samples: Intermethod Accuracy ............; ........................ 31

Water Samples: Intermethod Precision ..................................... 32

7 . Application Assessment .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

8 References................................................... .................... . 35

vi
List of Figures

Figure Paae

6-l FASP PCP Method vs. Confirmatory Analysis: Total Soil Data Set ....................... 26

6-2 FASP PCP Method vs. Confirmatory Analysis: Former Koppers Site Soil Samples ........... 27

6-3 FASP PCP Method vs. Confirmatory Analysis: Wrnon a Post Soil Samples ................. 27

64 FASP PCP Method vs. Confirmatory Analysis: Total Water Data Set. ..................... 31

6-5 FASP PCP Method vs. Confirmatory Analysis: Former Koppers Site Water Samples ......... 32

6-6 FASP PCP Method vs. Confirmatory Analysis: Winon a Post Water Samples ............... 32

List of Tables

5-l Soil Matrix Spike Sample Results for EPA Methods 8270A and 8151A ..................... 15

5-2 Water Matrix Spike Sample Results for EPA Methods 8270A and 515.1 ................... 15

6-l Soil Matrix Spike Sample Results for the FASP PCP Method ............................ 24

6-2 Water Matrix Spike Sample Results for the FASP PCP Method .......................... 24

6-3 Soil Laboratory Duplicate Sample Results for the FASP PCP Method ..................... 25

64 Water Laboratory Duplicate Sample Results for the FASP PCP Method .................... 25

6-5 Soil Field Duplicate Sample Results for the FASP PCP Method .......................... 25

6-6 Water Field Duplicate Sample Results for the FASP PCP Method ........................ 25

6-7 Summary of Demonstration Data: Former Koppers Site Soil Samples ..................... 28

6-8 Summary of Demonstration Data: Winon a Post Soil Sample s ........................... 29

6-9 Summary of Demonstration Water Data ............................................. 30

6-10 Summary of Regression and Residual Statistics Soil Accuracy ........................... 30

vii
List of Abbreviations and Acronyms

Beazer

CCAL

DCAA

ECD

EMSL-LV

EPA

ERA

ESAT

FASP

FID

GC

ICAL

IDW

ITER

Koppers

4&l

&I/L

mg/kg

MMTP

MtBE

NRMRL

ORD

OSWER

PCP

PE

ppb

ppm

PRC

QA

QADE

QAPP

QC

RCRA

RECAP

RPD

RSD

SARA

SITE

SMO

SVOC

USI

Beazer East, Inc.

continuing calibration

2,4-dichlorophenylacetic acid

electron capture detector

Environmental Monitoring Systems Laboratory-Las Vegas

Environmental Protection Agency

Environmental Resource Associates

Environmental Services Assistance Team

Field Analytical Screening Program

flame ionization detector

gas chromatograph

initial calibration

investigation-derived waste

Innovative Technology Evaluation Report

Koppers Company

micrograms per kilogram

microgram per liter

milligram per kilogram

Monitoring and Measurement Technologies Program

methyl tert-butyl ether

National Risk Management Research Laboratory

Office of Research and Development

Office of Solid Waste and Emergency Response

pentachlorophenol

performance evaluation

parts per billion

parts per million

PRC Environmental Management, Inc.

quality assurance

quality assurance and data evaluation

Quality Assurance Project Plan

quality control

Resource Conservation and Recovery Act

Region 7 Environmental Collection and Analysis Program

relative percent difference

relative standard deviation

Superfund Amendments and Reauthorization Act of 1986

Superfund Innovative Technology Evaluation

Sample Management Office

semivolatile organic compounds

Unit Structures, Inc.

. . . VIII
Acknowledgments

This demonstration and the subsequent preparation of this report required the services and support of numerous

personnel from the EPA Environmental Monitoring Systems Laboratory (Las Vegas, Nevada); EPA Region 7 (Kansas

City, Kansas); Beazer East, Inc. (Pittsburgh, Pennsylvania); Winona Post, Inc. (Winona, Missouri); and PRC

Environmental Management, Inc. (Kansas City, Kansas; Cincinnati, Ohio; and Chicago, Illinois). The cooperation

and efforts of these organizations and personnel are gratefully acknowledged.

Additional information concerning the demonstration and technology described in this report can be obtained by

contacting Mr. Lary Jack, EPA Environmental Monitoring Systems Laboratory, technical project manager, at (702)

798-2373, or Mr. Eric Hess, PRC Environmental Management, Inc., project manager, at (913) 573-1822.

ix
Section 1

Executive Summary

This innovative technology evaluation report (ITER)

presents information on the demonstration of the

U. S . Environmental Protection Agency (EPA) Region 7

Superftmd Field Analytical Screening Program (FASP)

method for determining pentachlorophenol (PCP)

contamination in soil and water. This method was

demonstrated in Morrisville, North Carolina, in August

1993. The demonstration was conducted by PRC

Environmental Management, Inc. (PRC), under contract

to the EPA Enviromnental Monitoring Systems

Laboratory-Las Vegas (EMSL-LV). The demonstration

was developed under the Monitoring and Measurement

Technologies Program (MMTP) of the Superfund

innovative Technologies Evaluation (SITE) Program.

The FASP PCP Method was demonstrated in

conjunction with the demonstrations of four other field

screening technologies: (1) the HNU-Hanby Test Kit

developed by HNU Systems, (2) the Penta RISc Test

Systems developed by EnSys Incorporated, (3) the

EnviroGard PCP Test Kit developed by Millipore

Corporation, and (4) the Penta RaPID Assays developed

by Ohmicron Corporation. The results of these

demonstrations are presented in separate reports similar to

this one.

The first objective of this demonstration was to

evaluate the FASP PCP Method for accuracy and

precision in detecting high and low levels of PCP by

comparing its results to those from a confirmatory

laboratory that used standard EPA-approved analytical

methods. These EPA-approved methods are used to

provide legally defensible analytical data to monitor or

enforce environmental regulations. Because these EPAapproved methods are used by the regulatory community,

this demonstration also used these methods. While these

methods may include inherent tendencies that may bias

data or may include procedures that developers disagree

with, they are the best methods for providing legally

defensible data as defined by the regulatory community.

To remove as much of these inherent tendencies as

possible, PRC used post hoc residual analysis to remove

data outliers. The FASP PCP technology was also

qualitatively evaluated for the length of time required for

analysis, ease of use, portability, and operating cost.

The second objective of the demonstration was to

evaluate the specificity of the technology. The specificity

was evaluated by examining the effects of

naturally-occurring matrix effects, site-specific matrix

effects, and chemical cross-reactivity. Information on the

technology’s specificity was gathered from literature, the

analysis of demonstration samples, and through a

specificity study.

The site selected for demonstrating the technology

was the former Koppers Company (Koppers) site in

Morrisville, North Carolina. This site was selected

because a National Risk Management Research Laboratory

(NRMRL) SITE demonstration was planned for this site,

allowing a conjunction of logistical and support efforts

between NRMRL and EMSL-LV. Another reason for

selecting the former Koppers site was that historical

documentation indicated that PCP contamination ranged

from none detected to 3,200 parts per million @pm) in soil

and from none detected to 1,490 parts per billion (ppb) in

groundwater. The PCP carrier used at this site was a

mixture of isopropyl ether and butane. Soil and water

samples also were collected from the Winona Post site in

Winona, Missouri. Samples from the Winona Post site

were shipped to the former Koppers site for inclusion as

demonstration samples. Winona Post samples were

included to broaden the scope of the demonstration by

introducing a different sample matrix and a different PCP

carrier, diesel fuel.

The FASP PCP Method is designed to provide quick,

accurate results for PCP concentrations in soil and water

samples. This method also can detect and quantify other

phenols. PCP concentrations are reported in either parts

per billion or parts per million for soils and parts per

billion for waters. This method was developed by the

EPA Superftmd Branch for use at Superfund sites.

 1
The FASP PCP Method uses a gas chromatograph

(GC) equipped with a megabore capillary column and

either a flame ionization detector (FID) or an electron

capture detector (ECD) to identify and quantify PCP.

Gas chromatography is an EPA-approved method for

determining PCP concentrations in soil, water, and

waste samples. The FASP PCP Method is an

abbreviated, modified version of these methods.

Soil and water samples require extraction before GC

analysis. To remove interferences caused by petroleum

hydrocarbons, including PCP carriers such as mineral

spirits, kerosene, diesel fuel, and fuel oil, an acid-base

partition cleanup step. In this step, the method includes

petroleum hydrocarbons are removed from the reagent

water, while potassium phenates remain in the reagent

water. Sample extracts are injected onto a GC,

separated with a DB-5 megabore capillary column, and

the PCP is identified and quantified using an FID. The

sample extracts are then compared to standards to

determine whether PCP is present in the sample and, if

so, at what concentration. The FASP PCP Method will

only provide high parts per billion detection levels of

PCP in water when an FID is used. To achieve a lower

detection limit, the sample extracts are reanalyzed using

an ECD.

The FASP PCP method is field-portable only in a

mobile laboratory. It should be used indoors in a

temperature-controlled environment. Reagents required

for soil and water sample analysis require refrigeration

and the GC and extraction fume hood require electricity.

The FASP PCP Method requires experienced GC

operators to produce reliable results. The average

number of demonstration samples extracted,

concentrated, and analyzed in one lo-hour day during

the demonstration was 14. The detection limit reported

by this method for soil samples is 0.8 ppm and 1 .O ppb

for water samples.

The FASP PCP Method can be affected by naturally

occurring matrix effects such as humic acids, pH, or

salinity. Other matrix effects include PCP carriers such

as petroleum hydrocarbons or solvents. Due to the

nature of chromatography, this method is not greatly

influenced by chemical cross-reactivity. The FASP PCP

Method was found to be most affected by the diesel fuel

used as a PCP carrier solvent. A specificity study

performed during the demonstration showed that diesel

fuel would provide a positive response when present at

a concentration of 10 ppm. Petroleum hydrocarbon

interferences were found to affect results for the Winona

Post samples.

PRC used linear regression and inferential statistics

to compare the technology’s data to that from the

confirmatory laboratory. When the data sets were

evaluated as a whole, a less accurate performance on the

Winona Post samples was observed due to the diesel fuel

PCP carrier solvent. Both the entire data set and the

Winona Post data alone showed that the method

produced Level 1 data. However, the method performed

well when the samples from the former Koppers site

were examined separately. Within this data grouping,

the technology produced Level 2 data, which was

statistically similar to that from the confirmatory

laboratory or that could be mathematically corrected to

become similar to that from the confirmatory laboratory.

Generally, if 10 to 20 percent of the soil samples (not

contaminated with petroleum) are sent to a confirmatory

laboratory, then the results from the other 80 to 90

percent can be corrected. This could result in a

significant savings in analytical costs. The water

analysis portion of this demonstration produced similar

results. The FASP PCP Method produced Level 2 data

for the samples collected from the former Koppers site.

The regression analysis and the Wilcoxon Signed Ranks

Test indicated that the technology’s data is strongly

correlated to the confirmatory data, but is statistically

different. This means that the FASP PCP Method’s data

must be mathematically corrected by having 10 to

20 percent of its samples slated for confirmatory

analysis. The Winona Post data showed that even when

using sample cleanup, the method produces Level 1 data

that is both dissimilar to the confirmatory data and that

cannot be mathematically corrected.

PRC evaluated field duplicate samples to determine

the technology’s precision relative to the confirmatory

laboratory’s. PRC found no significant difference

between the precision of the FASP PCP Method and that

of the confirmatory laboratory’s for soil and water

analysis. In addition, no PCP carrier effect on precision

was observed.
Section 2

Introduction

This ITER presents information on the demonstration

of the FASP method designed to detect PCP in soil and

water. PRC conducted the demonstration under the EPA

SITE Program. The FASP technology was demonstrated

in conjunction with the demonstrations of four other

technologies: (1) the Penta RISc Test System developed by

EnSys Incorporated, (2) the EnviroGard PCP Test Kit

developed by Millipore Corporation, (3) the Penta RaPID

Assay developed by Ohmicron Corporation, and (4) the

HNU-Hanby Test Kit developed by HNU Systems. The

results of these other technologies are presented in

separate reports similar to this one. All tables and figures

referenced in this document are presented at the end of

their respective sections.

EPA Site Program and MMTP: An Overview

At the time of the. Superfund Amendments and

Reauthorization Act of 1986 (SARA), it was well

recognized that the environmental cleanup problem needed

new and better methods. As a result, the SITE Program

was created to fulfill a requirement of SARA that EPA

address the potential of alternative or innovative

technologies. EPA made this program a joint effort

between the Office of Solid Waste and Emergency

Response (OSWER) and the Office of Research and

Development (ORD). The SITE Program includes four

parts:

: The Demonstration Program (for remediation

technologies)

l The Emerging Technology Program

6 The Monitoring and Measurement Technologies

Program (MMTP)

l The Technology Transfer Program

The largest part of the SITE Program is concerned

with treatment technologies and is administered by ORD’s

NRMRL in Cincinnati, Ohio. However, the MMTP

component is administered by EMSL-LV. The

MMTP is concerned with monitoring and measurement

technologies that identify, quantify, or monitor changes in

contaminant occurring at hazardous waste sites or that are

used to characterize a site.

The MMTP seeks to identify and demonstrate

innovative technologies that may provide less expensive,

better, faster, or safer means of completing this monitoring

or characterization. Managers of hazardous waste sites

are often reluctant to use any method, other than

conventional ones, to generate critical data on the nature

and extent of contamination. In addition, the courts

generally recognize data generated by conventional

laboratory methods; nevertheless, there is a tremendous

need to generate data more cost- effectively. Therefore,

the EPA must identify innovative approaches, and through

verifiable testing of the technologies under the SITE

Program, insure that the innovative technologies are

equivalent to or better than conventional technologies.

The Role of Monitoring and Measurement

Technologies

Measurement and monitoring technologies are needed

to assess the degree of contamination, to determine the

effects of contamination on public health and the

environment, to supply data for selection of appropriate

remedial action, and to monitor the success or failure of

selected remedies. Thus, the MMTP is concerned with

evaluating screening technologies, including remote

sensing, monitoring, and analytical technologies.

Candidate technologies may come from within the

federal government or from the private sector. Through

the program, developers are allowed to rigorously evaluate

the performance of their technologies. By distributing the

results and recommendations of those evaluations, the

market for the technologies is enhanced.
Defining the Process

The demonstration process begins by canvasing the

EPA 10 regional offices (with input by OSWER and

ORD) to determine their needs. Concurrently, classes

of technologies are identified. An ideal match is made

when there is a clear need by EPA regions and anumber

of technologies that can address that need.

Demonstrations are designed to judge each technology

against existing standards and not “one against the

other.”

A demonstration is designed to provide for detailed

quality assurance and quality control (QA/QC) to insure

that a potential user can evaluate the accuracy, precision,

representativeness, completeness, and comparability of

data derived from the innovative technology. In

addition, a description of the necessary steps and

activities associated with operating the innovative

technology is prepared. Cost data, critical to any

environmental activity, are generated during the

demonstration to allow a potential user to make

economic comparisons. Finally, information on

practical matters such as operator training requirements,

detection levels, and ease of operation are reported.

Thus, the demonstration report and other informational

materials produced by the MMTP provide a real-world

comparison of the demonstrated technology to

conventional technologies. With cost and performance

data, as well as “how to” information, users can

determine whether a new technology better meets their

needs.

Components of a Demonstration

Once a decision has been made to demonstrate

technologies to meet a particular EPA need, the MMTP

performs a number of activities. First, MMTP identifies

potential participants and determines whether they are

interested in participating. Each developer is advised of

the general nature of the demonstration and is provided

with information common to all MMTP demonstrations.

Information is sought from each developer about its

technology to insure that the technology meets the

parameters of the demonstration. After evaluating the

information, MMTP informs all respondents whether or

not they have been accepted into the demonstration.

While participants are being identified, potential sites

also are identified, and basic site information is obtained.

The next component, probably the most important,

is the development of plans that describe how the

demonstration will be conducted. A major part of the

EPA’s responsibility is to develop a demonstration plan,

a quality assurance project plan (QAPP), and a health

and safety plan. While the EPA pays for and has the

primary responsibility for these plans, each is developed

with input from all of the demonstration’s participants.

The plans define how activities will be conducted and

how the technologies will be evaluated. MMTP also

provides each developer with site information and often

provides predemonstration samples so the developer can

maximize the field performance of its innovative

technology. Generally, the developers train EPAdesignated personnel to operate the technologies so that

performance is not based on the special expertise of the

developers. This approach also insures that potential

users have valid information on training requirements

and the types of operators who typically use a technology

successfully.

The field demonstration itself is the shortest part of

the process. During the field demonstration, data is

obtained on cost, technical effectiveness (compared to

standard methods), and limiting factors. In addition,

standardized field methods are developed, and daily logs

of activities and observations (including photographs or

videotapes) are produced. EPA is also responsible for

the comparative, conventional method analytical costs

and the disposal of any wastes generated by the field

demonstration.

The final component of an MMTP demonstration

consists of reporting the results and insuring distribution

of demonstration information. The primary product of

the demonstration is an ITER, like this one, which is

peer-reviewed and distributed as part of the technology

transfer responsibility of the MMTP. The ITER fully

documents the procedures used during the field

demonstration, QA/QC results, the field demonstration’s

results, and its conclusions. A separate QA/QC data

package is also made available for those interested in

evaluating the demonstration in greater depth. Two-page

“Technical Briefs” are prepared to summarize the

demonstration results and to insure rapid and wide

distribution of the information.

Each developer is responsible for providing the

equipment or technology product to be demonstrated, its

own mobilization costs, and the training of EPAdesignated operators. The MMTP does not provide any

funds to developers for costs associated with preparation

of equipment for demonstration or for development, and

it does not cover the costs developers incur to

demonstrate their products.

Rationale for this Demonstration

PCP is a regulated chemical, is included in the EPA

Extremely Hazardous Substances List, and is reported in

the EPA Toxic Substances Control Act. Recently, PCP

regulations under the Resource Conservation and

4
Recovery Act (RCRA) have been created specifically for

wood treatment facilities. PCP is included as a target

compound of many EPA-approved analytical methods

including: EPA 500 Series Methods 515.1 and 525,

EPA 600 Series Methods 604 and 625, and

EPA SW-846 Manual Methods 8040, 8151, 8250, and

8270. All these methods use solvent extraction and gas

chromatography. Detection and quantitation is

performed with FIDs, ECPs, or mass spectrometer

detectors. Analyzing samples for PCP using these

methods is typically costly and time consuming.

EMSL-LV identified the need for effective, accurate,

low cost screening technologies that could provide near

real-time analytical data for PCP to Superfund and

RCRA decisionmakers.

Demonstration Purpose, Goals,

and Objectives

The FASP PCP Method was evaluated on its

accuracy and precision in detecting high and low levels

of PCP in environmental samples, and on the effects, if

any, of both PCP carrier and natural matrix

interferences. The accuracy and precision of the method

was statistically compared to the accuracy and precision

of a conventional confirmatory laboratory that used

EPA-approved analytical methods. This comparison was

also used to determine the highest data quality level that

the technology could attain in field applications. For the

purpose of this demonstration, three primary data quality

levels were defined as follows (EPA 1990):

Level 1: Level 1 data is not necessarily analytespecific. Technologies that generate

Level 1 data provide only an

indication of contamination. Generally, the use of these technologies

requires sample documentation, instrument calibration, and performance

checks of equipment.

Level 2: Level 2 data is analyte-specific. To

provide an accuracy check, verification analysis by an EPA-approved

method is necessary for at least

10 percent of the samples. The

method’s analytical error is also

quantified. Use of QC procedures such

as sample documentation, chain-ofcustody procedures, sample holding

time criteria, initial and continuing

instrument calibration, method blank

analysis, rinsate blank analysis, and

trip blank analysis is recommended.

Level 3: Level 3 data is considered formal or

confirmatory analysis. These data are

analyte-specific and generally involve

second-method confirmation on

100 percent of critical samples.

Analytical error is quantified (including precision, accuracy, and

coefficient of variation) and monitored. The following QC measures are

used: sample documentation, chain of

custody, sample holding time criteria,

initial and continuing instrument

calibration, rinsate blank analysis, trip

blank analysis, and performance

evaluation samples. Detection limits

are determined and monitored.

Inherent in this concept of data quality levels is

accuracy. Although PRC could not find a reference that

defined the expected and quantified accuracy of each

data quality level, it imposed common accuracy criteria

in defining these data quality levels. Data quality Level

3 is considered the most accurate and is based on a

formal analysis by approved methods. Data quality

Level 2 is less accurate, but it still does quantify

compound concentrations. Data quality Level 1 is the

least accurate and is often considered survey data, useful

only in identifying the presence or absence of a

compound or class of compounds. Because no existing

quantification of the criteria defining these data quality

levels was found, PRC set the criteria used in this ITER

based on the experience of the EPA and PRC personnel

involved and on a general survey of environmental

consultants who use data.

The FASP PCP Method was also qualitatively

evaluated for specificity, the length of time required for

its analysis, ease of use, portability, and operating cost.

5
Section 3

Predemonstration Activities

Several activities were conducted by EMSLLV,

PRC, and other demonstration participants before the

demonstration began. These activities included identifying

developers, selecting demonstration sites, selecting the

confirmatory laboratory and analytical methods,

conducting predemonstration sampling, and training

technology operators. Predemonstration sampling and

analysis are normally used to allow developers to refine

their technologies and revise their operating instructions,

if necessary, prior to the demonstration.

Identifying Developers

EMSL-LV asked that PRC search for technologies

that could be included in this demonstration. Based on

PRC’s search, the FASP method was included.

The Sites and Their Principal Contaminants

To evaluate the field screening technology under field

conditions, hazardous waste sites suitable for the

demonstration were needed. The following criteria were

used to select appropriate sites:

l The technology needed to be demonstrated at

sites with a wide range of PCP contamination.

l PCP concentrations at the sites had to be well

characterized and documented.

l The sites had to be accessible for conducting

demonstration activities without interfering with

other activities being conducted on site.

l Because various carriers have been used with

PCP and because those carriers may influence

the technology, it was determined that the sites

used should offer two different carriers.

The former Koppers wood treatment site was selected

as one of the two sites for this demonstration based on

these criteria. This site also was selected because EPA’s

NRMRL was planning a SITE demonstration of the ETG

Environmental, Inc., Base-Catalyzed Decomposition

technology at the site, and choosing the former Koppers

site would allow for a conjunction of logistical and support

efforts between NRMRL and EMSL-LV. The second

demonstration site selected was the Winona Post site wood

treatment facility. The Winona Post site is contaminated

with PCP in a diesel fuel carrier solvent. The former

Koppers site is contaminated with PCP in butane and

isopropyl ether carrier solvents.

The former Koppers site is located in Morrisville,

North Carolina, at the intersection of Highway 54 and

Koppers Road. The site is currently owned by two

companies : Beazer East, Inc. (Beazer), and Unit

Structures, Inc. (USI). The portion of the site owned by

Beazer is inactive. The portion of the site owned by US1

is currently used as a wood laminating facility. The site

occupies about 52 acres and includes the wood laminating

building, an office, and several warehouses. Surrounding

land use is a mixture of commercial, light industrial, and

rural residential. During previous investigations at the

former Koppers facility, samples were collected from the

following media: soil, groundwater, surface water,

sediment, and fish. Sampling revealed PCP concentrations

ranging from not detected to 3,200 ppm in soils and from

not detected to 1,490 ppb in water.

The Winona Post site is located in Winona, Missouri,

on Old Highway 60 West. It has operated as a sawmilling

and wood preserving facility since at least the early 1950s.

The sawmilling, wood preserving, and storage areas of the

facility cover about 4 acres. The remaining portion of the

40-acre facility is wooded and largely undeveloped. The

main features of the facility include a sawmill, office,

treatment building, debarker, storage building, and pond.

Currently, the company uses a premixed solution of

5 percent PCP in diesel fuel. The solution is stored in a

20,000-gallon aboveground storage tank located adjacent

to the treatment building. In the past, the Winona Post

Company mixed its own solution from concentrated PCP.

Prior to the mid-1950s. the Winona Post Company treated

wood with cresol. In 1992, six samples collected at the

Winona Post site revealed PCP concentrations ranging

from 886 to 24,000 ppm in soil and sediment samples and

6
from 10 to 528 ppm in surface water samples.

PCP is an organic chemical with an empirical formula

of C&&OH and a molecular weight of

266 grams per mole. PCP has a melting point of 191 “C

and a boiling point of 310 “C. The specific gravity of

PCP is 1.978 grams per cubic centimeter. PCP is

described as almost insoluble in water, with 8 milligrams

able to dissolve into 100 milliliters of water. The octanol

ratio coefficient of PCP is 6,400, which indicates that PCP

is tightly bound to the soil matrix when it is released into

the environment. PCP is used as a wood preservative, an

insecticide, a preharvest defoliant, a slimicide, and a

defoaming agent. The largest user of PCP is the wood

treating industry. For treating wood, PCP is usually

diluted to a 5 percent solution with solvents such as

mineral spirits, kerosene, diesel fuel, or fuel oil. PCP

also has been applied to wood with methylene chloride and

liquified petroleum gas, such as butane. It has been

manufactured under numerous trade names.

Selecting the Confirmatory Laboratory and

Analytical Methods

Before this demonstration, the EPA Region 7

Laboratory arranged for all soil samples to be analyzed

under the Region 7 Environmental Collection and Analysis

Program (RECAP) Contract and all water samples to be

analyzed under its Environmental Services Assistance

Team (ESAT) Contract. SW-846 protocols for Level 3

data were to be used to analyze soil and water samples

during this demonstration. All samples were to be

extracted by EPA Method 354OA and analyzed by EPA

Method 8270A. Any soil samples in which PCP was not

detected using Method 8270A were to be reanalyzed by

Method 8151A calibrated to PCP. Any groundwater

samples in which PCP was not detected using

Method 8270A were to be reanalyzed using

Method 515.1. All of these analytical methods are well

established and approved by EPA. QA procedures,

reporting requirements, and data quality objectives of

these methods are consistent with the goals of the SITE

Program.

Training Technology Operators

Analysis with the FASP PCP Method was conducted

by a PRC operator. Before the demonstration began, this

individual was trained in how to use the method. The

training involved a review of operating procedures and

instruction provided by the lead chemist.

Predemonstration Sampling and Analysis

In July 1993, PRC prepared a predemonstration

sampling plan (PRC 1993a), and on July 12, 1993, PRC

collected predemonstration soil samples from areas at the

former Koppers facility previously identified as containing

high, medium, low, and not detected concentrations of

PCP. PRC analyzed one replicate of each sample using

the FASP PCP Method. Predemonstration samples did

not exhibit their expected PCP concentrations. These

samples were not analyzed by a confirmatory laboratory

because the contracts for the confirmatory analyses were

not yet finalized. No predemonstration samples were

collected from Winona Post because this site had not been

added to the demonstration plan at the time of the

predemonstration sampling.

7
Section 4

Demonstration Design and Description

This section describes the organization of the

demonstration, presents an overview of the

demonstration’s design, and details all deviations from

the developer- and EPA-approved, demonstration plan.

Among the key portions of the demonstration plan

presented here are the types of data collected and the

statistical methods used to determine the accuracy and

precision of the technology. A detailed description of

the demonstration is presented in the demonstration plan

(PRC 1993b).

Demonstration Design

The primary objective of the demonstration was to

evaluate the FASP PCP Method for its effectiveness in

detecting PCP in soil and water when operated in field

conditions. This objective included defining the

precision, accuracy, cost, and range of usefulness for the

technology. A secondary objective was to define data

quality objectives that the technology can be used to

address. The evaluation was designed so that results

from the technology could be compared to those of a

confiiatory laboratory that analyzed each sample using

standard EPA-approved methods. The design limited, as

much as possible, those elements of sample collection

and analysis that would interfere with direct comparison

of the results. These elements included heterogeneity of

the samples and interference from other chemicals or

other controllable sources.

The design also insured that the data was collected

in a normal field environment. To achieve this, the

method was used in a trailer located at the former

Koppers site. The operator was trained by the PRC lead

chemist. However, the operator obtained all results on

his own and reported the results once he believed the

results were accurate and precise. Standard QC samples

were analyzed with each batch of environmental

samples. Numerous laboratory and field duplicate

samples were included among those analyzed to insure

a proper measure of precision. The technology was also

tested for common interferants. Qualitative measures,

such as portability and ease of operation, were noted by

the operator.

Overall, the demonstration was executed as

described in the demonstration plan (PRC 1993b), which

included the QAPP. The final version of the plan was

approved by all participants and developers before the

demonstration began.

Implementation of the Demonstration Plan

For the demonstration, PRC collected 98 soil

samples, 14 soil sample field duplicates, 10 water

samples, and 6 water sample field duplicates. Each soil

sample was thoroughly homogenized and then split into

replicate samples. One replicate from each sample was

submitted to the confirmatory laboratory; another

replicates was analyzed in a trailer at the former

Koppers site using the FASP PCP Method. In addition

to these samples, two soil performance evaluation (PE)

samples and three water PE samples were analyzed.

The final demonstration plan called for the

collection of 90 soil samples with the following

distribution: (1) 40 samples containing 0 to 100 ppm

PCP; (2) 25 samples containing 100 to 1,000 ppm PCP;

and (3) 25 samples containing greater than 1,000 ppm

PCP. During this demonstration, 98 soil samples were

collected. The actual distribution of these samples,

when the demonstration was complete, was as follows:

(1) 60 samples contained 0 to 100 ppm PCP;

(2) 16 samples contained 100 to 1,000 ppm PCP; and

(3) 22 samples contained greater than 1,000 ppm PCP.

This skewing of the sample set to the 0 to 100 ppm range

should not affect the usability of this report, because the

majority of EPA PCP soil action levels occur in the

20 to 100 ppm range.

Of the samples collected for the demonstration,

53 soil samples, 9 soil field duplicates, 5 water samples,

and 5 water field duplicate samples were collected at the

former Koppers site. Soil samples were collected from

8
areas known to exhibit a wide range of PCP

concentrations. The areas sampled ranged in PCP

concentration from not detected to 3,220 ppm. Most of

the samples were collected from areas characterized

during the remedial investigation. Water samples were

collected from five existing grotmdwater monitoring

wells located on the former Koppers site. The PCP

concentrations in these wells were well documented from

past sampling. The PCP concentrations sampled ranged

from not detected to nearly 1,500 ppb.

Of the samples collected for the demonstration,

45 soil samples, 5 soil field duplicates, 5 water samples,

and 1 water duplicate sample were collected at the

Winona Post site. Soil samples were collected in areas

believed to be contaminated with high (greater than

1,000 ppm), medium (100 to 999 ppm), and low (less

than 99 ppm) concentrations of PCP. The identification

of these areas was based on past sampling data and

visual signs of waste disposal. Water samples were

collected from the only surface water located on or near

the site. All of the Winona Post samples were collected,

packaged, and shipped to the former Koppers site using

methods detailed in the demonstration plan (PRC

1993b).

Field Modifications to the Demonstration

Plan

Two field modifications were made to the approved

demonstration plan. First, fluorescein was not added to

soil samples from the former Koppers site. The nature

of the soil samples at both the former Koppers site and

the Winona Post site allowed easy and thorough

homogenization. The saturated stiff clay matrix for

which the fluorescein additions were designed was not

encountered at the former Koppers site and thus, for

consistency, this technique was eliminated at both sites.

PRC believes that the elimination of the fluorescein from

the homogenization process was offset by the long

homogenization times used during this demonstration.

To further examine this approach, PRC conducted a

side-by-side comparison of homogenization with and

without fluorescein. Samples from the former Koppers

site were used for this comparison. The dry nature of

the soil required that it be hydrated with water to allow

visible distribution of the fluorescein. The addition of

water and fluorescein caused a two-unit increase in the

soil sample pH. This alteration of the sample chemistry

coupled with the reactive nature of PCP invalidated the

fluorescein homogenization approach for environmental

applications. PRC used an EPA-approved homogenization method and applied it to each sample for 10

to 15 minutes. This method involved vigorous kneading

of the sample in a clear plastic bag.

The second modification to the approved

demonstration plan involved sampling the water matrix.

This change was made because the EPA Region 7

project sponsor altered the design of the demonstration

with regard to the evaluation of the water assays. The

EPA sponsor required that the number of water samples

collected and analyzed for the demonstration be reduced

to a total of 5 to 10 samples. The approved demonstration plan called for the collection of 50 groundwater

samples. To maximize the usefulness of the reduced

number of water samples, PRC and EMSL-LV agreed to

combine data from both sites if they could be shown

statistically to come from the same distribution, thereby

increasing the sample set size. Also, the EPA Region 7

sponsor agreed to allow the following: (1) the Region 7

Laboratory would split and analyze samples from

Winona Post in sample-plus duplicate (split) pairs;

(2) excess water from the original Winona Post water

sample that was duplicated would be used for laboratory

QA/QC; and (3) only five monitoring wells would be

sampled at the former Koppers site, and each sample

would be duplicated. This approach would have resulted

in five paired samples (the sample plus its duplicate)

from each site. This in turn would have provided five

samples from each site for an accuracy assessment, and

five paired samples from each site for a precision

assessment. Although these are minimal sample sizes,

this design was believed to provide the most useful data

given the reduction in analytical resources that the EPA

Region 7 sponsor required. However, when PRC

delivered the soil and water samples from the former

Koppers site, it learned that the Winona Post water

samples had been extracted and analyzed as they were

delivered, that is, as five environmental samples with

one duplicate. This failure to follow the modified

experimental design resulted in only four single sample

results and one duplicate result for precision analysis for

this data set. The Koppers data set consisted of five

duplicate pairs.

Data Collection

The technology operator prepared a subjective

evaluation of how difficult the technology was to use.

Other qualitative measures assessed included portability,

ruggedness, instrument reliability, and health and safety

considerations. Information on these qualitative factors

was collected both by the operator of the technology and

by the lead chemist. To evaluate accuracy and

precision, all samples collected for analysis were split

between the technology and the confirmatory laboratory.

Statistical methods used to compare the results of the

two methods are detailed below. The cost of using this

technology was also assessed. Cost, for the purposes of

this demonstration, included expendable supplies,

nonexpendable equipment, labor, and investigation9
Instrument reliability was evaluated by monitoring

the equipment’s ability to maintain its calibration. An

initial calibration (ICAL) was performed at the start of

the demonstration. The instrument calibration was

monitored daily through continuing calibrations (CCAL)

using the mid-level concentration of the PCP standards.

During the CCAL the peak response obtained is

compared to the average peak response obtained during

the ICAL. These responses are compared by determining the RPD between responses. An RPD value of less

than or equal to 25 percent is required to continue sample analysis. If the RPD is higher than 25 percent,

another ICAL must be performed. Over the 13 days of

the demonstration, three ICALs and 13 CCALs were

performed. Out of three ICALs, two were performed

for soil analysis, and one was performed for water

analysis. Eleven CCALs were performed for the

analysis of soil samples, and two CCALs were

performed for the analysis of water samples. CCALs

were performed on each day of sample analysis. On the

eleventh day of the demonstration, the CCAL for soil

analysis was out of control as a result of analyzing soil

samples from the Winona Post site, which contained

large amounts of petroleum hydrocarbons. Due to the

heavy contamination with petroleum hydrocarbons in the

samples and extracts, the septa and the glass liner in the

injection port became contaminated, and the column

became saturated with hydrocarbons. After determining

the problem, the septa and the glass liner were replaced,

and the column was conditioned at elevated oven

temperature to desorb the petroleum hydrocarbons.

Another ICAL was performed after column

conditioning; although the relative standard deviation

(RSD) for PCP was 33 percent in the second ICAL, this

RSD was deemed acceptable, and the average calibration

factor was used for sample quantitation. The two

CCALS performed after the second ICAL were within

the new control limits.

A new ICAL was performed for the analysis of

water samples. The CCAL performed for water analysis

was within control limits; however, the CCAL

performed at the end of the analysis did not fall within

control limits. The retention time of the specific PCP

peak also was monitored through the CCALs. The

retention time of this peak shifted throughout the

demonstration. To maintain an accurate retention time

window for this peak, the window was adjusted.

Another reliability factor evaluated was the

consistency of the data system to properly draw a

baseline for standards and samples. Baselines were

drawn consistently for samples from the former Koppers

site. However, samples from Winona Post site were

highly contaminated with petroleum hydrocarbons,

causing the baseline to drift.

Operators of the method need to be aware of

hazards due to the chemicals used, particularly methyl

tert-butyl ether (MtBE), sodium sulfate, and sulfuric

acid. MtBE is used to extract PCP from samples and to

dilute standard solutions. MtBE is an explosive and

flammable solvent and should be handled only under a

flame hood. Care should be taken when using MtBE to

avoid inhalation and direct contact with the liquid and

fumes. Ignition sources such as open flames should also

be avoided, and a dry chemical fire extinguisher should

be available in case of fire. Sodium sulfate is used to

chemically dewater soil samples. Sodium sulfate is a

fine granular powder and can be a skin and eye irritant.

Protective clothing and safety glasses should be worn

when using sodium sulfate. Sulfuric acid is used to

reduce the pH of the samples. Sulfuric acid can cause

chemical burns when spilled on the skin. Chemicalresistant clothing, gloves, and safety glasses are required

for protection from sulfuric acid. An adequate source of

water should be available in case the acid comes in

contact with the skin. Eyewash solutions also should be

available.

This method uses various types of glassware to

analyze samples. Using glass always presents a

possibility of breakage and injury. Glassware should be

handled in a safe, careful manner. Broken glassware

should not be used and should be disposed of in a safe

manner. The ECD contains Nickel-63, a radioactive

material. The amount of radioactive material in the

ECD is minimal, and it is stored in a sealed container.

Nevertheless, the container must be checked for possible

leakage twice a year. Leakage of the radioactive

material above federally regulated limits requires

immediate attention. The FID uses hydrogen gas, which

is explosive and stored under high pressure. Care must

be taken to secure the hydrogen gas cylinders to avoid

cylinder damage.

The total cost of the analytical equipment used

during this demonstration was $23,214. This cost

includes the GC equipped with an ECD and FID, the

autosampler, the data system, all equipment required to

set up the GC, and installation. Costs per component

are: $13,149 for the GC; $3,865 for the autosampler;

and $6,200 for the data system. Analytical equipment

can also be rented from a number of companies. A

general survey of current market costs for comparable

equipment indicates ranges from $1,500 to $2,500 per

month. Most rental companies require a minimum

rental time period, but this may be negotiable. Rental

rates usually include delivery and setup but do not

include GC columns. Many companies also offer rentto-own or lease-to-own options for analytical equipment.

The cost of reagents and equipment needed to perform

the extraction, preparation, and analysis of soil samples

19
derived waste (IDW) disposal. These costs were tracked

during the demonstration.

Statistical Analysis of Results

For both the innovative technology and the

confirmatory laboratory, two data sets were created: one

for soil samples and the other for water samples. In

addition, each water and soil data set was composed of

two subsets, one for the samples taken from the former

Koppers site and one for those collected at the Winona

Post site. This grouping was intended to assess potential

PCP carrier effects. A third data separation involved

grouping the site-specific data sets into results greater

than 100 ppm PCP and less than 100 ppm PCP. This

grouping was intended to assess potential concentration

effects on the data analysis.

These data sets were prepared for the statistical

analysis following methods detailed in the approved

demonstration plan. When comparing duplicate samples

or when comparing the results of a technology to those

from the confirmatory laboratory, sample pairs that

contained a nondetect were removed from the data sets.

While other statistical methods can be used when

nondetects are encountered, PRC believed that the

variance introduced by eliminating these data pairs

would be less than, or no more than equal to, the

variance produced by giving not detected results an

arbitrary value.

lntramethod Comparisons

Sample results from the technology were compared

to their duplicate sample results and to other QA/QC

sample results. These comparisons are called

intramethod comparisons. Intramethod accuracy was

measured by assessing each technology’s performance in

analyzing PE samples. If the method produced a result

considered accurate by the company that produced the

PE samples, the technology was considered to have

acceptable intramethod accuracy for this demonstration.

Intramethod precision was assessed through the statistical

analysis of relative percent differences (RPD). First,

RPDs of the results for each sample pair, in which both

the sample and its duplicate were found to contain PCP,

were determined. RPDs then were compared to upper

and lower control limits. When using conventional

technologies, such data is often available from analysis

of samples collected during previous investigations.

Because the technology being demonstrated was itself

being assessed, the control limits used were calculated

from data provided during this investigation. To

determine these control limits, the standard deviation of

the RPDs was calculated for each technology. This

standard deviation was then multiplied by two and added

to its respective mean RPDs. This established the upper

control limit for the technology. Because an RPD of

zero would mean that the duplicate samples matched

their respective samples perfectly, zero was used as the

lower control limit. This resulted in a large range of

acceptable values. Because duplicate analyses seldom

match perfectly, even for established technologies, all

samples that fell within the control limits were

considered acceptable. PRC determined that if at least

90 percent of the duplicate samples fell within these

control limits, the technology had acceptable intramethod

precision.

Intermethod Comparisons

Data sets from the FASP PCP Method also were

statistically compared to results from the confirmatory

laboratory, and the precision of the method was

statistically compared to the precision of the

confirmatory laboratory. These comparisons are called

intermethod comparisons. In both cases, results from

the confiiatory laboratory were considered to be as

accurate and precise as analytically possible. Statistical

methods used to determine intermethod accuracy

included linear regression analysis and the Wilcoxon

Signed Ranks Test. Before undertaking the regression

analysis, PRC further prepared the data sets by

averaging the field duplicate results. This approach

ensured that samples were not unduly weighted. PRC

calculated linear regression by the method of least

squares. Calculating linear regression in this way makes

it possible to determine whether two sets of data are

reasonably related, and if so, how closely. Calculating

linear regression produces an equation that can be

visually expressed as a line. Three factors are

determined during calculations of linear regression: (1)

the y-intercept, (2) the slope of the line, and (3) the

correlation coefficient, also called an 3. All three of

these factors must have acceptable values before a

technology’s accuracy was considered to meet Level 3

data quality requirements.

The ;L expresses the mathematical relationship

between two data sets. If the 3 is one, then the two data

sets are directly related. Lower ? values indicate less of

a relationship. Because of the heterogeneous nature of

environmental samples, ? values between 0.85 and

1 were considered to meet data quality Level 3 accuracy

requirements; r;? values between 0.75 and 0.85 were

considered to meet data quality Level 2 accuracy

requirements; and ? values below 0.75 were considered

not accurate, meeting only Level 1 accuracy

requirements at best.

If the regression analysis resulted in an ? between

0.85 and 1, then the regression line’s y-intercept and

10
slope were examined to determine how closely the two

data sets matched. A slope of one and a y-intercept of

zero would mean that the results of the technology

matched those of the confirmatory laboratory perfectly.

Theoretically, the farther the slope and y-intercept differ

from these expected values, the less accurate the

technology. Nevertheless, a slope or y-intercept can

differ slightly from their expected values without that

difference being statistically significant. To determine

whether such differences were statistically significant,

PRC used the normal deviate test statistic. This test

statistic results in a value that is compared to a table.

The value at the 90 percent confidence level was used

for the comparison. To meet data quality Level 3

requirements, both the slope and y-intercept had to be

statistically the same as their ideal values.

If the 3 was between 0.75 and 0.85, and one or

both of the other two regression parameters were not

equal to their ideal, the technology was considered to be

inaccurate but producing Level 2 quality data. Results

in this case could be mathematically corrected if 10 to 20

percent of the samples were sent to a confiitory

laboratory. Analysis of a percentage of the samples by

a confiimatory laboratory would provide a basis for

determining a correction factor. Only in cases where the

?, the y-intercept, and the slope were all found to be

acceptable did PRC determine that the technology was

accurate, meeting Level 3 data quality requirements.

Data placed in the Level 1 category had ? values

less than 0.75, the data was not statistically similar to the

confirmatory data, based on parametric testing, or the

results did not meet the manufacturer’s performance

specifications.

A second statistical method used to assess the

intermethod accuracy of the data from each technology

was the Wilcoxon Signed Ranks Test. This test is a

nonparametric method used to compare matched pairs of

data. It can be used to evaluate whether two sets of data

are significantly different. The test requires no

assumption regarding the population distribution of the

two sets of data being evaluated other than that the

distributions will occur identically. In other words,

when one data point deviates, its respective point in the

other set of data will deviate similarly. Because the only

deviation expected during the demonstration was a

difference in the concentrations reported by each

technology, the two sets of data were expected to deviate

in the same way. The Wilcoxon Signed Ranks Test

calculation uses the number of samples analyzed and a

ranking of the difference between the result obtained

from the demonstrated technology and the corresponding

result from the confirmatory laboratory. The rankings

can be compared to predetermined values on a standard

Wilcoxon distribution table, which indicates whether,

overall, the two methods have produced similar results.

Finally, the precision of the technology was

statistically compared to the precision of the

confirmatory laboratory using Dunnett’s Test. This test

was used to assess whether the precision of the

technology and that of the confirmatory laboratory were

statistically equivalent. First, PRC determined the mean

RPD for all samples and their respective duplicates

analyzed by the confirmatory laboratory. The RPD of

each duplicate pair analyzed by each of the technologies

was then statistically compared to this mean. It should

be noted that a Dunnett’s result showing the precisions

are not similar does not mean that the precision of the

technology was not acceptable, only that it was different

from the precision of the confirmatory laboratory. In

particular, the Dunnett’s Test has no way of determining

whether or not any difference between the two data sets

actually resulted because a technology’s data was more

precise than the confirmatory laboratory’s. The

Dunnett’s results were verified by the Wilcoxon Signed

Ranks Test.

11
Section 5

Confirmatory Analysis Results

All samples collected during this demonstration

were submitted to the EPA Region 7 Laboratory for

confirmatory analysis. Water samples were analyzed by

the EPA Region 7 Laboratory under the ESAT Contract,

and soil samples were analyzed under the RECAP

contract. The ESAT Contract analysis was conducted at

the EPA Region 7 Laboratory. The EPA Region

7 Laboratory forwarded all soil samples to the RECAP

Laboratory. Discussion of the analyses at both

laboratories is presented below. Analytical data

provided by the confirmatory laboratories is shown in

Section 6 with that of the FASP PCP Method.

Confirmatory Laboratory Procedures

EPA Region 7 Laboratory Quality Assurance and

Data Evaluation (QADE) Branch personnel conducted a

Level 2 data review on results provided by the

confirmatory laboratories. A Level 2 data review does

not evaluate raw data or check calculated sample values.

A review of the raw data and a check of the calculations

was performed by QC personnel from each of the

confirmatory laboratories before submitting the data

package to the EPA Region 7 Laboratory QADE

Branch. PRC was not able to review all of the raw data

generated from the analysis of samples. However, PRC

did review the laboratory case narratives and the EPA

Region 7 Laboratory QADE Branch comments generated

by the Level 2 data review.

The following sections discuss specific procedures

used to identify and quantitate semivolatile organic

compounds (SVOC), and specifically PCP, using the

following methods: SW-846 Method 8270A (soil and

water), SW-846 Method 8151A (soil), and EPA Method

515.1 (water).

Sample Holding Times

All of the analytical methods used for confirmatory

analysis require that all sample extractions be completed

within 7 days from the time a sample is collected. Due

to the stability of PCP, EPA’s ORD Methods Validation

Section extended these holding time requirements by

4 days for this demonstration. All sample extracts must

be analyzed within 40 days of validated sample receipt.

All holding time requirements were met for samples

collected during this demonstration.

Sample Extraction

EPA Method 3550 was used to extract soil samples

prior to analysis by EPA Method 8270A. This method

involves sonication extraction of the soil using methylene

chloride. The confirmatory laboratory used both the low

concentration extraction method and the high

concentration extraction method discussed in EPA

Method 3550. To determine the appropriate extraction

method to use for the analysis of individual soil samples,

the confirmatory laboratory screened each sample using

the screening techniques recommended in EPA Method

8270A. EPA Method 3510A was used to extract water

samples and involves a separatory extraction of the water

with methylene chloride. To ensure that phenolic

compounds, such as PCP, were adequately extracted

from the water samples, two extractions of each water

sample were performed. The pH of the water was

adjusted to greater than 12 and extracted, then the pH of

the water sample was adjusted to below 2 and extracted.

The two sample extracts were then combined for sample

analysis.

Low-level detection analytical methods for PCP

included different procedures for sample extraction. The

method used for the soil samples, EPA Method 8151A,

involves an acidification of the soil sample, followed by

an ultrasonic extraction with methylene chloride. This

extraction is similar to the EPA Method 3550 sonication

extraction. The soil sample extract was then taken

through an acid-base partition to remove potentially

interfering compounds from the sample extract. The

sample extract was then concentrated and taken through

12
a diazomethane derivatization. This procedure replaces

the hydrogen atom of the alcohol group with a methyl

anion. This derivatization removes the polarity

associated with PCP and enables improved

chromatographic behavior. PCP standards used for

sample identification and quantitation were taken through

the same derivatization steps as samples to allow a direct

comparison of concentration. That is, no correction

factor needs to be used for the molecular weight of the

derivatization product.

The low level detection analytical method used for

water samples, EPA Method 515.1, involves a separatory extraction of the water sample with methylene

chloride. The pH of the water samples was adjusted in

a similar manner to the pH adjustment used for the water

samples extracted with EPA Method 3510A. In EPA

Method 515.1, the solvent extract from the basic

extraction is discarded because it contains no PCP. This

step also removes potential interferences. The water

sample extract is then concentrated and derivatized in the

same manner as the soil sample extracts. Again, this

derivatization removes the polarity associated with PCP

and provides improved chromatographic behavior. PCP

standards used for sample identification and quantitation

were taken through the same derivatization steps as the

samples to allow a direct comparison of concentration.

Detection Limits and Initial and Continuing

Calibrations

The detection limit for soil samples analyzed by

EPA Method 8270A was reported as 0.330 ppm. The

detection limit for soil samples analyzed by EPA Method

8151A was reported as 0.076 ppm. The reported

detection limit for water samples analyzed by EPA

Method 8270A was 50 ppb. The detection limit for

water samples analyzed by EPA Method 515.1 was

reported as 0.076 ppm. Method-required initial and

continuing calibration procedures were appropriately

conducted, and all method-required criteria for these

calibrations were met.

Sample Analysis

The confirmatory laboratories performed sample

analysis by first analyzing samples using EPA

Method 8270A. Based upon the screening results, the

samples were extracted with either the low concentration

method or the high concentration method found in EPA

Method 3550. Samples that did not provide a positive

response for PCP with EPA Method 8270A were

analyzed by one of two low-level detection methods:

EPA Method 8151A for soil samples and EPA Method

515.1 for water samples.

For EPA Method 8270A, compound identification

was required to meet two criteria: (1) the sample

component relative retention time was to fall within

f 0.06 relative retention time units of the standard

component, and (2) the mass spectrum of the sample

compound was to correspond with the standard

compound mass spectrum.

Soil and water samples found to contain no PCP

during the EPA Method 8270A analysis were analyzed

using EPA Methods 8151A and 515.1, respectively.

The presense of PCP was identified if a sample peak

eluted within the retention time window established

during the initial calibration.

Quality Control Procedures

Method blanks are used to monitor the presence of

laboratory-induced contamination. The EPA Region

7 Sample Management Office (SMO) provided blank soil

and blank water samples for use as method blank

samples during the analysis of demonstration samples.

An acceptable method blank must not provide a positive

response for the target compounds above the reported

detection limit. Method blank samples were stored,

extracted, and analyzed in exactly the same manner as

the demonstration samples. Results for all method blank

samples extracted and analyzed along with the

demonstration were found to be acceptable.

Internal standards were used to analyze

demonstration samples by EPA Method 8270A. Internal

standards were added to all standards, blanks, samples,

and QC samples prior to injection into the analytical

system. The internal standards were used to provide

response factors for each of the target compounds.

During the analysis of soil samples, seven samples

exhibited internal standard responses that were outside of

the QC limits of 50 to 150 percent recovery. All of the

affected samples provided internal standard responses

that were less than 50 percent. The soil samples affected

were samples 038, 060, 062, 068, 090, 091, and 095.

Three of these samples (090, 091, and 095) were found

to contain no detectable levels of PCP, and no corrective

action was taken. Instead, they were reanalyzed using

EPA Method 8151A. The remaining samples were

reanalyzed to verify that the internal standard response

was below 50 percent recovery. The reanalysis showed

that internal standard response was below 50 percent

recovery. No corrective action was taken by the

laboratory, which attributed the low recovery to matrix

effects inherent to the samples. In the Region

7 Laboratory QADE Branch review of the data, the

same conclusion was reached.

13
Surrogate standards were used to evaluate the

efficiency of the extraction and analysis processes and to

evaluate matrix affects. Surrogate standards used for

EPA Method 8270A include deuterated standards that

provide a different mass spectrum when compared to the

nondeuterated compound. All surrogate standard

recoveries for soil samples fell within the acceptance

ranges. The data review performed by Region 7 QADE

indicated that surrogate recoveries for some of the water

samples were outside of the acceptance ranges, but no

information indicated which samples or how many

samples fell outside surrogate recovery acceptance

ranges. Corrective action was not taken because the

acceptance ranges listed in the method are for advisory

purposes only. The surrogate standard used for EPA

Methods 8151A and 515.1 was 2,4 dichlorophenylacetic

acid (DCAA). The acceptance range for DCAA was

determined by the RECAP and Region 7 Laboratories

through a statistical analysis of 30 or more standard

surrogate recoveries. The mean and standard deviation

were then calculated, and the acceptance range was

determined by applying a f 3 standard deviations

around the mean. All samples analyzed by EPA

Methods 8151A and 515.1 provided surrogate recoveries

that fell within the laboratory-generated control limits.

Matrix spike samples consisted of aliquots of

original sample with a known concentration of the target

compounds added. The EPA Region 7 Laboratory SMO

designated the samples to be used as matrix spike

samples. Designated soil samples included samples

036, 048, 053, 073, 087, and 098, all analyzed using

EPA Method 8270A. and sample 089, analyzed using

EPA Method 8151A. Designated water samples

included samples 101 and 111, analyzed using EPA

Method 515.1, and sample 104, analyzed using EPA

Method 8270A. Soil matrix spike samples analyzed

using EPA Method 8270A were spiked with all the target

compounds reported by the method. Water sample

matrix spike samples analyzed using EPA Method

8270A were spiked with nine of the target compounds

reported by the method. Matrix spike samples analyzed

with EPA Methods 8151A and 515.1 were spiked with

only PCP. Soil matrix spike data for PCP is shown in

Table 5-1, and water matrix spike data for PCP is shown

in Table 5-2.

Soil sample matrix spike recoveries were greatly

influenced by the high concentrations of PCP present in

the original sample relative to the amount spiked. Only

sample 098 resulted in recoveries for both the matrix

spike and matrix spike duplicate sample that could be

considered acceptable. A clear evaluation of the effects

of matrix on PCP recovery is not possible due to the

high concentrations of PCP in the original sample and

the comparatively low levels of PCP added to the matrix

spike samples. The water sample matrix spike sample

analyzed by EPA Method 8270A resulted in high

recoveries. These recoveries are on the high end of the

QC acceptance criteria for PCP recoveries listed in EPA

Method 8270A (14 to 176 percent recovery). However,

the agreement between the matrix spike and matrix spike

duplicate was excellent as determined by the RPD of the

matrix spike recoveries. The water matrix spike samples

analyzed using EPA Method 515.1 were affected by the

concentration of PCP in the original sample. Although

the matrix spike recoveries for sample 101 were found

to be acceptable, the recoveries of PCP spiked into the

sample were affected by the much larger concentration

of PCP in the original sample. Sample 111 also was

affected by the concentration of PCP in the original

sample. Results of both the matrix spike sample and the

matrix spike duplicate sample were less than the result

for the original sample, which may indicate a

heterogeneity problem with the sample. The low levels

of PCP added to this sample were not enough to obtain

an accurate indication of matrix spike recovery.

The EPA Region 7 Laboratory SMO prepared blank

spike samples for water samples analyzed by EPA

Methods 8270A and 5 15.1. These samples were used to

evaluate the accuracy of the laboratory. Blank spike

samples were stored, extracted, and analyzed in the

same manner as all other samples. The percent

recoveries of the blank spike samples fell within the

14 to 176 percent QC acceptance criteria listed in EPA

Method 8270A and the 67.6 to 192.4 percent acceptance

criteria listed in EPA Method 515.1. The accuracy of

the analysis of water samples using EPA Methods 8270A

and 5 15.1 was found to be acceptable, based on the

blank spike sample results.

Data Reporting

The data report PRC received from the EPA Region

7 Laboratory included a standard EPA Region 7 Analysis

Request Report. Results were reported on a dry weight

basis, as required in the methods. PRC obtained data on

the loss-ondrying determination for each of the samples.

The loss-on-drying values were used to convert the

confirmatory laboratory data from a dry weight basis to

a wet weight basis.

Results were reported by the confirmatory

laboratory in micrograms per kilogram (pg/kg) for soil

samples and micrograms per liter (pg/L) for water

samples. Soil sample results were converted to

milligrams per kilogram (mg/kg) so they could be

compared to the results from the technology, which

reported results for soil samples in milligrams per

kilogram. The technology’s results for water samples

14
TABLE 5-1. SOIL MATRIX SPIKE SAMPLE RESULTS FOR EPA METHODS 8270A AND 8151A

Amount Found Amount Added to Amount Amount Found Duplicate Relative

in Original Matrix Spike and Found in Percent in Matrix Spike Percent Percent

Sample Sample Duplicate Matrix Spike Recovery Duplicate Recovery Difference

No. (ppm) (ppm) (ppm) (%) @pm) (%) %

036 40.0 1.90 66.0 1,370 51 .o 579 81

048 30,000 46.0 22,000 0 24,000 0 0

053 2.30 1.50 12.0 647 5.20 193 108

073 86.0 11.0 130 400 93.0 64 145

087 46.0 1.40 57.0 786 64.0 1,285 48

089 0.247 0.098 0.315 69 0.241 0 200

098 0.70 0.41 0.82 29 0.98 68 80

TABLE 5-2. WATER MATRIX SPIKE SAMPLE RESULTS FOR EPA METHODS 8270A AND 515.1

Amount Found Amount Added to Amount Amount Found Duplicate Relative

in Original Matrix Spike and Found in Percent in Matrix Spike Percent Percent

Sample Sample Duplicate Matrix Spike Recovery Duplicate Recovery Difference

No. (ppb) (ppb) (ppb) (%) (ppb) (%) (%)

101 4.14 0.446 4.46 72 4.24 22 106

104 50.0 u . 200 348 174 353 177 2

111 1.85 0.398 1.55 0 1.64 0 0

were reported in micrograms per liter, so no conversion

of the confirmatory laboratory data was needed.

Data Quality Assessment

Accuracy refers to the difference between the

sample result and the true concentration of analyte in the

sample. Bias, a measure of the departure from complete

accuracy, can be caused by such processes as loss of

analyte during the extraction process, interferences, and

systematic contamination or carryover of an analyte from

one sample to the next. Accuracy for the confirmatory

laboratory was assessed by using PE samples. Four of

the PE samples used for this demonstration were

purchased from Environmental Resource Associates

(ERA). Two of these PE samples were soil and two

were water. These samples contained a known quantity

of PCP. ERA supplied data sheets for each PE sample

that included the true concentration and an acceptance

range for the sample. The acceptance range was based

on the 95 percent confidence interval taken from data

generated by ERA and EPA interlaboratory studies. A

third water PE sample was prepared by the PRC lead

chemist to widen the range covered by the PE samples.

These samples were extracted and analyzed in the

same manner as the other water and soil samples. The

confirmatory laboratory did not know which samples

were PE samples or the certified values and acceptance

ranges. The true value concentration of soil PE sample

099 (the low-level sample) was 7.44 ppm, with an

acceptance range of 1.1 to 13 ppm. The result reported

by the confirmatory laboratory for this sample was

4.02 ppm, which was within the acceptance range. The

percent recovery of this sample by the confirmatory

laboratory was 54 percent. The true concentration of soil

PE sample 100 (the high-level sample) was 101 ppm

with an acceptance range of 15 to 177 ppm. The result

reported for this sample by the confiiatory laboratory

was 52.4 ppm, which was within the acceptance range.

The percent recovery of this sample by the confirmatory

laboratory was 52 percent.

The true value concentration of water PE sample

106 (the low-level sample) was 68.4 ppb with an

acceptance range of 10 to 120 ppb. The result reported

by the confirmatory laboratory for this sample was

10.3 ppb, which was within the acceptance range. The

percent recovery of this sample by the confirmatory

laboratory was 15 percent. The true concentration of

15
water PE sample 107 (the high-level sample) was

2,510 ppb with an acceptance range of 377 to 4,420 ppb.

The result reported for this sample by the confirmatory

laboratory was 2,050 ppb of PCP, which was within the

acceptance range. The percent recovery of this sample

by the confirmatory laboratory was 82 percent. The true

value concentration of water PE sample 113 (the PE

sample prepared by PRC) was 7.50 ppb. No acceptance

range was statistically determined for this PE sample.

Instead, PRC established a 30 to 170 percent window of

acceptable values around the true value result of the

low-level PE sample. This window is consistent with

both the acceptance ranges of the PE samples prepared

by ERA and the QC Acceptance Criteria for PCP

recovery stated in EPA Method 8270A. The

confirmatory laboratory result for this PE sample was

within the acceptance range. Based on results for all of

the PE samples, the accuracy of the confirmatory

laboratory was acceptable.

Precision refers to the degree of mutual agreement

among individual measurements and provides an estimate

of random error. Precision for results obtained by

confirmatory laboratory was determined by using field

duplicate samples. Normally, laboratory duplicates are

used to determine precision. However, no laboratory

duplicates were analyzed by the confirmatory

laboratories. Field duplicates are two samples collected

together but delivered to the laboratory with separate

sample numbers. Typically, field duplicate samples are

used to measure both sampling and analysis error. PRC

established control limits for field duplicate RPDs.

These control limits are similar to those used to

determine matrix spike recovery acceptance control

limits. To establish the control limits, all sample pairs

that did not produce two positive results were removed

from the data set. Then the RPD for each pair was

calculated, and the mean RPD and standard deviation

were determined. The lower control limit was set at

zero because this would mean that the results from a

duplicate and its sample matched perfectly. The upper

control limit was set by multiplying the standard

deviation by two and adding it to the mean RPD. The

RPD of each sample pair was then compared to these

control limits. Each sample pair RPD was expected to

fall within the control limits.

Fourteen soil field duplicate samples were collected

and analyzed by the confiiatory laboratory during this

demonstration. Field duplicate samples represented

17 percent of all soil samples collected and analyzed.

The original results ranged from 0.10 to 26,100 ppm.

Duplicate sample results ranged from 0.09 to

30,260 ppm. RPD values for the soil field duplicate

pairs ranged from 1 to 168 RPD. The mean RPD value

of the soil field duplicate pairs was 33 percent, with a

standard deviation of 47 percent. For the soil field

duplicate pairs the control limits were found to be 0 to

128 RPD. Thirteen of the fourteen, or 93 percent, of

the field duplicate sample pairs fell within this range.

Six water field duplicate samples were collected and

analyzed by the confirmatory laboratory during this

demonstration. Field duplicate samples represented

32 percent of all water samples collected and analyzed.

The original results ranged from 0.175 to 1,810 ppb.

The field duplicate sample results ranged from 0.63 to

2,020 ppb. RPD values for the water field duplicate

pairs ranged from 0 to 113 RPD. The mean RPD value

of the water field duplicate pairs was 30 percent with a

standard deviation of 41 percent. For the water field

duplicate pairs, the control limits were found to be 0 to

112 RPD. Five of the six, or 83 percent of the field

duplicate sample pairs, fell within this range.

Completeness refers to the amount of data collected

from a measurement process compared to the amount

expected (Stanley and Vemer 1983). For this

demonstration, completeness referred to the proportion

of valid, acceptable data generated by the confirmatory

laboratory. The completeness objective for this project

was 95 percent. This demonstration resulted in the

analysis of 98 soil samples, 14 soil sample duplicates,

2 soil PE samples, 10 water samples, 6 water sample

duplicates, and 3 water PE samples. Results were

obtained for all of these samples. Completeness for the

confirmatory laboratory was 100 percent.

Confirmatory Laboratory Costs

and Turnaround Times

The cost for performing PCP analysis by EPAapproved analytical methods varies from laboratory to

laboratory. The cost of analysis depends on the number

of samples submitted for analysis, the matrix, and the

level of QC performed. The following costs are given

as general guidelines. EPA Method 8270A analysis

costs range from $250 to $400 per sample. EPA

Method 8151A analysis costs range from $150 to

$250 per sample. EPA Method 515.1 analysis costs

range from $125 to $200 per sample. Turnaround times

for samples submitted for analysis with EPA-approved

analytical methods range from 14 to 30 days. The

turnaround time also depends on the number of samples

submitted for analysis, the matrix, and the level of QC

performed. Faster turnaround times may be available

for an additional cost.

16
Section 6

EPA Region 7 Supetfund Program: FASP PCP Method

The FASP PCP Method was developed by the EPA

Region 7 Superfund Branch under the Field Investigation

Team Contract for use at Superfund sites. It was

designed to provide quick, accurate results to determine

PCP concentrations in soil and water samples. This

method can also detect and quantify other phenols. PCP

concentrations are reported in either ppb or ppm for soils

and in ppb for water. The method uses a GC equipped

with a megabore capillary column and an FID and ECD

to identify and quantify PCP. Gas chromatography is an

EPA-approved method for determining PCP

concentrations in soil, water, and waste samples. The

FASP PCP Method is an abbreviated, modified version

of the EPA-approved methods.

Operational Characteristics

The instruments and equipment required for the

FASP PCP Method are not very portable because of

their large sizes. The equipment used includes the

following: (1) a Shimadzu GC-14A equipped with an

FID and ECD, (2) a Shiiadzu AOC-14 autosampler,

(3) a Shimadzu CR-4AX data system, and (4) a

COMPAQ SLT/286 laptop computer. The GC weighs

100 pounds with its autosampler attached and measures

18 inches by 24 inches by 12 inches. The data system

weighs another 25 pounds and is the same size. In

addition to this equipment, the following laboratory

equipment is necessary: (1) Nitrogen carrier gas; (2) a

DB-5, 30-meter, 0.53~millimeter inside diameter, or

equivalent capillary column; (3) l0-, 50-, and

l00-microliter micropipettes; (4) l0-, 25-, 50-, l00-,

and 5OO-microliter micro syringes; (5) l-, 5-, and

lo-milliliter glass volumetric pipets; (6) 2- to

lo-milliliter repipetter with Teflon liners; (7) l0-, 50-,

and l00-milliliter glass volumetric flasks with groundglass stoppers; (8) 2-milliliter glass vials with Teflonlined cap for storing stock standards; (9) 2-milliliter

autosampler vials with Teflon-lined cap; (10) a bubble

flow meter used to check GCcolumn flows; (11) 4-fluidounce standard bottles with Teflon-lined screw cap for

calibration standard storage; (12) 5.75- and 9-inch

disposable glass Pasteur pipets; (13) 40-milliliter

extraction vials with Teflon-lined screw caps; (14)

13- by l00-milliieter test tubes with Teflon-lined screw

caps; (15) stainless-steel spatulas; (16) top loader balance

with O.Ol-gram accuracy; (17) a high speed vortex

mixer; (18) a digital timer; (19) large and small pipet

bulbs to fit volumetric and Pasteur pipets; (20) labels;

(21) permanent markers; (22) paper towels; (23) surgical

gloves; (24) safety glasses; (25) laboratory.coats or other

protective clothing; (26) refrigerator; (27) a fume hood;

and (28) floppy disks. The following reagents are

needed for sample extraction and analysis using the

FASP method: (1) pesticide-grade or equivalentmethyltert-butyl ether; (2) granular, pesticide-grade sodium

sulfate; (3) concentrated Fisher Scientific or equivalent

sulfuric acid; (4) powdered sodium bicarbonate for

neutralizing acid spills; (5) Fisher Scientific or

equivalent potassium hydroxide; and (6) 98 percent

purity or greater phenol standards.

The FASP PCP Method must be performed indoors

in a temperature-controlled environment to protect the

analytical equipment from moisture and temperature

extremes. Most of the other equipment and reagents

also require this protection. During this demonstration,

the FASP method was performed in an air conditioned

trailer.

Another logistical requirement of the technology is

electricity. Electricity was provided to the trailer

through a temporary power pole. An alternative source

of electricity may be used, such as a gasoline-powered

generator. The use of a generator allows the analytical

equipment to be operated even at the most remotely

located sites. Electricity is also required for various

support equipment. The method requires using a fume

hood to evacuate solvent and acid fumes from the work

area. The fume hood may be vented directly outdoors or

internally through a charcoal filter that traps harmful

fumes. A refrigerator is needed to store the PCP

standards. The refrigerator used for this demonstration

was 3.5 cubic feet in size. Carrier, make-up, and FID

flame gases are required for gas chromatography.

17
The work space required for the analytical

equipment is 12 square feet. Another 8 square feet is

needed to perform sample extraction and preparation

steps. Storage space for equipment, reagents, and

glassware also is needed. A solvent storage cabinet for

flammable solvents is recommended for safely storing

solvents. Soil and water samples should be cooled until

sample analysis. They also should not be stored with

PCP standards,

The operator chosen to analyze samples for this

demonstration was Mr. Ramarao Rayavarapu, an

employee of PRC. Mr. Rayavarapu earned a B.S.

degree in civil engineering in 1983 from Andhra

University in India. Mr. Rayavarapu also earned an

M. S. in environmental engineering in 1990 from the

University of Missouri. While at PRC, Mr. Rayavarapu

has conducted RCRA facility inspections, compliance

evaluation inspections, and field sampling and oversight

work. His experience also includes using several types

of wet chemical analytical methods. While attending the

University of Missouri, Mr. Rayavarapu worked as a

laboratory research assistant for 2 years, analyzing liquid

and soil samples using a GC and a high performance

liquid chromatograph. Mr. Rayavarapu was also the

operator for a similar demonstration of the FASP

Polychlorinated Biphenyl Method, also a GC method.

Mr. Rayavarapu was trained for this demonstration by

the lead chemist. Training included 1 week of hands-on

work using and maintaining the GC, as well as training

in specific procedures required for the extraction,

preparation, and analysis of samples.

The FASP PCP Method involves two steps: sample

preparation and sample analysis. Soil sample

preparation involved weighing a known amount of soil

into an extraction vial. A measured portion of sodium

sulfate was added to and mixed with the soil in the

extraction vial, A measured amount of methyl-tert-butyl

ether was added to the extraction vial. The vial was then

mixed with a vortex shaker for 2 minutes. The organic

sample extract was now ready to be analyzed for PCP.

In soil samples suspected of containing petroleum

hydrocarbons, an acid-base cleanup was used to separate

the petroleum hydrocarbons from PCP. The cleanup

was performed by transferring an aliquot of the organic

sample extract to a test tube. A small amount of a

37 percent solution of potassium hydroxide was added to

the test tube and mixed with the organic sample extract

for 1 minute. PCP in the organic sample extract was

converted to a potassium salt that is soluble in the

aqueous solution. After this basic wash, the organic

solvent was removed from the test tube and the aqueous

phase, containing the PCP-potassium salts, was washed

twice with organic solvent. A small amount of a

1: 1 solution of sulfuric acid was carefully added to the

test tube. The pH of the solution was lowered to less

than 2 with the sulfuric acid solution. This step

converted the PCP-potassium salts back to PCP, which

was soluble in the organic solvent. The acidic aqueous

extract was extracted three times with methyl-tert-butyl

ether. The organic sample extract was adjusted to a

known concentration and was ready for analysis.

Water extraction was performed by measuring a

volume of water into an extraction vial. The pH of the

sample was adjusted to greater than 10 with a 37 percent

solution of potassium hydroxide. The basic water

sample was extracted three times with methyl-tert-butyl

ether, and the organic solvent containing petroleum

hydrocarbons and other interferences was discarded.

The basic water sample’s pH was first adjusted to less

than 2 with a 1: 1 solution of sulfuric acid and then

extracted three times with methyl-tert-butyl ether. This

organic sample extract contained PCP. The organic

sample extract was concentrated to a known volume and

was ready for analysis.

Sample preparation, as noted by the operator, was

exhaustive and time-consuming and required an operator

experienced in laboratory procedures. The sample

preparation became more complicated when the sample

had to undergo additional cleanup steps to remove matrix

interferences. Sample analysis required that the operator

be familiar with GC techniques. A minimum of

6 months experience in using a GC and a minimum of

1 month experience in analyzing PCP is recommended

to effectively use the FASP PCP Method. The operator

noted that operation of the GC was easier for those with

prior GC experience and with a basic knowledge of

analytical chemistry.

The ruggedness of field portable GC equipment has

been demonstrated through years of use. Maintenance

of the GC and other equipment is essential to ensure

quick and accurate PCP results in the laboratory or field.

Because of the rigors of working in the field, the

equipment should be on site and operating correctly at

least 1 to 2 days before beginning sample collection.

This lead time allows any travel-induced damage to be

corrected prior to sample collection. Routine

maintenance includes gas bottle changes, septum

changes, and column conditioning. Nonroutine

maintenance may include column changes or electronic

board replacement. Agreements with equipment

suppliers for overnight delivery of replacement parts and

in-the-field servicing by equipment service

representatives may be required to provide all needed

maintenance.

18
Instrument reliability was evaluated by monitoring

the equipment’s ability to maintain its calibration. An

initial calibration (ICAL) was performed at the start of

the demonstration. The instrument calibration was

monitored daily through continuing calibrations (CCAL)

using the mid-level concentration of the PCP standards.

During the CCAL the peak response obtained is

compared to the average peak response obtained during

the ICAL. These responses are compared by determining the RPD between responses. An RPD value of less

than or equal to 25 percent is required to continue sample analysis. If the RPD is higher than 25 percent,

another ICAL must be performed. Over the 13 days of

the demonstration, three ICALs and 13 CCALs were

performed. Out of three ICALs, two were performed

for soil analysis, and one was performed for water

analysis. Eleven CCALs were performed for the

analysis of soil samples, and two CCALs were

performed for the analysis of water samples. CCALs

were performed on each day of sample analysis. On the

eleventh day of the demonstration, the CCAL for soil

analysis was out of control as a result of analyzing soil

samples from the Winona Post site, which contained

large amounts of petroleum hydrocarbons. Due to the

heavy contamination with petroleum hydrocarbons in the

samples and extracts, the septa and the glass liner in the

injection port became contaminated, and the column

became saturated with hydrocarbons. After determining

the problem, the septa and the glass liner were replaced,

and the column was conditioned at elevated oven

temperature to desorb the petroleum hydrocarbons.

Another ICAL was performed after column

conditioning; although the relative standard deviation

(RSD) for PCP was 33 percent in the second ICAL, this

RSD was deemed acceptable, and the average calibration

factor was used for sample quantitation. The two

CCALS performed after the second ICAL were within

the new control limits.

A new ICAL was performed for the analysis of

water samples. The CCAL performed for water analysis

was within control limits; however, the CCAL

performed at the end of the analysis did not fall within

control limits. The retention time of the specific PCP

peak also was monitored through the CCALs. The

retention time of this peak shifted throughout the

demonstration. To maintain an accurate retention time

window for this peak, the window was adjusted.

Another reliability factor evaluated was the

consistency of the data system to properly draw a

baseline for standards and samples. Baselines were

drawn consistently for samples from the former Koppers

site. However, samples from Winona Post site were

highly contaminated with petroleum hydrocarbons,

causing the baseline to drift.

Operators of the method need to be aware of

hazards due to the chemicals used, particularly methyl

tert-butyl ether (MtBE), sodium sulfate, and sulfuric

acid. MtBE is used to extract PCP from samples and to

dilute standard solutions. MtBE is an explosive and

flammable solvent and should be handled only under a

flame hood. Care should be taken when using MtBE to

avoid inhalation and direct contact with the liquid and

fumes. Ignition sources such as open flames should also

be avoided, and a dry chemical fire extinguisher should

be available in case of fire. Sodium sulfate is used to

chemically dewater soil samples. Sodium sulfate is a

fine granular powder and can be a skin and eye irritant.

Protective clothing and safety glasses should be worn

when using sodium sulfate. Sulfuric acid is used to

reduce the pH of the samples. Sulfuric acid can cause

chemical burns when spilled on the skin. Chemicalresistant clothing, gloves, and safety glasses are required

for protection from sulfuric acid. An adequate source of

water should be available in case the acid comes in

contact with the skin. Eyewash solutions also should be

available.

This method uses various types of glassware to

analyze samples. Using glass always presents a

possibility of breakage and injury. Glassware should be

handled in a safe, careful manner. Broken glassware

should not be used and should be disposed of in a safe

manner. The ECD contains Nickel-63, a radioactive

material. The amount of radioactive material in the

ECD is minimal, and it is stored in a sealed container.

Nevertheless, the container must be checked for possible

leakage twice a year. Leakage of the radioactive

material above federally regulated limits: requires

immediate attention. The FID uses hydrogen gas, which

is explosive and stored under high pressure. Care must

be taken to secure the hydrogen gas cylinders to avoid

cylinder damage.

The total cost of the analytical equipment used

during this demonstration was $23,214. This cost

includes the GC equipped with an ECD and FID, the

autosampler, the data system, all equipment required to

set up the GC, and installation. Costs per component

are: $13,149 for the GC; $3,865 for the autosampler;

and $6,200 for the data system. Analytical equipment

can also be rented from a number of companies. A

general survey of current market costs for comparable

equipment indicates ranges from $1,500 to $2,500 per

month. Most rental companies require a minimum

rental time period, but this may be negotiable. Rental

rates usually include delivery and setup but do not

include GC columns. Many companies also offer rentto-own or lease-to-own options for analytical equipment.

The cost of reagents and equipment needed to perform

the extraction, preparation, and analysis of soil samples

19
using the FASP PCP Method is estimated to be $5,000.

This demonstration required about 370 sample

extractions and injections; these 370 sample extractions

include initial sample analysis, subsequent sample

dilutions, and QA/QC samples. At $5,000, this equates

to about $13.50 per sample.

Operator costs will vary depending on the technical

level of the operator. As discussed earlier, a minimum

of 6 months experience in using a GC and a minimum of

1 month experience in analyzing samples for PCP is

recommended. Other costs associated with this method

include electricity, use of a refrigerator, use of an indoor

work area, and disposal costs. This demonstration

generated a 55-gallon drum of laboratory waste. The

appropriate way to dispose of this waste is through an

approved incinerator facility, with an estimated cost of

$2,080 per drum of waste.

Performance Factors

The sensitivity of the FASP PCP Method depends

on the detection limits of the FID and ECD. The

sensitivity of the detectors, especially the ECD, is such

that it always gives some background response; this

response is called “noise level.” For most methods that

use gas chromatography, the detection limit is defined as

the minimum amount of a compound that will give a

response greater than three times the noise level of the

instrument. The response of the low PCP standard was

well above three times the noise level for the instrument.

The FASP PCP Method’s detection limit depends on

the type of detector used with the instrument. The FID

has a lower sensitivity than the ECD and hence, the

detection limits for the FID are higher than those for the

ECD. The detection limit for soil samples from the

former Koppers site was 0.8 ppm; for soil samples from

the Winona Post site was 1.6 ppm. The detection limit

for water samples, if analyzed using the FID was

0.2 ppm. The ECD was used to analyze water samples

when the FID analysis produced a nondetect. The

detection limit for the ECD was 0.5 ppb PCP. Detection

limits were based on the low PCP calibration standard

used, and the dilution or concentration factors produced

during sample extraction and preparation.

The majority of the soil samples were silty clay to

silty sand. Sodium sulfate was added to all soil samples

to bind the moisture present. Some of the samples from

the Winona Post site contained wood chips. The wood

chips were not segregated before sample extraction. The

operator noted that these matrix characteristics did not

pose a physical problem with the extraction. Samples

from the Winona Post site showed large interferences

from petroleum hydrocarbons. The FASP PCP Method

includes a cleanup step to eliminate contamination from

petroleum hydrocarbons. However, even after extensive

cleanup of the sample extract, the interferences from

petroleum hydrocarbons were not totally eliminated.

The interference from these petroleum hydrocarbons

made the PCP quantitation very difficult. In addition, as

evidenced by the matrix spike recoveries, PCP appeared

to have been lost during these cleanup steps.

Some water samples from the Winona Post site

contained an oil sheen on ‘top of the water layer. The

PCP carrier used at this site was diesel fuel. To reduce

any matrix effects from free-phase petroleum, the pH of

the water samples was increased to greater than 12. The

water sample was then washed one time with MtBE to

remove petroleum hydrocarbons. The MtBE wash was

discarded. The water sample was then acidified to a pH

less than 2.0. The acidified water sample was extracted

with MtBE, and the MtBE extract was analyzed. This

cleanup procedure worked well except for two samples.

Samples 102 and 103, and their duplicates, showed large

interferences from petroleum hydrocarbons even after

the cleanup steps for petroleum hydrocarbons. These

interferences may be due to inadequate washing of the

water sample with MtBE prior to acidification and

extraction. Additional cleanup may have eliminated this

interference.

Another sample matrix effect was the high levels of

PCP found in many samples. If the initial extract was

analyzed and it produced a detect outside the method

calibration range, the extract was diluted. Of 134 soil

samples, 34 samples were diluted more than 10 fold.

Any time dilution is attempted, measurement errors may

be introduced.

The FASP PCP Method can use an autosampler to

increase analysis efficiency. The autosampler allows

samples to be analyzed 24 hours a day. Once loaded

with samples, the autosampler can be operated without

the presence of an operator. The FASP PCP Method’s

operator observed that up to 20 samples could be

analyzed in each 24-hour period. More than

181 samples were weighed, extracted, cleaned,

concentrated, and analyzed during the 13&y

demonstration period, for an average of 14 samples per

day. The sample throughput was reduced by the timeconsuming cleanup process required for the samples

from the Winona Post site.

The linear range of the analysis for PCP was

established during the ICAL by analyzing the three

different calibrators. The three concentrations used

during the ICAL ranged from 4 to 400 ppb for the FID.

These concentrations correspond to a PCP calibration

range of 0.8 to 80 ppm in the soil samples. For water

20
samples, the calibration range for the FID was 0.2 to

20 ppm. The PCP calibration range for the ECD was

1 to 50 ppb. Any soil sample that exceeded a PCP

concentration of 80 ppm, and any water sample that

exceeded 20 ppb of PCP was diluted to bring the

response within the calibration range. Forty-eight

samples collected during this demonstration required

dilution to obtain PCP peaks within the linear range of

the calibration. Twenty-three of the samples required a

1: 10 dilution; 12 required a 1: 100 dilution; 11 required

a 1: 1,000 dilution; and two required a 1: 10,000 dilution.

The linear range for the FASP PCP Method is

comparable to the linear ranges used in formal

laboratory analysis.

Drift is a measurement of an instrument’s variability

in quantitating a known amount of a standard. The drift

associated with the FASP PCP Method was evaluated

through daily CCALs. The responses exhibited during

the CCALs were compared to those exhibited during the

ICAL. During sample analysis, the retention time of the

PCP peak was observed to be shifting. The shifts were

small, but they eventually exceeded the acceptable

retention time ranges calculated during the ICAL. The

corrective action for this drift involved establishing new

retention time ranges. The retention times of the PCP

peak for the CCALs were used to establish the new

ranges.

Specificity

Sample interferences may arise due to the presence

of soil organic matter, cocontaminants such as

phthalates, other chlorophenols, and PCP carrier

solvents. Interferences due to PCP carrier solvents are

especially important because they have a strong potential

to give false positive results.

Phthalates , which are common laboratory

contaminants, are found in many of the plastic materials

that can be used in the extraction process. Organic

solvents used to extract PCP will also extract phthalates

from the containers. To prevent such extraction of

phthalates along with PCP, use of plastic materials in

any stage of sample storage, extraction, or analysis is

discouraged. Interferences may also be introduced by

other means, such as carrier gas contamination and

carryover from highly contaminated samples. Potential

for carrier gas contamination is reduced by using ultrahigh purity grade gases. The use of carrier gas filters

also helps eliminate these problems. The extraction and

analysis of highly contaminated samples followed by the

extraction and analysis of less contaminated samples

frequently results in sample carryover contamination.

During this demonstration, sample carryover

contamination was reduced by using disposable

glassware. Glassware was replaced after the extraction

and analysis of each sample. To reduce contamination

of the GC and ECD, only those extracts that the FID

indicated contained no PCP or too little to be detected

were analyzed on the ECD. The use of solvent washes

added to the GC after the analysis of highly

contaminated samples also reduced sample carryover

contamination.

Sample matrix interferences are more difficult to

eliminate. Common manmade sample matrix

interferants include phthalates, halogenated solvents,

halogenated pesticides, polar halogenated compounds,

and chlorinated paraffins. In addition, natural organics

present in soil may affect PCP extraction. Research has

shown that PCP not only adsorbs to soil organic matter

but also forms complexes with humic material. The

FASP PCP Method is based on the belief that adding

acid to bring down the pH to less than or equal to

2.0 will free PCP from such complexes. A concern

raised by EPA Region 7 was that PCP and

pentachlorophenate elute at different times, resulting in

incorrect identification and quantitation. Both of these

compounds can be present at wood treatment facilities.

Acidification of the soil sample should convert all of the

pentachlorophenate ions into PCP.

Cross-reactivity from other phenols was not of

concern, because gas chromatography can identify

specific phenols. However, one problem associated with

high concentrations of other phenols is that such a

sample would require dilution, which would raise the

detection limits for PCP. None of the samples analyzed

during this demonstration contained large amounts of

other phenols.

The major problem associated with PCP quantitation

during this demonstration was interference caused by the

carrier solvent used for PCP application. At the former

Koppers site, PCP was applied to the wood by dissolving

it into isopropyl ether and butane. At the Winona Post

site, diesel fuel was the carrier solvent for PCP

application. The samples from the former Koppers site

did not show any carrier effect. PRC believes this was

due in part to the high volatility of isopropyl ether and

butane. Also, because these carriers elute well before

PCP, they do not cause interference. However, sample

quantitation was affected by the presence of petroleum

hydrocarbons in the Winona Post samples, because PCP

elutes within the petroleum hydrocarbon pattern.

Although the FASP method includes cleanup steps to

eliminate these interferences, interferences were not

removed completely.

21
To evaluate the method for cross-reactivity, the lead

chemist prepared 21 spiked samples. SS-01 through SS17 were spiked soil samples, and SS-18 through SS-21

were spiked water samples. Samples SS-01 to SS-04

were spiked with 2,4,6-trichlorophenol; SS-05 to SS-08

were spiked with diesel fuel; SS-10 to SS-13 were spiked

with 2,4-dichlorophenol; SS-14 to SS-17 were spiked

with 2,3,4,6-tetrachlorophenol; and SS-09 was a blank

sample. Water samples SS-18 to SS-21 were spiked

with PCP and diesel fuel. All chlorophenols in soil

samples were spiked at the 5 ppm level; the diesel fuel

was spiked at a 50 ppm level in soil samples; and the

PCP and diesel fuel were spiked in water samples at

50 ppb and 125,000 ppb, respectively.

The FASP PCP Method operator did not identify

PCP in any of the samples spiked with chlorophenols.

Samples spiked with diesel fuel did give false positive

results for PCP. The mean PCP concentration in these

samples was 2.85 ppm, which indicates that about six

percent of the diesel fuel chromatograph was identified

as PCP. The mean percent recovery from the samples

spiked with 2,4,6-trichlorophenol was 75 percent.

Similarly, the mean percent recoveries for 2,4dichlorophenol and 2,3,4,6-tetrachlorophenol were 76.8 and

68.8, respectively. This data shows that the method is

capable of separating the phenols. The resultant

recoveries are within control limits. The percent PCP

recoveries in water samples ranged from 220 to

288 percent. The mean recovery of PCP was

245 percent, and the standard deviation was 30 percent.

The diesel fuel interference is not thought to be the

source of these high recoveries. These samples were

analyzed by ECD, which is specific to halogenated

compounds and should not detect petroleum hydrocarbons. Currently PRC has not identified the cause of

these elevated recoveries.

lntramethod Assessment

Intramethod measures of the technology’s

performance included its results on reagent blanks, the

completeness of its results, its intramethod accuracy, and

its intramethod precision. Reagent blank samples were

prepared by taking reagents through all extraction,

cleanup, and injection steps of the analysis. Reagent

blanks were prepared with each batch of 20 samples.

Ten reagent blanks were prepared and analyzed during

the demonstration: nine reagent blanks for soil analysis

and one reagent blank for water analysis. No PCP was

detected in any of the blanks above method detection

limits. These results indicate that no laboratory-induced

PCP contamination was present.

None of the FASP PCP Method data was

invalidated, and results were reported for every sample

analyzed. Therefore, the completeness was 100 percent

for soil samples and 100 percent for water samples.

The surrogate standard used for the FASP PCP

Method is 2,4,6-tribromophenol, which like PCP, is a

polar compound. The partitioning of this compound

during the extraction and cleanup process is similar to

the partitioning of PCP. The surrogate was added to all

blanks, samples, their duplicates, matrix spikes, and

matrix spike duplicates at a level of 2 ppm. Surrogate

recoveries were calculated only from the concentrated

sample extract. Whenever the sample extract was not

concentrated or the sample extract was diluted, no

surrogate recoveries were reported. These samples were

coded DL to indicate that the sample was diluted.

In all, 76 surrogate recovery values were obtained

with an average surrogate recovery of 65.8 percent. The

standard deviation of the surrogate recovery was

29.2 percent. Control limits for surrogate standards

were defined as f 3 standard deviations from the mean.

For the surrogate standards analyzed during this

demonstration, the calculated control limits were from

0 to 153 percent recovery. Two of the 76 surrogate

standard recoveries were outside of these control limits.

No corrective action was taken. These control limits are

advisory limits only. Water samples were also spiked

with 2,4,6-tribromophenol, at a concentration of 1 ppb.

The surrogate recoveries were calculated from data

generated by the FID. The surrogate recoveries from

those samples were diluted and are flagged as DL.

Surrogate recoveries were not calculated from the

ECD data because the surrogate showed a very high

response on the ECD. This response exceeded the

calibration limits of the instrument. In all, 15 surrogate

recovery values were obtained. The average surrogate

recovery was 30.8 percent and the standard deviation

was 13.1. The surrogate recoveries ranged from 0 to

70 percent. Surrogate recoveries of all samples fell

within the established control limits.

Intramethod accuracy was assessed for the FASP

PCP Method by using PE samples and matrix spike and

matrix spike duplicate samples. Five PE samples were

analyzed during the demonstration, two for the soil

matrix and three for the water matrix. Four of them

were purchased from ERA. Water PE sample 113 was

prepared by PRC. These samples were extracted and

analyzed in the same way as the other soil and water

samples. The operator did not know that the samples

were PE samples, nor did the operator know the true

concentrations and acceptance ranges.

The true concentration of soil PE sample 100 (the

high-level sample) was 101 ppm, with an acceptance

22
range of 15 to 177 ppm. The result reported for this

sample by the FASP PCP Method was 94.2 ppm, which

was within the acceptance range. The true value

concentration of soil PE sample 099 (the low-level

sample) was 7.44 ppm, with an acceptance range of

1.1 to 13 ppm. The result reported by the FASP PCP

Method was 4.44 ppm, which also was within the

acceptance range. The true concentration of water PE

sample 107 (the high-level sample) was 2,510 ppb, with

an acceptance range of 377 to 4,420 ppb. The result

reported for this sample by the FASP PCP Method was

1,712 ppb of PCP, which was within the acceptance

range. The true value concentration of water PE sample

106 (the low-level sample) was 68.4 ppb; with an

acceptance range of 10 to 120 ppb. The result reported

by the FASP PCP Method was 78.2 ppb, which was

within the acceptance range. The true value

concentration of water PE sample 113 (the sample

prepared by PRC) was 7.5 ppb, with an acceptance

range of 3.75 to 11.3 ppb. The result reported by the

FASP PCP Method for this sample was 42 ppb, which

was outside the acceptance range. Accuracy of the

samples analyzed by the FASP PCP Method was found

to be 100 percent for soil analysis and 66 percent for

water analysis based on the results of the PE samples.

However, the accuracy for the water analysis could not

have been improved unless all three sample results fell

within the PE sample accuracy ranges.

Matrix spike samples were used to evaluate the

extraction and analysis efficiency of the technology.

They also were used to determine accuracy. Matrix

spike samples were prepared by adding a known quantity

of PCP to a sample. Matrix spike samples were spiked

with PCP at a level of 10.0 ppm in soil samples and

50 ppb in water samples. The spiked sample was also

duplicated to produce a matrix spike duplicate sample.

Recovery results of the matrix spike samples and their

duplicates are listed in Tables 6-l and 6-2. Six matrix

spike samples and matrix spike duplicate sample pairs

were extracted and analyzed using the FASP PCP

Method for soil analysis. The recoveries for these

samples ranged from 0 to 89 percent. Matrix spike and

matrix spike duplicate results for sample 058D indicated

0 percent recoveries. The original sample contained

about 3.0 ppm of PCP, which is not high enough to

affect any spike recoveries. These results were excluded

as outliers, and the remaining matrix spike and matrix

spike duplicate pair results were used to evaluate the

technology. The average recovery for these samples was

52 percent. The standard deviation was 39 percent.

Based on this data, control limits for matrix spike

recovery samples ranged from 0 to 130 percent

recovery. All matrix spike samples analyzed fell within

these control limits. One matrix spike and one matrix

spike duplicate sample were analyzed during the analysis

of water samples. These samples were spiked with PCP

at a level of 50 ppb. The sample had an original PCP

concentration of 45.5 ppb. The spike recoveries from

these two samples were 193 and 173 percent. No

statistical evaluation of the data was performed due to

the small size of the data set. The mean recovery

calculated from these two sample recoveries is

183 percent.

For this demonstration, three types of intramethod

precision data was generated: data from laboratory

duplicate samples, data from field duplicate samples, and

data from matrix spike duplicate samples. Laboratory

duplicate samples consist of two analyses performed on

a single sample delivered to a laboratory. Six laboratory

duplicate soil samples and one laboratory duplicate water

sample were analyzed using the FASP PCP Method.

Only samples with detectable levels of PCP were used

for laboratory duplicate analysis. The initial analyses of

the duplicate soil samples ranged from 107 to

9,777 ppm, and the single water sample result was

5,236 ppb. When the analysis was duplicated, the

results ranged from 107 to 4,323 ppm for soil analysis,

and the water sample result was 6,303 ppb. The results

for the soil and water laboratory duplicate samples are

presented in Table 6-3 and Table 6-4, respectively.

Field duplicate samples were also analyzed during this

demonstration. Field duplicates consist of two samples

collected together, but submitted to the laboratory with

separate sample numbers. PRC collected 14 field

duplicate soil samples and 10 field duplicate water

samples during this demonstration. The results for the

soil and water field duplicate samples are presented in

Table 6-5 and Table 6-6, respectively.

Typically, field and laboratory duplicate samples are

used to determine error induced by sample collection and

analysis. Laboratory duplicates are compared to a

window of acceptable values, and if any fall outside that

window, corrective action is taken by the laboratory.

Field duplicates are used to identify sampling analysis

and matrix variability. To control the problems usually

detected by laboratory duplicates, PRC used only one

operator for each technology. It was assumed that any

variance in that operator’s laboratory techniques would

be the same for each sample, and therefore, statistically

insignificant. For field duplicates, PRC put each sample

through a homogenization process designed to ensure

that there was little difference between the PCP

concentration in a sample and its duplicate. Only in a

very few samples does the homogenization appear not to

have been complete. Because the samples were

homogenized and because only one operator was used,

PRC used the laboratory and field duplicates together to

determine the technology’s precision. There are

20 duplicate pairs for soil analysis and 11 duplicate pairs

23
TABLE 6-1. SOIL MATRIX SPIKE SAMPLE RESULTS FOR THE FASP PCP METHOD

Sample

No.

004

033

046

058D

087D

089

Amount Found In Amount Added To

Original Sample Matrix Spike Sample

@pm) (ppm)

0.82 9.60

ND 10.1

0.95 11.5

3.2 10.8

1.78 10.0

ND 10.2

Amount Found In Percent

Matrix Spike Sample Recovery

(ppm) (%)

8.4 79

9.02 89

10.8 86

2.67 0

6.26 45

1.44 14

Sample

No.

004

033

046

058D

087D

089

Amount Added To

Matrix Spike

Duplicate Sample

(ppm)

15.3

9.4

11.8

9.62

9.95

10.6

Amount Found In

Matrix Spike

Duplicate Sample

(ppm)

12.8

8.5

11.5

2.04

10.65

1.84

Percent Relative

Recovery Percent Difference

(%) (%)

78 1.3

90 1.1

89 3.4

0 0

89 66

17 19

Note:

ND Not detected above soil quantitation limit of 0.80 ppm

Sample

No.

1lOD

Amount Found In

Original Sample

(ppb)

45.5

Amount Added To

Matrix Spike Sample

(ppb)

50.0

Amount Found In

Matrix Spike Sample

(ppb)

142

Percent

Recovery

(%)

193

Sample

No.

IIOD

Amount Added To

Matrix Spike

Duplicate Sample

(ppb)

50.0

Amount Found In

Matrix Spike

Duplicate Sample

(ppb)

132

Percent

Recovery

(%)

173

Relative

Percent

Difference

(%)

11

Note:

ND Not detected above soil quantitation limit of 0.80 ppm

24
TABLE 6-3. SOIL LABORATORY

DUPLICATE SAMPLE RESULTS FOR THE

FASP PCP METHOD

Laboratory

Original Duplicate Relative

Sample Sample Percent

Sample Result Result Difference

No. (ppm) (ppm) (%)

015 649 339 63

036 40.7 58.9 37

049 501 212 81

059 9,777 4,323 77

072 1,345 1,826 30

084 107 107 0

TABLE 6-5. SOIL FIELD DUPLICATE

SAMPLE RESULTS FOR THE FASP PCP

METHOD

Sample

No.

001

011

020

030

Original Relative

Sample Field Duplicate Percent

Result Sample Result Difference

(ppm) (ppm) (%)

2.40 2.96 21

115 107 7

ND ND NA

32 40 22

040 11.5 11.8 3

048 29,773 30,464 2

050 1.12 1.84 49

055 1,928 2,580 29

058 30.7 3.2 162

059 9,777 4,731 70

073 59.8 70.7 17

074 486 545 11

086 3.93 3.57 10

087 9.32 1.78 137

Notes:

ND Not detected above soil quantitation limit of

0.80 ppm.

NA Not applicable due to ND result.

TABLE 6-4. WATER LABORATORY

DUPLICATE SAMPLE RESULTS FOR THE

FASP PCP METHOD

Laboratory

Original Duplicate Relative

Sample Sample Percent

Sample Result Result Difference

No. (ppb) (ppb) (%)

112 5,236 6,303 18

TABLE 6-6. WATER FIELD DUPLICATE

SAMPLE RESULTS FOR THE FASP PCP

METHOD

Sample

No.

101

Original

Sample

Result

(ppb)

74.5

Field

Duplicate

Sample

Result

(ppb)

60.4

Relative

Percent

Difference

(%)

21

102 43,804 53,439 20

103 55,900 68,900 21

104 11,307 14,106 22

105 95.1 70 30

108 120 81.3 38

109 89 46 64

110 45 45.5 1

111 11.2 48.7 125

112 5,236 6,288 18

for water analysis. Intramethod precision was evaluated

for each sample matrix using all the duplicate pairs.

Even the best technology that determines results

quantitatively cannot reproduce its results every time.

Therefore, PRC established control limits like those

sometimes used to evaluate laboratory duplicates. These

control limits were then used to determine whether the

difference between a result from a duplicate and the

result from its respective sample was reasonable. To

establish the control limits, all sample pairs that did not

produce two positive results were removed from the data

population. The RPD for each sample pair was then

calculated, and the mean RPD and population standard

deviation were determined. The lower control limit was

set at 0, which means that the results from a. duplicate

25
and its sample matched perfectly. The upper control

limit was set by multiplying the standard deviation by

two and adding it to the mean RPD. The RPD of each

sample pair was then compared to these control limits.

Each was expected to fall within them.

The FASP PCP Method detected PCP in both the

sample and its duplicate in 19 of the 20 sample pairs for

soil analysis and in all duplicate pairs for water analysis.

Control limits were established for each sample matrix.

For the soil matrix, the mean RPD was calculated to be

43.6, with a standard deviation of 45.5. Therefore, the

control limits were set at 0 and 135. Two of the sample

duplicate RPDs fell outside the range. The resulting

precision is 89 percent, which is less than the required

90 percent, and thus unacceptable. Similarly, the

control limits for RPDs established for water sample

duplicates ranged from 0 to 102 percent. One RPD was

outside control limits (sample pair 111). This data

shows that 90 percent of the sample RPDs fell within the

control limits, so the precision of the technology was

deemed acceptable for water samples.

Matrix spike duplicate samples were used to further

evaluate the precision of this method. RPD values for

the six sets of soil matrix spike and matrix spike

duplicate samples ranged from 0 to 66 percent. The

mean RPD for these samples was 15 percent, and the

standard deviation was 26 percent. The resultant upper

control limit was 67 percent. All RPD values for the

matrix spike and matrix spike duplicates fell within this

range. Only one matrix spike and matrix spike duplicate

sample was analyzed for water. Based on the small size

of the data set, no control limits were calculated.

However, the RPD value for this sample was 11 percent.

Comparison of Results to Confirmatory

Laboratory Results

PRC used the statistical methods detailed in Section

3 to determine how well the results from the FASP PCP

Method matched those from me confirmatory laboratory.

The results used for the various data sets are presented

in Tables 6-7 through 6-9, and a summary of the

statistics is presented in Table 6-10. The purpose of this

statistical data evaluation is to assess whether the method

meets Level 3 criteria for accuracy and precision.

Soil Samples: lntermethod Accuracy

The initial linear regression analysis on the entire

data set was based on results from 84 samples. The

other results indicated that no PCP was detected above

the method’s detection limits. Figure 6-l illustrates the

comparability between the FASP PCP Method and

confirmatory data. A hypothetical 100 ppm action level

FIGURE 6-1 TOTAL SOIL DATA SET.

is also noted on this figure. The 3 for this regression

was 0.35, indicating that little or no relationship exists

between the data sets. However, a residual analysis of

the data identified samples 21, 44, 47, 48, 55, 59, 60,

75, and 76 as outliers. PRC removed these nine points

and recalculated the linear regression. This regression

had an 3 of 0.41, indicating that there is still little

correlation between the two data sets. The Wilcoxon

Signed Ranks Test indicated that the FASP PCP

Method’s data was significantly different from that of the

confirmatory laboratory. This supported the regression

analysis. These results indicate that this technology is

not accurate and that it cannot be mathematically

corrected to estimate corresponding confiiatory data.

Based on these results and depending on the intended

data use, all of the samples analyzed by this method may

need confirmation analysis. This places this technology,

for the combined soil data set, into the Level 1 data

quality category.

The second tier of the accuracy evaluation involved

the separation of the data by site. This tier of data

evaluation was conducted to assess potential carrier

effects on the method’s performance. Fifty samples

from the former Koppers site were initially used for the

regression analysis. Figure 6-2 illustrates the

comparability between the FASP PCP Method and

confirmatory data. The 3 for this regression was

0.37, indicating that a relationship may exist between

the data sets. A residual analysis of the data identified

samples 21, 44, 47 and 48 as outliers. PRC removed

these four points and recalculated the linear regression.

When the regression was recalculated on the

46 remaining sample results, it defined an ? factor of

0.82, indicating that little or no relationship exists

between the two data sets. The Wilcoxon Signed Ranks

Test also indicated, at a 90 percent confidence level, that

the FASP PCP Method’s data was not significantly

different from that of the confirmatory laboratory.

Based on these results, 10 to 20 percent of the samples

26
FIGURE 6-2 FORMER KOPPERS SITE SOIL

SAMPLES.

FIGURE 6-3 WINONA POST SOIL SAMPLES.

analyzed by this method may need confirmation analysis.

This places this technology, for the combined soil data

set, into the Level 1 data quality category.

The second tier of the accuracy evaluation involved

the separation of the data by site. This tier of data

evaluation was conducted to assess potential carrier

effects on the method’s performance. Fifty samples

from the former Koppers site were initially used for the

regression analysis. Figure 6-2 illustrates the

comparability between the FASP PCP Method and

confirmatory data. The ? for this regression was

0.37, indicating that a relationship may exist between

the data sets. A residual analysis of the data identified

samples 21, 44, 47 and 48 as outliers. PRC removed

these four points and recalculated the linear regression.

When the regression was recalculated on the

46 remaining sample results, it defined an ? factor of

0.82, indicating that little or no relationship exists

between the two data sets. The Wilcoxon Signed Ranks

Test also indicated, at a 90 percent confidence level, that

the FASP PCP Method’s data was not significantly

different from that of the confirmatory laboratory.

Based on these results, 10 to 20 percent of the samples

analyzed by this method need confirmation analysis to

calculate a correction factor, converting the FASP PCP

method’s data into estimates of corresponding

confirmatory data. This places this method, for the

Koppers soil data set, into the Level 2 data quality

category.

Thirty-two samples from the Winona Post site were

initially used for the second tier regression analysis.

Figure 6-3 illustrates the comparability of the FASP PCP

Method and confrrrnatory data. The rZ for this

regression was 0.53, indicating that a relationship may

exist between the data sets. A residual analysis of the

data identified samples 59, 60, 72, and 77 as outliers.

PRC removed these four points and recalculated the

linear regression. The regression then defined an 3

I . I

. I. i

factor of 0.71. This is slightly below the 0.75 required

for Level 2 classification. The Wilcoxon Signed Ranks

Test indicated that the FASP PCP Method’s data was

significantly different from that of the confirmatory

laboratory, which supported the findings of the

regression analysis. These results indicate that this

technology is not accurate, and that it cannot be

mathematically corrected to estimate corresponding

confirmatory data. Depending on the data quality

requirements, all samples analyzed by this technology

may need confirmatory analysis. This factor places this

technology, for the Winona Post soil data set, in the

Level 1 data quality category.

The demonstration results indicate that there is a

carrier effect on this method. The accuracy and

comparability to the confiiatory data is higher in the

samples contaminated with PCP in an isobutyl ether and

butane carrier. The diesel fuel carrier solvent causes

interference that lowers accuracy and comparability with

confirmatory data.

The data was also evaluated by concentration.

Overall, the confirmatory laboratory found that

46 samples had concentrations of less than 100 ppm.

The initial linear regression of these 46 samples defined

an r2 of 0.63, indicating that a relationship may exist

between the two data sets. However, a residual analysis

of the data identified samples 14, 38, 85 and 100 as

outliers. PRC removed these four points, recalculated

the linear regression, and defined an 9 of 0.50, also

indicating that a relationship may exist between the two

data sets. However, the Wilcoxon Signed Ranks Test

indicated, at a 90 percent confidence level, that the

FASP PCP Method’s data was not significantly different

from that of the confiiatory laboratory. This

contradicts the regression analysis and indicates that one

of the data sets may not have normal distribution. For

this reason, the regression data was considered suspect.

The results, therefore, indicate that this technology

27
TABLE 6-7. SUMMARY OF DEMONSTRATION DATA: FORMER KOPPERS SITE SOIL SAMPLES

Sample No.

FASP PCP Confirmatory

Method Laboratory

(0.80 ppm)a (ppm)

001 2.40 4.42

001 D 2.96 4.18

002 1.50 1.64

0 0 3 co.80 U 0.13b

0 0 4 0.82 2.04

0 0 5 2.24 3.70

0 0 6 1.44 1.89

0 0 7 6.00 J 2.66

0 0 8 0.31 J 0.66

0 0 9 2.50 3.52

0 1 0 1,100 435.0

011 115 106.0

011D 107 112.0

0 1 2 co.80 U 0.056b

0 1 3 58.2 32.80

0 1 4 93.9 99.60

0 1 5 6 4 9 1,190

0 1 6 195 273.0

0 1 7 346 1,335

0 1 8 5.20 J 2.13

0 1 9 5.70 J 6.89

0 2 0 co.80 U 0.10

020D ~0.80 U 0.09b

021 3,600 5,320

0 2 2 17.6 1.85

0 2 3 21.6 1.86

0 2 4 3.87 1.57

0 2 5 521 593.0

0 2 6 39.1 0.42

0 5 2 29.2 28.20

0 5 3 3.67 2.23

0 5 4 ~0.80 U 0.47

0 5 5 1,930 3,135

055D 2,580 3,003

Notes:

a Detection limit.

Sample

No.

FASP PCP

Method

(0.80 ppm)a

Confirmatory

Laboratory

(ppm)

0 2 7 11.5 11.30

028 ~0.80 U 0.45

029 0.33 J 1.06

0 3 0 32.0 28.60

030D 40.0 29.00

031 0.58 1.43

032 17.2 0.62b

0 3 3 co.80 U 0.40

0 3 4 co.80 U 0.31b

0 3 5 201 145.0

0 3 6 40.7 36.80

037 1.86 1.19

038 107 77.00

0 3 9 4.10 3.32

0 4 0 11.5 400.0

040D 11.8 34.40

041 6.53 6.44

042 4.72 4.0 9

0 4 3 739 655.0

0 4 4 17,600 6,956

0 4 5 41.0 22.10

0 4 6 0.95 0.95

0 4 7 127,000 13,920

048 29,800 26,100

048D 30,500 30,260

049 501 255.0

050 1.12J 2.16

050D 1.84 1.25

051 0.30 J 0.43

0 5 6 26.1 9.90

0 5 7 9.35 8.74

058 30.7 3.53

058D 3.20 9.13

D Sample analyzed by Method 8151 A; all other samples were analyzed by Method 8270A.

J Reported amount is below detection limit or not valid by approved QC procedures.

U PCP was not detected.

28
TABLE 6-8. SUMMARY OF DEMONSTRATION DATA: WINONA POST SITE SOIL SAMPLES

FASP PCP Confirmatory

Method Laboratory

Sample No. (1.60 ppm)’ (ppm)

059 9,780 9,600

059D 4,730 10,260

060 4,570 1,008

061 457 2,744

062 76.0 138.0

063 219 1,610

064 408 1,978

065 348 1,577

066 32.4 57.80

067 37.4 110.0

068 38.0 47.70

069 664 798.0

070 1,120 2,888

071 249 289.0

072 1,350 336.0

073 59.8 74.80

073D 70.7 78.20

074 486 836.0

074D 545 1,520

075 860 3,692

076 679 4,590

077 273 2,040

078 361 1,720

079 155 792.0

Sample

No.

D80

081

082

083

084

085

086

086D

087

087D

088

089

090

091

092

093

094

095

096

097

098

099

100

FASP PCP Confirmatory

Method Laboratory

(1.60 ppmIa (ppm)

605 2,550

70.0 125.0

965 2,400

18.6 270.0

107 1,140

11.5 57.70

3.93 6.59

3.57 6.88

9.32 34.00

1.78 51.80

e1.60 U 2.58

cl .60 U 0.21b

<I .60 U 0.55b

cl.60 U 0.28b

0.87 J 0.57b

~1.60 U 0.19b

cl.60 U 1.02b

cl.60 U 0.088b

18.2 59.80

4.16 14.60

>I .60 U 0.57

4.44 4.02

94.2 52.40

Notes.

a Detection limit; this value was raised due to interference from the diesel fuel carrier.

b Sample analyzed by Method 8151A; all other samples were analyzed by Method 8270A

J Reported amount is below detected limit or not valid by approved QC procedures.

U PCP was not detected.

meets Level 2 criteria, when analyzing samples with

concentrations of less than 100 ppm, but its data cannot

be mathematically corrected to estimate corresponding

confiitory data.

The confirmatory laboratory identified 38 samples

with concentrations greater than 100 ppm. The initial

linear regression on these 38 samples defined an 3 of

0.31, indicating that little or no relationship exists

between the two data sets. A residual analysis of the

data identified samples44,47,48, 59 and 60 as outliers.

PRC removed these five points, recalculated the

regression, and defined an t-2 of 0.41. The Wilcoxon

Signed Ranks Test indicated that the FASP PCP

Method’s data was significantly different from that of the

confirmatory laboratory, which confirmed the regression

analysis. These results indicate that this technology is

not accurate and that it cannot be mathematically

corrected to estimate corresponding confiiatory data.

This factor places this technology, for the combined soil

data set for PCP concentrations above 100 ppm, in the

Level 1 data quality category. The data indicates a

29
TABLE 6-9. SUMMARY OF DEMONSTRATION

WATER DATA

FASP PCP Confirmatory

Method Laboratory

Sample No.~ (0.002 ppm)b (ppm)

101 0.075 0.00414c

102 44 15.90

103 56 13.50

104 11 0.0123

105 0.095 0.849

105D 0.070 0.640

106 0.078 0.0103c

107 4.4 2.050’

108 0.12 0.00185c

108D 0.81 0.00221c

109 0.089 0.000175c

109D 0.046 0.00063c

110 0.045 0.0181c

110D 0.046 0.0181c

111 0.011 J 0.000348c

111D 0.49 0.00032c

112 5.2 1.810

112D 6.3 2.020

113 0.042 0.00227c

Notes:

a

b

C

J

Samples 101 through 105D were from the

VVinona Post site; Samples 108 through 112D

were detected from the former Koppers site.

Samples 106,107 and 113 were PE samples.

Detection limit

Sample analyzed by Method 515.1; all other

samples were analyzed by Method 8270A.

Reported amount is below detection limit or

not valid by approved QC procedures.

trend for the technology to have slightly better accuracy

and comparability when used to analyze samples

containing less than 100 ppm PCP.

The confirmatory laboratory found that 35 samples The evaluation of the Koppers data for those

from the former Koppers site had concentrations of less samples the confirmatory laboratory found had results

than 100 ppm. The initial linear regression on these

samples defined an ? of 0.84, indicating that a

greater than 100 ppm was based on 15 samples. The

initial regression defined an ? of 0.27, indicating that

TABLE 6-10. SUMMARY OF REGRESSION

AND RESIDUAL STATISTICS SOIL ACCURACY

N 3 Y-int Slope Wilcoxon

Probabilitv

All Data 75 0.41 70.1 0.26

All Data

cl00 ppm

All Data

HO0 ppm

KoppersAll Data

Koppers

<IO0 ppm

Koppers 13 0.71 -779.9

HO0 ppm

WinonaAll Data

Significant

Difference

Winona 9 0.51 -4.64 0.61 Significant

cl00 ppm Difference

Winona 19 0.57 84.4 0.23

HO0 ppm Difference

Significant

42 0.50 5.3 0.64

33 0.41 116.7 0.34

46 0.82 28.4

31 0.76 2.0

0.68

1.2

1.85

28 0.71 27.4 0.24

No Significant

Difference

Significant

Difference

Significant

Difference

Significant

Difference

No Significant

Difference

Significant

Difference

Notes:

Y-int

Number of data points

Coefficient of determination adjusted for

variance

Y-axis intercept of the regression line

relationship exists between the two data sets. A residual

analysis of the data identified samples 13, 14, 26, and 38

as outliers. PRC removed these four points, recalculated

the regression,and defined an 9 of 0.76, indicating that

a relationship exists between the two data sets. The

Wilcoxon Signed Ranks Test indicated, at a 90 percent

confidence level, that the FASP PCP Method’s data was

significantly different from that of the confirmatory

laboratory. These results indicate that this technology is

not accurate, but that it can be mathematically corrected

to estimate correspo nding confirmatory data. Based on

these results, 10 to 20 percent of the samples analyzed

by this method need confirmation analysis. This factor

places this technology, for these samples, in the Level 2

data quality category.

30
little or no relationship exists between the two data sets,

but samples 47 and 48 were identified as outliers. PRC

removed these two points, recalculated the regression,

and defined an ti of 0.71 indicating that a relationship

may exist between the two data sets. The Wilcoxon

Signed Ranks Test confirmed the regression data,

indicating that the FASP PCP Method’s data was

significantly different from that of the confirmatory

laboratory. These results, therefore, indicate that this

method is not accurate and cannot be reliably

mathematically corrected to estimate corresponding

confirmatory data. This places the method, for this data

set, in the Level 1 data quality category. This data

indicates that the method tended to have greater accuracy

and comparability to confirmatory data for samples

containing less than 100 ppm PCP.

The same types of analyses were conducted on data

from samples from the Winona Post site. The

confirmatory laboratory found that nine of the samples

had concentrations less than 100 ppm. The initial

regression defmed an 9 of 0.51, indicating that a

relationship may exist between the two data sets. A

residual analysis of the data identified no outliers. The

Wilcoxon Signed Ranks Test indicated that the FASP

PCP Method’s data was significantly different from that

of the confirmatory laboratory. These results indicate

that this technology is not accurate and that it cannot be

mathematically corrected to estimate corresponding

confirmatory data. This factor places this technology,

for Winona Post site samples with less than 100 ppm

PCP, in the Level 1 data quality category.

The confirmatory laboratory found that 23 samples

from Winona Post site had concentrations greater than

100 ppm PCP. The initial regression defined an rr of

0.49, indicating that little or no relationship exists

between the two data sets. A residual analysis of the

data identified samples 26, 59, 60 and 80 as outliers.

PRC removed these points, recalculated the regression,

and defined an ? of 0.57, indicating that a relationship

may exist between the two data sets. The Wilcoxon

Signed Ranks Test verified these results, which indicates

that this technology is not accurate and that it cannot be

mathematically corrected to estimate corresponding

confirmatory data. All samples analyzed by this method True Positives

need confumation analysis. This factor places this

technology, for these samples, in the Level 1 data quality

category. This data indicates a tendency for this method

to be more comparable to the confirmatory data for

samples containing less than 100 ppm PCP. This

conclusion is based on an examination of the slopes and

y-intercepts for the data sets.

Soil Samples: Intermethod Precision

When the Dunnett’s Test compared the RPDs

between the FASP PCP Method’s entire field duplicate

data set and the corresponding confirmatory laboratory

data set, the precisions were found to be statistically

similar. When the precision was examined relative to

the site from which the duplicates were collected, the

precision between the methods were found to be

statistically similar at both sites. The Wilcoxon Signed

Rank Test confirmed this conclusion.

Water Samples: Intermethod Accuracy

Nineteen water samples were found to have

concentrations of PCP above detection limits by both the

confirmatory laboratory and FASP methods. These

samples, therefore, were eligible for the regression

analysis. Figure 6-4 illustrates the comparability

between the FASP PCP Method and confirmatory data.

The EPA maximum contaminant level (MCL) of 1 ppb

is also shown on this figure. The 3 for this regression

was 0.92, indicating that a relationship exists between

the data sets. The regression analysis produced a slope

of 3.3, and a y-intercept of 0.36. However, residual

analysis of this data identified samples 102 and 103 as

significantly influencing the regression. When these

points were removed as outliers, the rZ dropped to

0.18 and the slope and intercept changed to 12.0 and

0.76 respectively. This confirmed the strong influence

these points exhibited over the regression analysis. The

Wilcoxon Signed Ranks Test was used to verify these

results. It indicated, at a 90 percent confidence level,

that the FASP PCP method’s data was significantly

different from that of the confirmatory laboratory. This

supported the regression analysis. These results indicate

that this technology is not accurate and that its data

FIGURE 6-4 TOTAL WATER DATA SET.

%

. c

TTT

l . . . . .

. .

31
cannot be mathematically corrected to estimate

corresponding confirmatory data. This places the

method, for the combined water data set, in the Level

1 data quality category.

Of these samples, 10 were collected at the former

Koppers site. The r2 for this regression was

0.99, indicating that a strong relationship exists between

the data sets. Figure 6-5 illustrates the comparability

between the FASP PCP Method and confirmatory data.

An examination of the slope (3.0) and y-intercept

(0.042) showed that both of these parameters are not

statistically equivalent to their expected values. The

Wilcoxon Signed Ranks Test was used to verify these

results, but it indicated that the FASP PCP Method’s

data was significantly different from that of the

confirmatory laboratory. The method, therefore, does

not produce Level 3 data, but rather Level 2 data. The

data produced from this technology must be corrected to

simulate confirmatory data by submitting 10 to

20 percent of the samples for confirmatory analysis.

Six of the 19 water samples eligible for regression

analysis were from Winona Post site. The rZ for

regression on these six samples was 0.87, indicating that

a strong relationship exists between the data sets. Figure

6-6 illustrates the comparability between the FASP PCP

Method and confirmatory data. An examination of the

slope (3.2) and y-intercept (2.2) showed that both of

these parameters are not statistically equivalent to their

expected values. A residual analysis of this data,

though, showed that samples 102 and 103 had a large

influence on the regression, and when these outliers

were removed and the regression was recalculated, the

r2 was zero.

The Wilcoxon Signed Ranks Test, however,

indicated at a 90 percent confidence level that the FASP

PCP Method’s data was not significantly different from

that of the confirmatory laboratory, without the outliers.

The regression analysis, therefore, did not agree with the

Wilcoxon Signed Ranks test when it was run on the data

set without the outliers. This indicates that the condition

of normality was not satisfied by one or both of the data

sets, and it makes the regression analysis suspect. This

indicates that the technology does not produce Level

3 data but rather Level 2 data. Data produced from this

technology is statistically similar to confirmatory data

*‘ --1--‘-‘ r--.“_l~...--“.-_~_-~--,._~_~8

FIGURE 6-6 WINONA POST WATER

SAMPLES.

but cannot be corrected. This data indicated that the

method is affected by PCP carrier interferences. This

method produced the greatest accuracy and

comparability to confirmatory data for PCP in an

isobutyl ether and butane carrier.

Wafer Samples: lntermethod Precision

For water sample analysis, the Dunnett’s Test

compared RPDs between the FASP PCP Method’s field

duplicate data set and the corresponding confirmatory

laboratory data set. This indicates that the technology’s

precision is not different from the confirmatory

laboratory’s. The Wilcoxon Signed Rank Test

confirmed this data.

32
Section 7

Applications Assessment

The principal advantage of the FASP PCP Method

is that it is very specific to PCP. This specificity

reduces the chances of determining that a sample

contains PCP when, in fact, it does not. This specificity

also greatly reduces the chances of determining that a

sample contains no PCP, when it actually does. Other

advantages of the FASP PCP Method include the

following: (1) it is inexpensive when compared to

formal laboratory analysis using EPA-approved methods

for PCP, (2) it is portable enough to use in the field,

(3) it has a high sample throughput, and (4) it is capable

of providing sample results quickly. In addition, the

detection limit for water samples analyzed with the

FASP PCP Method is less than the MCL of 1.0 ppb.

The MCL is an EPA-enforceable action limit for PCP in

water samples.

The FASP PCP Method provides quantitative

estimates of PCP concentrations in soil and water

samples. It estimates sample results through a

quantitative comparison to a standard curve. However,

its estimation of PCP concentrations in samples may not

always agree with results from the analysis of the same

sample by EPA-approved methodologies. The results

from this demonstration indicate that this technology has

a carrier solvent sensitivity. The technology produced

data that were more consistent with confirmatory results

for samples from the former Koppers site. The high

level of diesel fuel contamination in the Winona Post site

samples required extensive cleanup steps to remove interferences. These cleanup steps were not sufficient to

remove all of the interferences. Thus, the Winona Post

site results were all significantly different than the

confirmatory results. Method results, when compared to

confirmatory laboratory results, may include both false

positive results, which overestimate the concentration of

PCP in the sample, and false negative results, which

underestimate the concentration of PCP in the sample.

Both false positive and false negative results have

important implications on investigative and remedial

activities. Another limitation of the FASP PCP Method

is that it can be affected by chemicals found naturally in

environmental samples, such as humic acids, as well as

by chemicals associated with PCP treatment of wood

products. These chemicals may affect the technology’s

performance even when cleanup steps are employed.

The FASP PCP Method is best operated by

individuals with at least 6 months of experience using a

GC and at least 1 month of experience performing PCP

analysis. Logistical limitations of the FASP PCP

Method include the need for a large capital investment

for the purchase of the analytical instrumentation and

extraction equipment. This equipment may also be

rented. The FASP PCP Method’s equipment requires

electricity for operation, and the instruments must be

operated indoors in a temperature-controlled

environment. The method uses hazardous chemicals

such as MtBE, sodium hydroxide, and sulfuric acid.

Proper safety and disposal practices need to be employed

when using the FASP PCP Method.

The FASP PCP Method is designed to provide

quantitative screening results for PCP in water and soil

samples. Applications for the FASP PCP Method

include both laboratory and field uses. The FASP PCP

Method can be used by laboratories as a rapid screening

tool for PCP. Its results can be used to determine

appropriate sample extraction techniques as well as to

determine dilutions that may be required for sample

analysis. Its results also can be used to determine the

appropriate analytical method to be used for

confirmatory sample analysis. The use of this method in

this mode can protect more sensitive instruments from

damage exposure resulting from highly contaminated

samples. The FASP PCP Method also can be used to

guide the following field investigations and sample

collection activities: (1) determining the vertical and

horizontal extent of PCP contamination in soil,

(2) tracking PCP groundwater contamination plumes,

and (3) determining PCP contamination in surface

waters. Another use of the FASP PCP Method is to

monitor the effectiveness of remediation techniques

employed to reduce or eliminate PCP contamination. In

33
particular, it can be used to determine whether PCP

concentrations in soil or water samples exceed

site-specific action limits.

The FASP PCP Method is best used at sites where

PCP is a known contaminant where petroleum products

are not the carrier solvents, and where large

concentrations of other organic chemicals are not present

in the samples. Generally, the larger the site or the

larger the number of samples collected, the greater the

advantage of using the FASP PCP Method. The use of

this method at large sites will decrease the cost of the

investigation by decreasing the number of samples

requiring confirmatory laboratory analysis and by

enabling more work to be completed during a single

sampling visit. The primary advantage of this method is

that it can allow work to continue without having to wait

for confirmatory laboratory results.

The technology can be used to guide field work and

sampling efforts, provided that at least 10 to 20 percent

of the samples are submitted to a confirmatory

laboratory for EPA-approved method analysis. These

samples must constitute PCP concentrations from all

levels found. Results from the confirmatory laboratory

can be used to formulate correction factors for the

technology’s results or verify its similarity to the

confirmatory data. Correction factors, if needed, can be

applied to its results to obtain a more precise estimation

of PCP contamination. Correction factors are site

specific and may, in fact, be sample-matrix specific.

Any time sites or sample matrices change, new

correction factors should be established by comparing

the FASP PCP Method’s results to confirmatory

laboratory results of the same samples.

Particular attention needs to be paid to samples with

PCP concentrations near the action limit of the site,

because the method can provide both false positive

results and false negative results when compared to

confirmatory laboratory results. False positive results

will cause remediation efforts to be performed in areas

that do not require cleaunup. False negative results will

cause no remediation to take place in areas where

cleanup is needed. To limit the impact of false negative

results, working action levels for this method should be

set at 80 to 90 percent of the target action level. Field

investigators should recognize that the FASP PCP

Method is designed as a screening tool to assist in

evaluating PCP contamination. The technology is an

abbreviation of an approved method for determining

PCP concentrations. When in doubt, samples should be

submitted for confirmatory laboratory analysis using

EPA-approved methods.

34
Section 8

References

PRC Environmental Management, Inc. (PRC). 1993a. “Predemonstration Sampling Plan For The Evaluation of

Pentachlorophenol Field Screening Technologies. EPA Contract 68-CO0047.

PRC. 1993b. “Final Demonstration Plan for the Evaluation of Pentachlorophenol Field Screening Technologies.”

EPA Contract No. 68-CO-0047.

Stanley, T. W. and S. S. Vemer. 1983. “Interim Guidelines and Specifications for Preparing Quality Assurance

Project Plans. ' " U.S. Environmental Protection Agency, Washington DC. EPA/600/4-83/004.

U.S. Enviromnental Protection Agency. 1990. “Quality Assurance/Quality Control Guidance for Removal

Activities. " EPA/540/G-90/004. April.

35