INNOVATIVE APPROACHES TO DATA
VALIDATION
UNITED STATES ENVIRONMENTAL
PROTECTION AGENCY
REGION
JUNE 1995
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INNOVATIVE APPROACHES FOR
VALIDATION OF ORGANIC AND INORGANIC DATA-
STANDARD OPERATING PROCEDURES
JUNE.1995
U.S. .ENVIRONMENTAL PROTECTION AGENCY
REGION III
ANALYTICAL SERVICES AND QUALITY ASSURANCE BRANCH
201 "DEFENSE HIGHWAY, SUITE 200
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NOTICE
The procedures set forth herein are intended as guidance. They do not constitute
rulemaking by the Agency and may not be relied on to create a substantive or
procedural right.enforceable by any other person. The Government may take
action that is at variance with the procedures in this manual.
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INTRODUCTION
There are five levels of data validation within this manual approach. The levels consist of three
(3) organic review procedures (M-l, M-2, M-3) and two inorganic review procedures (IM-1,
IM-2). (The term "level" is perhaps misleading because it implies succession, which is not the
case with this or any other level presented in this document. The "levels " are independent of
each other.) M-3 and IM-2 review procedures represent full validation as described in the EPA
National Functional Guidelines for Data "Review. Should the intended data use dictate review
by the protocols presented in the National Functional Guidelines for Data Review (IM-2 and M-
3) refer to the most recent version of Region m Modifications to the National Functional
Guidelines. The remaining data review levels are described in detail in this document The
SOPs describing how to apply these levels to a data-package are in Appendices A through D.
All procedures require(full CLP or^ C^ equivalent data .package, deliverable^. -\
- ป . '-.' ' !"'' - '
In general, organic Level M-l's emphasis is on reviewing positive (detected) :data. The primary
question asked is whether or not a compound is present If it is, the next question addressed is
whether the compound is potentially from field or laboratory-induced contamination. If the
answer is negative, men the presence of the compound is considered confirmed, and the reported
concentrations are considered usable for some predefined data uses. If information regarding
data quality and usability is required, then the emphasis is shifted accordingly to an evaluation
of data quality parameters, false negatives, and detection limits (Level M-2 oriM-1). If legally
defensible data are necessary, then a full, CLP-equivalent data validation is performed (Level
M-3 or IM-2). There is a definite focus at every step of the process. This allows for a clear
differentiation in the levels of data validation.
For guidance purposes, general data use categories and suggested levels of review are provided
in Table 1-3. However, it is important to note that the selected level of review will be specific
to the intended data use and specific project objectives.
Standard Operating Procedures
SOPs have been developed for Levels M-l, M-2, and IM-1 and are in the following sections
of this document:
Volatiles (Appendix A)
Semivolatiles (Appendix B)
Pesticides/PCB (Appendix C)
, Metals and Cyanide (Appendix D)
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CONTENTS
Page
Introduction
Glossary of Acronyms and Terms
Appendices (SOPs)
A. Validation of Volatile Organic Analyte Data (Levels Ml and M2)
A-l. Manual Level Ml (for VOAs)
1. Purpose and Applicability . .. ... . . 1
2. Quality Control Measures Checked .... 1
3. Procedure ..-,..*;;>*,.,.... ........ป-,-...-.;. .1
3.1 Action Level Notification 3
3.2 Evaluation of Mass Spectra for Detected
Compounds .6
3.3 Evaluation of Chromatograms . . . . ; ... . ...... . . 10
3.4 Evaluation of Retention Times ...................... 14
3.5 Evaluation of Blanks . . . . 16
3.6 Sample Paperwork 17
Tables
Ml-VOA-1 QC Checklist for Level Ml CLP RAS Volatile Organics .-.-... . 2
Ml-VOA-2 Volatile Organic Analytes and Action Levels 5
Ml-VOA-3 VGA Mass Spectral Evaluation Summary. '..,.:..- 11
A-2. Manual Level M2 (for VOAs)
1. Purpose and Applicability 1
2. Quality Control Measures Checked 3
3. Procedure . . 3
3.1 Action Level Notification 7
3.2 Technical Holding Times 10
3.3 GC/MS Instrument Performance Check 12
3.4 Initial Calibration . 14
3.5 Continuing Calibration 18
3.6 Blanks . . .20
3.7 System Monitoring Compounds (Surrogate
Spikes . . 25
3.8 Matrix Spike/Matrix Spike Duplicate 28
3.9 Internal Standards 29
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CONTENTS (Continued)
Page
3.10 Reported CRQLs . 31
3.11 Tentatively Identified Compounds 32
Tables
M2-VOA-1 QC Checklist for Level M2 CLP RAS Volatile Organics ....... 2
M2-VOA-2 VGA Qualifier Summary .. . . . .... .... . . > ;ป ., .'-i . . 5
M2-VOA-3 VGA Surrogate and Matrix Spike Quality Control Summary... . . .... 6
M2-VOA-4 Volatile Organic Analytes and Action Levels ....;.;. . ...w;v;.yj,. . . * 9
M2-VOA-5 Qualification of Volatile Analytes Based on technical Holding Times . .11
M2-VOA-6 Qualification of Volatile Analytes Based on System Monitoring
Compound Recoveries................. . . . . . :^.;.. , . . .27
B. Validation of Semivolatile Data (Levels Ml and M2)
B-l. Manual Level Ml (for SVGAs)
1. Purpose and Applicability ........... . ..... ... . . .... ... . .1
2. Quality Control Measures Checked ... :.., . . . .,. . . 1
3; Procedure V ' '.,.."..........'.-........ //;.',,;'.:..,... . .1
3.1 Action Level Notification :............ ,3
3.2 Evaluation of Mass Spectra for Detected
Compounds ^ .... .5
3.3 Evaluation of Chromatograms . . ^ 9
3.4 Evaluation of Retention Times ...................... 15
3.5 Evaluation of Blanks 16
3.6 Sample Paperwork . . . 17
Tables v .
Ml-SVOA-1 QC Checklist for Level Ml 2
Ml-SVOA-2 Semivolatile Organic Analytes and Action Levels. .4
Ml-SVOA-3 Mass Spectral Evaluation Summary 1Q
: . ' " ..'.''.
B-2. Manual Level M2 (for SVGAs) ,
1. Purpose arid Applicability ......' i
2. Quality Control Measures Checked 3
3. Procedures 3
3.1 Action Level Notification . . . 9
3.2 Technical Holding Times 11
3.3' GC/MS Instrument Performance Check 13
3.4 Initial Calibration 16
3.5 Continuing Calibration 20
3.6 Blanks 22
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CONTENTS (Continued)
Page
3.7 Surrogate Spikes . . . 28
3.8 Matrix Spike/Matrix Spike Duplicate ... ........... 32
3.9 Internal Standards ....:............... 34
3.10 Reported CRQLs ... .... . , .. . 36
3.11 Tentatively Identified Compounds ..... .;.;*ป ^.,.,.,.... . 37
Tables
M2-SVOA-1 QQ Checklist for Ijevel M2 .'. . .;. . ... . .;.:^&smasmwK8w:^.-.'. 2
M2-SVOA-2 SVOA^Qiiii^Smnm .......... .Vv-^^sss^^j^^ ;... 5
M2-SVOA-3 SVGA Surrogate and Matrix Spike QC Summary '.-:,^:ws^'<': : '' 7
M2-SVOA-4 Semivolatile Action Levels ... . . . . . . . .,;..'^^^^^m-i.;-.. . 10
M2-SVOA-5 Qualification of Semivolatiles Based on Surrogate Recoveries . .. . . . . 31
C. Validation of Pesticide/PCB Data (Levels Ml and M2)
' ' . '' V;.;^f%^';.^' ' / ; .
C-l. Manual Level Ml (forPesticides/PCBs)
1. Purpose and Applicability .......... . '^^Sj^^fj^s....... I
2. Quality Control Measures Checked ...... .:. .^^||fi^.. '. .'... . . . 1
3. Procedure ..-..;.--:.;,:.,'.,.......'....-...;. ^'ฅฃjฃ,'ฃ*.--..i'. .-.-'. . .1
3.1 Action Level Notification ...... .,'i;^fv :..;.... ..3
3.2 Evaluation of Retention Times', ... . ..i,.';-;'-'.^; >''..'..; 5
3.3 Evaluation of Chromatograms ..... .-.i ., *. ; . .Cr% ... . . . . .7
3.4 Evaluation of Blanks ........\ ......... 14
3.5 Sample Paperwork 19
Tables
Ml-PEST-1 Checklist for Level Ml PEST/PCB .2
Ml-PEST-2 PEST/PCB Action Levels. . 4
Ml-PEST-3 PEST/PCB Retention Time for Windows 8
Ml-PEST-4 PEST/PCB Retention Time for Evaluation Summary .9
C-2. Manual Level M2 (for Pesticides/PCBs)
1. Purpose and Applicability 1
2. Quality Control Measures Checked . . . 3
3. Procedures 3
3.1 Action Level Notification . 7
3.2 Technical Holding Times 9
3.3 GC/ECD Instrument Performance Check 11
3.4 Initial Calibration 16
3.5 Continuing Calibration . . .18
3.6 Blanks ., . 21
3.7 Surrogate Spikes ....;. 25
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CONTENTS (Continued)
3.8 Matrix Spike/Matrix Spike Duplicate 27
3.9 Pesticide Cleanup Checks ... . ... . . 28
3.10 Reported CRQLs , 30
-.".-. . /:.:.-';,.-. :, Tables , . ''-. ..'-.-
M2-PEST-1 QC Checklist for Level M2 .'. ............ .*..>, 2
M2-PEST-2 PEST$^ฃi^ :..... ....;,:.%.-> v;, ,.. .5
M2-PEST-3 ^PKTYPl^ '.,. '..... .. .^^Xjj^^xy*. &
M2-PEST-4 PEST/piGB .v.... ^.:f:;..!.'.:J.. .8
Attachment to Appendix C-2
- .'--".^X.-..-.'.V;..i-..
' '" ' """"* *~''xttfy\/P.l*rJjฃpjฃ!>?--&.*!?* ' . ' ' ' '
D. Validation of Inor^nlc Analyte Data (Level Ml)
1. Purpose^d^i^liclbiiity , ;......... .1
' ''"'.''-, ':-^ฃ:^ฃ'^:-l ' '' '' ' .."'' '.>?.''. . ' ''
2. QualityCoh^l/Measiireis.Checked ....'.-... .... .> 2
' ' 2.1'':Krckieduie$-%^............ ....... /....:.... ,>:. '.. '....... .2
2.2 Reporting Requirements ..................... . . :. . .4
2.3 Action Level Notification .... . . ...... r......... . . . . .6
2.4 Holding Times ...... . 8
2.5 Calibration .,........ . .... . .. .... ..... ..v^. ..... .9
2.6 Blanks .. T: 13
2.7 ICP Interference Check Sample (ICS) ...... . . 14
2.8 Laboratory Control Sample (LCS) 16
2.9 Duplicate Sample Analysis 17
2.10 Matrix Spike Sample Analysis . 18
2.11 Furnace Atomic Absorption QC 20
2.12 ICP Serial Dilution 21
2.13 Field Duplicates . 22
2.14 Reporting Limit Verification 23
2.15 Sample Paperwork ... 24
Tables
IM-l-INORG-QC. QC Checklist for Level Ml-CLP RAS TAL Inorganics . 3
IM-1-INORG-AL Target Analyte List Metals and Action Levels 7
IM-1-INORG-HT. Holding Time Summary (back)
IM-1-INORG-CAL. Calibration Summary J (back)
IM-1-INORG-SPK. Summary of Spike Recovery /DuplicatePrecision (back)
IM-1-INORG-QL. Summary of Data Qualifiers (back)
1M-1-INORG-IRDA Inorganic Regional Data Assessment. (back)
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Glossary of Acronyms and Terms
Acronyms
%D
%R
AA
AOB
APO
BPB
BNA
CADRE
CARD
CCB
CCS
ccy
CF
CLP
CLPRAS
CRDL
CRQL
CSF
CV
DAS
DFTPP
DPO
DQOs
DV
BCD
EICP
EMSL-LV
EPA
GC
GC/EC
GC/MS
GPC
HAZRAP
ICB
ICP
ICS
ICV
IDL
IRDA
IS
LCS
percent difference
percent recovery of spiked amounts of analytes
atomic absorption
analytical opei^Jions
''^.vtt^s
Bromofluorobene(volatik instrument
(ปmputer aided dare^aew
Cl^P analytical .result^ database
cx>ntinumg
.' k *". , -v'
calibration factr
contract
con
contract
computer required ;qitioiQ -Unoit
complete SDG file
Coefficient of Variation
delivery of analytical services .
Decafluorotriphenylphosphine (semivolatile instrument performance
check)
deputy project officer .
data quality objectives
data validation
electron-capture detector .
extracted ion current profile
Environmental Monitoring Support; LaboratoryLas Vegas
United States Environmental Protection Agency
gas chromatography
gas chromatography/electron capture
gas chromatography/mass spectra
gel Permeation Chromatography
Hazardous Waste Remedial Actions Program
initial calibration blank
inductively coupled plasma
interface check sample
initial calibration verification
instrument detection limits,
Inorganic Regional Data Assessment
internal standards
library control sample
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MCL
ml
MS/MSD
MSA
m/z
NEESA
NET
QADS
RDA
PEST/PCB
PRP
QA/QC
XJAPjP
OC
QL
QN
RAS
RIG
RI/FS
RPD
RPM
RRF
RRT
RSD
RT
SAS
SDG
SMC
SMO
SOP
SOW
SVGA
TAL
TCL
TIC
TPH
TPO
VGA
maximum contamination limit
milliliter
matrix spike/matrix spike duplicates
Method of Standard Addition.
the ratio of mass (m) to charge (z) of ions measured by GC/MS
Naval Energy and Environmental Support Activity
National Institute of Standards and Technology
organic analysis datasheet (Form.I)
Assessment
bibhehvls
rป-v-.y .
ility study
.. .. Z^^^r---
remedial project 'manager
v. . * - )** .'"V-l ' ' '. **
relative retention time
relative standard deviation
retention time '
special analytical services
sample delivery group
system monitoring compound
sample management office
standard operating procedure
statement of work
semivolatile organic analyte
target analyte list
target compound list
tentatively identified compound
total petroleum hydrocarbons
technical project officer
volatile organic analytes
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TERMS
Associated Samples Any sample related to a particular QC analysis.
For example:
For ICV, all samples run under the same
calibration curve.
For duplicate RPD, all SDG samples digested/
distilled of the same matrix.
Calibration Curve A plot of absorbance versus concentration of standards.
Case
collected over a given time period for a particular site.
A Case consists of one of more Sample Delivery
Group(s).
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Appendix A
Validation of VolatUe Organic Analyte Data
Subappendix A-l coven; Level Ml
Subappendix A-2 covers Level M2
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Appendix A-l
Validation of Volatile Organic Analyte Data
Manual Level Ml
1. Purpose and Applicability
This procedure provides step-by-step instructions to manually validate the volatile organic
analyte '(VOA) data using the manual innovative data validation approach at Level Ml.
..The procedure is applicable tor^eJ'VOA-data^b
|fiojg;rain Statement of YYb^ (O3^^ CLP SOW
^specifications are essential in^ brd^|i^carr^out
.Data validated using this procedure are ^considered usable for the following types of
purposes; however, the data users^jnustidecide .on a case-by-case basis whether the
procedure is suitable for their intended data uses. The suggested data uses are:
Oversight of activities led by other parties
Comparison to action levels
Initial site investigation
Contamination sources
2. Quality Control Measures Checked
Table Ml-VOA-1 highlights the quality control (QC) indicators evaluated under this data
validation procedure.
3. Procedure
The following subsections describe for each of the QC indicators the acceptance criteria,
location and retrieval of QC data, evaluation of the QC data, actions taken in the event the
QC acceptance criteria are exceeded, and documentation of the QC violations in a
standardized report form.
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* Table Ml-VOA-1
QC CHECKLIST FOR LEVEL Ml
CLP RAS VOLATILE ORGANICS
QC MEASURES
InstrwnK
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Reporting requirements for Level Ml are:
Hand annotate the Form I's, including
Data validation qualifiers
- Sample identification number
Sampling location
" Provide a narrative that includes
- A statement mat defines the level of the data review, i.e., Ml
Major problems associated with analysis
Include the following attachments
List of data validation qualifiers
- - Support documentation including forms that support assigning data
.qualifiers :
Chain of custody form
3.1 Action Level Notification
' '*''. ' . ' .
The purpose behind action level notification is to make the EPA Remedial Project Officer
(RPM) or the Site Project Officer (SPO) aware of the potential human health risk at the
site. In accordance with the Region m Hazardous Waste Division policy, the EPA RPM
or SPO must be promptly notified of any contaminant exceeding the established action level
or the 10-day health advisory limit. The data for contaminants exceeding the action levels
must be validated as a top priority and reported to the RPM or SPO. Validation of the rest
of the data may then be completed normally.
3*1.1 Acceptance Criteria
EPA's Office of Solid Waste and Emergency Response has established 10-day health
advisory limits or the action levels for several organic compounds and elements of special
health risk concern based on the Safe Drinking Water Act. The volatile organic
compounds and their 10-day health advisory limits are listed in Table Ml-VQA-2. The
criteria for action level notification are as follows:
-The contaminant concentration must be equal to or above the established 10-
day health advisory limits.
Data for contaminants exceeding the action levels must be validated as a top
priority.
The following EPA personnel must be notified of the action level
exceedances:
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EPARPMorSPO
- EPA Section Chiefs:
- Site Investigation (SI)
"' .' ' - '
. Remedial
, Enforcement
- RCRA
-,'' EPA Section Toxicologists:
- ' Enforcement
Superfund
RCRA
The remaining data validation should be completed per normal procedures.
' Any special instructions from the Hazardous Waste Division should be
followed. .
Records should be kept of the data review, action level notification and any
follow-up instructions and actions.
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Procedure nor. Ml-VOA
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" Table Ml-VOA-2
VOLATILE ORGANIC ANALYTES AND ACTION LEVELS
Compound '.
Benzene
Chlorobenzene .:
1 , 1-Dichloroethylene
trans-1,2- .^.
Dichloroethylene ;':, J. '', ..;..
l,24)ichtoroprppane"i;^ ?%
Methylethyl ketone
(MEK, 2-butanone) V ^
Tetrachloroethylene .
1,1,1-Trichloroethane .
Xylenes
Action
Level*
,'.Vv'-233-:. .'.'-.:
:.ฃpOO,V'v
-1,000
:^2;720,;;- '
3^90 ^v>
}&**
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3.1.5 Reporting
Copies of Form I's can be used to highlight the contaminants above the action levels. The
findings of the focused validation can be summarized in a memorandum, and the data
qualifiers resulting from focused validation may be written on the Form I's, The marked
up forms should be clarified that they, represent validation of only the contaminants
exceeding the action levels,and.not all data.
32 Evaluation of Mass Spectra For Detected Compounds;:
''!*
The primary QC indicator checked in Level Ml is the mass spectra for the detected
compounds. This indicator pertains to evaluating a compound's presence by matching its
mass spectrum with a standard ;(knbwn) mass spectrum for the compound.'.No assessment
is made of the reported quantity of the compound or any quantitative quality control
indicators that could lend some uncertainty to the reported value.
3.2.7 Acceptance Criteria _
" : .*- -:-- .'.'
The acceptance criteria ^for inass spectral matching are given hi the CLP Functional
Guidelines and are as follows:,
. : . ' \
All ions present in the standard (known) spectrum at a relative intensity
greater than 10 percent must be present in the sample mass Spectrum.
The relative intensities of the qualifying ions (those above 10 percent relative
intensity), must be within +/-20 percent between the standard and sample
spectra, for example, an ion with a relative abundance of 50 percent in the
standard spectrum must be present between a relative abundance of 30 and
70 percent hi the sample spectrum).
Ions present in the sample above 10 percent relative abundance must be
accounted for.
3.2.2 Review Items
Form I's for each field sample, field blanks, and laboratory blanks included in a Sample
Delivery Group (SDG) are necessary to compile a list of the detected compounds. Mass
spectra are then necessary for each of the detected compounds in a sample. The required
mass spectra include both the sample spectra as well as the standard spectra.
With respect to the blanks, it may be beneficial to evaluate the blanks before the sample
mass spectra are evaluated. If a compound is found to be a common contaminant, i.e., it
is present in any one of the blanks and also in the sample, the concentration in the sample
should be evaluated with respect to the highest blank contamination using the 5 (or 10)
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times criteria before proceeding with the elaborate mass spectral evaluations. The effort
required for the sample mass spectral evaluation may be significantly reduced by
performing the blank evaluation first, The mass spectra for the blanks; however, should be
evaluated to ensure that the contaminants were identified properly.
All sample Form I's are generally located together in front of the data package. Copies of
the Form I's can .also be found in the detailed sample data package organized by sample;
i.e., the Form I and its substantiating raw data for a sample are placed together. The raw
data include a quantitation report and mass spectra for each detected compounds in that
sample are. A standard (known) mass spectrum, and two sample mass spectra (one
unaltered and another background-subtracted) are generally provided. The presentation of
the mass spectra differs for different instrument manufacturers, but information necessary
for evaluating mass spectra is always provided in some form. Hands-on experience with
different brands of mass spectrometers, although not essential, can be helpful in
interpreting the information.
Copies should be made of the Form I's, preferably from the summary data package, if
included.- Otherwise, the forms can be pulled out from the raw sample data package. All
detects should then "be highlighted with a marker or other convenient means. The. raw data
should then be tagged for every sample for evaluating the mass spectra and the
chromatograms (reconstructed ion current profiles).
3.2.3 Evaluation of Mass Spectra
Compare the highlighted Form I's with the tagged raw sample data. Verify that sample
results are present for all of the samples listed on the chain-of-custody form. Verify that
raw data are provided for every sample, and a Form I exists for every sample represented
by raw data. Verify on a sample-by-sample basis that mass spectra are provided for every
detected (highlighted) compound reported on the Form I's. A cross verification should
then be performed that all target compounds for which mass spectra are provided are also
reported as detected on Form I's. "
Mass spectral comparison routines based on the evaluation criteria presented earlier
(presence of major'ions and their relative intensities) are built into the instrument software;
therefore, performed automatically. A listing of ions and their relative intensities is not
produced; rather a score based on the extent of the fit of all criteria is produced. The
score is based on a basis of 100 or 1000 for a perfect match of the presence of major ions
and their relative abundances. The score is printed on the quantitation report as a "q"
value. A score upward of 60 percent of the maximum (upward of 60 or 600) is generally
considered acceptable for positive identification for a compound.
Visual comparison of a mass spectrum involves looking for the base ion (the mass fragment
with the highest intensity), the parent ion (mass fragment equal to the molecular weight of
the compound) and other characteristic ions representing removal of one or more functional
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groups (such as -CH3, -CH2-, -Cl, -OH, or a combination thereof) from tfte parent ion, the
base ion or other ions. The removal of functional groups is often successive and produces
a fingerprint pattern for a type of compound; i.e., straight-chain hydrocarbons produce a
characteristic envelope of mass fragments separated by 14 mass units. Similarly, aromatic
compounds produce a peculiar fingerprint. The base ion represents the most stable mass
fragment; therefore, it is always present. However, a parent ion often is unstable and may
not exist at all or may exist at a low abundance or relative intensity. .
Compare the standard (known) mass spectrum with the background-subtracted sample
spectrum for the presence of the base, parent and other characteristic ions. Although
background-subtracted and .unaltered mass spectra are generally provided, the; former type
of spectra are much cleaner looking due to the subtraction of column bleed or other broad-
based interferences; .therefore, better suited for comparison. Generally, the presence of
major ions and overall matching of the fingerprint-pattern between the standard and the
sample spectra can be considered satisfactory. The comparison is rather subjective, and
requires a trained-eye to deduce the information.
Interference still may be present in a background-subtracted mass spectrum due to co-,
eluting compounds ( as compared to column bleed or broad-based interferences). Unless
the interfering compound is an isomer or an analog of the target compound in question, the
fingerprints produced by the target .compound and the interfering compounds can be quite
different. Inseparable isdmers reflect a limitation of the gas chromaiography without any
recourse. Such isomers are reported as ' 'total'', for example, total xylenes (combination of
ortho-, meta- and para-xylenes). Analogous compounds generally have different retention
times; therefore, may not be of much concern. Thus, co-eluting compounds do not pose
any problems in evaluating the mass spectra.
Seldom does a CLP laboratory incorrectly interpret a mass spectrum, but there is a
subjective element to mass spectral interpretation. While working within the CLP
guidelines, the laboratories do have their own reporting practices at the limit of the
instrument's sensitivity. Most of the mass spectral identification problems occur near the
limit of detection where the differences in the relative intensities are not easily discernible.
Special attention should be paid in evaluating mass spectra for compounds detected at low
concentrations. In addition, oxygenated compounds such as acetone and 2-butanone
produce poor mass spectra. For such compounds, the standard spectrum may show the
presence of the parent ion, but the same may not be true of the sample spectrum.
Professional judgment should be exercised in evaluating such mass spectra.
Rearrangements and other side-reactions often occur inside a mass spectrometer. These
phenomena produce mass fragments that are not easily accountable from the structure of
the parent compound.
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3.2.4 Action
In the event the mass spectrum of a detected compound does not at all resemble the
standard spectrum or has extremely poor matching, the compound should be considered
undetected. In this case the detected value should be changed to the CRDL for that sample
and flagged as undetected, "U." (NOTE: This action is in, contrast to the EPA
Functional Guidelines which recommend rejection of data. It is felt that an outright
rejection of data is not justified. If the mass spectrum produced at a target compound's
retention time does not match the standard spectrum, a conclusion can be drawn that the
target compound is not present and the mass spectrum may be due to something else. In
such a case the target compound should be considered as undetected and data should not be
rejected. Make sure that the target compound in question does produce a good mass
spectrum by inspecting the standard mass spectrum from the calibration and the fit score on
the quantitation report
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NTentative identification. Partial proof of a compound's presence, but all
identification criteria not met.
UNo mass spectral match. Using professional judgment, the compound is
considered undetected.
RNo mass spectral match. Using professional judgment, the compound
data are rejectedfrom further use.
3.3 Evaluation of Chromatograms
The purpose behind evaluating the chromatograms is to get an idea regarding potential false
negatives, and gross analytical errors. Checking for positive data as described under mass
spectral'evaluation does not offer any insight intodata that are not reported (i.e., reported
as nondetecis). Laboratory error <ซ gross interference from other compounds could be the
reasons for erroneous reporting. The gas chromatograms or the reconstructed ion current
(RIG) profiles are the primary tools' used for the false negative evaluation under Level ML
3.3.1 Acceptance Criteria
There are no EPA-established criteria for evaluating chromatograms for false negatives.
The criteria used for evaluating chromatograms are based on good laboratory and scientific
practices, and these are not hard and fast requirements. The suggested evaluation criteria
are:' . . '''.-.
There should not be any significant peaks in the chromatograms that are not
accounted for as TCLs or TICs. Significant peaks are those with a
minimum peak height of 10 percent of the closest internal standard.
The chromatograms should ideally have base-line resolution between
adjacent peaks. Also, there should not be broad (unresolved) envelopes in
the chromatograms.
There should not be abrupt shifts in the baseline.
There should not be peak tailing or sharp rise in the peak fronts.
-------
Case No.:
SDG No.:]
Data Reviewer:
Site:
Procedure No.: Ml-VOA
Revision: 1
Date: 06/30/1995
Page 11 of 18
Table Ml-VOA-3
VGA MASS SPECTRAL EVALUATION SUMMARY
Dates Analyzed:
Instrument ID:
^sr .
OwpoouL ,
CaotomeOiMat
1
T ....
A . ' '' '" "
a ' . '. . '-:
7 ". ' ' ..-- '' ."
8 ' ' ' : ' '" ''*'''
Q. . :'' :'' '-. -V :_''
10 - .'.. '' '
t
V)
Biwnbme&MB -
Vinyl Chloride
(*)
Chlotoefl^ne
Memyfcne CUoride
Acetone
Carbon Dbalfide
1.1-Dichloroethene
1,1-Dichloroethane
(*)
(#)
1,2-Dichloroethene (total)
Chloroform
(*)
1 ,2-Dichloroethane
2-Butanone
1,1, 1-Trichloroethane
Carbon Tetrachloride
Bromodichloromethane
1 ,2-Dichloropropane (*)
cis-1 ,3-Dichloropropene
Trichloroethene
Dibromochloromethane
1 , 1 ,2-Trichloroelhane
Benzene
AR
trans-1 ,3-Dichloropropene
Bromoform
(#)
4-MethyI-2-Pentanone
2-Hexanone
Tetrachloroethene
1,1,2,2-Tetrachioroethane (#)
Toluene
*)(AR)
Chlorobcnzene (<0(AR)
Ethylbenzene
Styrene
Xylenes (total)
ซ)(AR)
(AR)
(AR)
i
>. .. _ _ ......
ซ= - - - ' .::
<.... ' ' ' .-.- . . . .
i; -.- . . : : . .. -':-..' ".'vsv.T-ifte; ' -y ; -.
7-.' -. .' ' - :: ' .-/'.' " ' *> '. '-. : .
'ซ' ' .' - = ' ..-,.:'.
,0-.7-::'---A'-.; .' - ,. ' ---':=, .'.:.' ./;"...:
^io/'- : - '". ... .-.-;.:,-.,>, :Vv. ' .'. :
'; ' ' ; .- ^.'''^"^''M^'j "'; Sample Identifier :. ^"-' v-!vv vv';''.:::^''-' . - ' '
^ 1
MS
;
RT
v "->
MS
..v
V. ."
'-
RT
'.i
'.-,'
.,.
*^^
MS
>i'?>
';:-fc:;
RT
V.;;?
''".- '
'^-4^
MS
-'
RT
:;v':..'
-- -
.
'-* ~
MS
'RT
'_;
>
6
MS
Rt
'
''.i '.
MS
r
RT
";*.
1
,'/ซviy..:'-
MS
/?- rv-
.'-''ซ
''!i'
. /:
. ~
.-
RT
K-;
-V.vv
. ป.
^:,^
"
.>:-9- '
MS
,-V';V
\-v'
-? -
'.
RT
/-.'
. '
10
MS
:. *
-
.
RT
-------
Procedure no.: Ml-VOA
Revision: 1
Date: 06/30/1995
Page 12 of 18
3.3.2 Review Items
Chromatograms, or the RIC profiles for each sample are necessary for the evaluation. The
RIC profiles can be found in the front of the raw data package for each sample. The
quantitation report for each sample is also necessary to retrieve either the retention times or
information regarding scan numbers to compare with the peaks on the Chromatograms.
3.3.3 Evaluation of Chromatograms
Visually inspect the chrontegrMjs for. all peaks that appear to be at least 10 percent in
height of the nearest internal standard. Compare that the scan number or the retention time
that appears on the x-axis of the.RIC profile with that listed on the qiiantitation report for
the TCLs or the Ubrary search record for the TICs. Make sure that all significant pealcs
are accounted for.
Also observe the RIC profile for peak resolution between adjacent peaks: Poor peak-to-
peak resolution is indicative of degrading performance of the gas chromatographic column.
The values obtamed from a degrading system are prone to be inaccurate. Obviously
certain isomeric or homologous compounds are difficult to separate. But generally, there
should beat least 90 percent valley between the neighboring peaks.
Inspect the RIC profile for broad, -unresolved envelopes. These are generally indicative of
outside interference from a series of homologous compounds such as- straight-chain
hydrocarbons. Especially, assess the interference with the internal standards and surrogates
under the envelope using the expected area counts. The standard values that are far from
the expected values may be indicative of potential problems with the TCL detection or
quantification.
'
Inspect the RIC profile for abrupt shifts in the baseline. Such shifts are indicative of
problems with instrument sensitivity or leakage in the system. The area counts obtained
from shifted baseline are inaccurate, or even the detection of a TCL at low concentration
may be missed.
I "...
Rapid peak rising or peak tailing indicate problems with the gas chromatographic column,
such as depleted stationary phase on the column, decomposition of the stationary phase or
creation of active sites. Again, a visual inspection of the RIC profile will yield information
on the shape of the peak.
3.3.4 Action
Professional discretion must be used when evaluating and qualifying data based on the
chromatographic evaluations. An experienced chemist can generally infer the magnitude
and the frequency of; the problem from the RIC profile. If the problem appears to be
-------
Procedure no.: Ml-VOA
Revision: 1
Date: 06/30/1995
Page 13 of 18
systematic, then it should be brought to the laboratories attention and resolved.
Intermittent problems may or may not require any action. The following guidelines are
suggested when acting on RIC profile observations:
Any unaccounted TCL peak with area equivalent to or greater than the
lowest reportable limit for the sample must be brought to the laboratory's
attention and resolved. Any unaccounted non-TCl^
-------
Procedure no.: Ml-VOA
Revision: 1
Date: 06/30/1995
- Page 14 of 18
problem. For example, the magnitude of a drop in tne oaseline below the
zero line may not be estimated and could be very significant. On the other
hand, a drop that yields a baseline still above zero can be put in a
perspective with the original baseline and a general appearance of the entire
RIC profile.
The .problems with peak symmetry are indicative of system degradation, and
should b^bjtpught: to the attention of the laboratory for a corrective action.
Professional judgment should be used when and if qualifying any data due to
-,. First the problem should be defined in terms of
perastenoe||bipuhout the chromatogram and also from sample to sample.
^shapes and area counts for the internal and surrogate
i evaluated to see if the problem could have affected
; and/or quantification. Data qualification may, be
area counts are acceptable.
3.3.5 Reporting
The Mass Spectral Bva^uation Form (Table Ml-VOA-3) presented earlier may be used to
note any brief comments bii tiie'chromatographic evaluations. The comments may be noted
against each sample identifier^ For more descriptive comments, a separate sheet may be
used. - . .-- ^''-' -- ' ; ; -
3.4 Evaluation of Retention Times
While not unequivocal in identifying a compound, the retention times are quite helpful in
confirming the presence of a detected compound. Matching of mass spectrum and
retention time of sample with those of a standard yields higher credibility and confidence
level to the detection in the sample. On the other hand, not matching the retention time
may or may not invalidate the detection. If a mass spectral match is made beyond any
doubt, poor matching of the retention time may not have adverse impact on the detection.
If mass spectral matching is unacceptable or only partial, and the retention times do not
match, then a strong doubt can be cast on a compound's presence.
ii '
3.4.1 Acceptance Criteria
The criteria for retention times are specified in the EPA's functional guidelines as follows:
The relative retention times (RRTs) must be within +/-0.06 RRT units of
the applicable internal standard RRT.
-------
Procedure no.: Ml-VOA
Revision: 1
Date: 06/30/1995
Page 15 of 18
3.4.2 Review Items
Quantitation reports for the sample and continuing calibration are required for the
evaluation. These are located in the raw data for samples and standards.' A copy of the
continuing calibration quantitation reports may be made or the reports pulled out from the
raw data to facilitate a comparison with the sample quantitation reports. -
3.4.3 Evaluation Procedures
For the detected compounds, determine the relative retention time for the compounds by
dividing their retention times with the retention time of their associated infernal standard in
the samples as well as in the applicable continuing (or initial) calibrations.The sample
RRTs must fall in range of standard RRT +/- 0.06. units.
3.4.4 Action
Action for retention time evaluation requires professional discretion. Action taken must be
based on other data such as mass spectra and not on retention times alone. .The following
actions are suggested for several potential situations. :
Acceptable matching of the mass spectra and the RRTsNo action
suggested.
Acceptable matching of the mass spectra but poor matching of the RRTs
No action suggested, but the cause of retention time shift may be
investigated. Check to see if similar discrepancies are observed in other
parts of the chromatogram. Often high concentration of a compound will
cause shifts in the retention times for other compounds in the nearby eluting
region, but shifts in retention times in other areas may not be observed.
Shifts all through the chromatogram may be indicative of an erratic system,
such as flow rate fluctuations, poor temperature regulation, restriction or
leakage in the system. There are likely chances that the sample values in
such conditions may be inaccurate. Positive data may be qualified as
estimated, "J," if deemed essential.
3.4.5 Reporting
The Ml-VOA-MS Form (Table Ml-VOA-3) presented earlier may be used to record any
problems in the RRT matching. For the detected compounds in each sample, the calculated
RRTs may be recorded under the "RT" column. A data qualifier code may be added to
the values exceeding 0.06 RRT and requiring qualification, such as "0.15J," for a
compound with a difference of 0.15 RRT units and where a professional judgment to
estimate the data is exercised.
-------
Procedure no.: Ml-VOA
Revision: 1
Date: 06/30/1995
Page 16 of 18
3.5 Evaluation of Blanks
Laboratory blanks and field blanks have a profound impact on false positives reported in
samples; i.e., compounds reported as positive detects but not originating from the samples
themselves. Cross contamination from the sampling equipment, incidental contamination
from the field conditions or contamination from the laboratory equipment or general
environmental are likely sources of false positives in the samples. .
' ..:'.'.:--!- ซ"'''-.'.", ' ' : " . . . ' ' ' :'. ."
3.5.1 Acceptance Criteria! >
./;^-;^^;-'>. .. '.- ''.''.- ; : ''> -.' '
Criteria for blank evaluation are specified in the EPA's functional guidelines. In addition,
Region m has some additional requirements modifying the guidance. The acceptance
criteria for blanks apply equally to any type of blanks associated with either sampling or
analysis, such as trip blanks^ rinsate blanks, field-or' bottle blanks, and laboratory method
blanks. While' there are several criteria for evaluating the blanks, the .only criterion
applicable to Level Ml is the comparison of the blank and sample concentrations. This
criterion is: ' ' ' .-;.^v.;^^.y/,.;.. ' ..'." ' '.'.
, ' '' ^;'^.-'-HryVffi'-;;.'',' '-. . :. --. ' . '
For common contaminants, such as methylene chloride, acetone and
2-butanone, the sample concentration must be minimally 10 times the blank
.concentration to be considered a positive detect. Other contaminants must
be present in the sample at or above 5 times the blank concentration. The
blank with the highest concentration must be used (this is, if the laboratory
blank has the highest concentration of methylene chloride, and the equipment
rinsate blank has the highest concentration of acetone, both of these blanks
must be used to qualify the respective contaminants). All blanks should be
checked and the highest concentration of contaminants in any blank should
be used for data qualification.
3.5.2 Review Items
Data requirements and data retrieval procedures for blanks are the same as those for the
field samples because the blanks as well as field samples are validated similarly. Form I's,
mass spectra, chromatograms, quantitation reports, etc., are essential for performing a
validation of the blanks first. .
3.5.3 Evaluation Procedure
Validate the blanks the same as the field samples, detailed validation procedures are
described above under appropriate sections. Use the validated blank results for a
comparison with the sample results. Make certain that the samples and blanks are
evaluated on the same basis of sample weight or volume, dilution factors, moisture content,
etc. Use the 5 (or 10) times the highest blank concentrations for qualifying the sample
data.
-------
Procedure no.: Ml-VOA
Revision: 1
Date: 06/30/1995
Page 17 of 18
3.5.4 Action
-i-.
meeting the blank
If the sample concentrations do not meet the criteria of 5 (or 10) times the blank
concentration, the sample results should be considered essentially undetected (or as not
detected substantially above the levels reported in the blanks); therefore, flagged "B" in
accordance with the Region ffl data validation guidelines. _
3.5.5 Reporting
Form I's may be used to write the "B" data qualifier for the.data not
'criteria. ' ' . ';' ('' . - '. ' . ./. ' '
3.6 Sample Paperwork " ; ' ;
The purpose for evaluating the sample paperwork is to determine that {he samples being
validated are indeed the ones taken from the site, and have not been tampered with.
Accurate sample identity is of paramount importance in substantiating "the sample data.
Without unequivocal sample identity and chain-of-custody procedures, the sample data may
not be defensible or enforceable. ':"
Under the current CLP contracts, the original paperwork (i.e., the purge package or the
administrative record) is included in the data package from the laboratory. It is assumed
that the data validator is not privy to the original paperwork; therefore^ the evaluation
criteria and procedures described below apply only to the documents that are generally
included in the data validation package. These documents are the chain-of-custody forms
and Region HI Shipping Record.
3.6.1 Acceptance Criteria
Criteria for acceptability or authenticity of the sampling paperwork, document control and
chain-of-custody have been established by the National Enforcement Investigations Center*
(NEIC), in support of the CLP. Overall criteria are too numerous and subjective to be
discussed here, but the criteria that apply to data validation are as follows:
The chain-of-custody form should be properly and completely filled out
including the sampler signatures, date and time of sampling, sampling station
identification, analyses requested, traffic numbers, tag numbers, etc. These
data are minimally required to confirm the authenticity of the sample and its
data.
The chain-of-custody must be maintained at all times. The custody transfers
between different parties must be signed and. dated.;
-------
Procedure no.: Ml-VOA
Revision: 1
Pate: 06/30/1995
Page 18 of 18
3.6.2 Review Items
A copy of the chain-of-custody form is,essential to confirm the identity of the samples. In
addition, the Region m Shipping Record is essential to identify the field QC samples. The
chain-of-custody and Shipping Record are generally located in front of the data package.
3.6.3 Evaluation Procedure
'. ...v-J.s-F:1/'?:-'-1-"' .-..-, .
' ' - . ' '-'#^$^;$&^; ' ... ' ' '"':''.
Ensure that the chain-of-custody fprm was signed and dated by the samplers, and a time
and date were entei^/for>sainpleVq)liection. The laboratory copy of the chain-of-custody
must have the signature of the laboratory sample custodian. Any errors on the form should
have been crossed out with a single line through the entry. Verify that all collected
samples have unique station identification^ traffic numbers and sample tag numbers.
Ensure that the Region HI Shipping Record correctly reflects the information on the chain-
" ''
3.6.4 Action
The action to be taken in qualifying the data is highly dependent on the nature of the
problem. Some errors in paperwork are practically unavoidable in real situations. An
effort should be made to reconcile the differences by cross checking the field notebooks
against the sampling paperwork. Occasionally, the samplers may forget to sign the chain-
of-custody; however, the field notebooks may amply describe the sampling event.
Problems are also inevitable in noting or cross-referencing sample tag numbers and traffic
numbers. Generally, there are several alternate sources of information to substantiate or.
refute the problem.
3.6.5 Reporting
Any discrepancies found in the paperwork must be immediately brought to the attention of
the EPA RPM or SPO. Clearly define the problems in a memorandum to the responsible
parties. Attach marked copies of the chain-of-custody forms to substantiate the findings.
-------
Procedure No.: M2-VOA
Revision: 1
Date: 06/30/1995
Page 1 of 34
Appendix A-2
Validation of Volatile Organic Analyte Data
Manual Level M2
1. Purpose and Applicability
:.':-.V^i-'!:'i:'.->..y j^-. ' " . . '-...-';'''-"<ฃ:
This procedure provides step-by-step instructions to manually validate the volatile organic
analyte (VOA) data using the /manual innovative data vah'dation approach at Level M2.
This approach focuses on the use of information contained on the GLPforms andla review
of chromatograms as summarized in Table M2-VOA-1. The procedures are based on
modifications to Regions Hi's National Functional Guidelines for Organic Data Review.
.' . *^ .'-"-. .--. _ -'.. . f .' *^ . .""-.:. . . .
The procedure is applicable -to rlhie VOA data obtained using '
Program Statement of Work (CLP SOW). Hard copy data conforming to the CXP SOW
specifications are essential in order, tp cany out the procedure.^/ V. c ;l!:-:; j" / : ;
Data validated using this procedure are considered usable for the following types of
purposes; however, the data -users must decide on a case-by-case basis whether the
procedure is suitable for their intended data uses. The suggested data uses are:
Oversight of activities led by other parties
Comparison to action levels
Initial site investigation
Contamination sources
Nature and extent of contamination
Preliminary risk assessment
Risk assessment with known high levels of toxics
Feasibility study
Preliminary design
Treatability study US' EPฃ,aH.ead3uarters Library
33 Mail code 3201
i T * 120ฐ Pennsylvania Avenue NW
cleanup verification Washington DC 20460
-------
Procedure No.: M2-VOA
Revision No.: 1
Date: 06/30/1995
Page 2 of 34
Table M2-VOA-1
QC CHECKLIST FOR LEVEL M2
CLP RAS VOLATILE ORGANICS
Action Level NotificaticaiW
Tune
Initial Calibration (RRF)
' '
Initial Calibration (%RSD)
'' ''' '
. . ...
Continuing Calibration C^Rl^
. .. .. .
Continuing Calibration (%D);
Labbratoiy .Blank
MS/MSD (%R,RPD)
Internal Standard Area
Field Blank
Sample Paperwork
Holding Time
Retention Time
Surrogate Recovery
Dilution Factor
Moisture Content
Mass Spectra
Chromatograms
Raw Data
'm^~:
X1"5 fc
... '':
X
M3
' X
X
Comhinfid
".X^tte
' ..'.j.;-S-'.-
X
C3
"...-'X
. , " -
-------
Procedure No.: M2-VOA
Revision: 1
Date: 06/30/1995
Page 3 of 34
2. Quality Control Measures Checked
Table M2-VOA-1 highlights the quality control (QC) indicators evaluated under this data
validation procedure. . .
l!3. Procedure
*&**&%ฃ'':, :--\
The following subsections describe for each of the QC indicators the acceptance criteria,
W . ...._, 'ฃ '. -" ..'>iwi*.-i:;--~ - - ' . . - - *. - *
data requirements and retrieyaTpTXJC data, evaluation of the QC data, actions taken in the
event the QC acceptanceIcnte^iureexceeded, and documentation of the QC violations in
a standardized report
The volatile data i^i^mentsltq^;.(ฑe6ked are listed below:
, - ' "_,"_ ' - ,V*"- f'.^.v";.' >**' - ' ' -
3.1 Action Level Notir|cation
3.2 Technical Holding Times (CCS - Contractual holding times only)
.\ " ..
3.3 GC/MS Instrument Performance Check (CCS)
3.4 Initial CalibrationXCCS)
3.5 Continuing Calibration (CCS)
3.6 Blanks
3.7 System Monitoring Compounds (CCS)
3.8 Matrix Spike/Matrix Spike Duplicate
3.9 Internal Standards
3.10 Reported Contract Required Quantitation Limits (CRQLs)
3.11 Tentatively Identified Compounds
Two forms have been developed to assist in the performance and documentation of
implementing Level M2. The first form, M2-VOA-QUAL, summarizes holding time,
calibrations, blanks, surrogates, and internal standards. The second form, M2-VOA-SPK,
summarizes surrogate and matrix spike quality control checks. These forms are presented
in Table M2-VOA-2 and Table M2-VOA-3.
-------
Procedure No- M2-VOA
Revision: 1
Date: 06/30/1995
Page 4 of 34
Reporting requirements for Level M2 are:
Hand annotate the Form I's, including
1 Data validation qualifiers
Sample identification number
Sampling location
. ..
Provide a i narrative ithat includes
A statement that defines the level of the data review, ie. M2
problems assockted with the analysis,
Highlight issues that may have affected detection limits
,' ' . .:-V-r:':-Vi;i"''v.5!v'^-' .V.' ' ' ' ' .-,.
1 -...'.':{ .>ป;'&. .u,*-a&*tฃ , . . ' " ..-
.-.,-' -.,1v:iJisr--.^j!-.-.iซ.":- . . . . ... --.':..
Include the following attachments ^ * . . '"""
- A Ustof^^Walidation qualifiers :
' ,. * '"-' 'j.'.J'ป^*W''*'1-.
-------
Case No..
SDG No.:.
Data Reviewer::
Site: ,
Procedure No,: M2-VOA
Revision: 1
Date: 06/30/1995
Page 5 of 34
Table MB-VOA-2. VOA Quali&r Summary (CaEbntipos, Blanks, Haldmt lime, Surrogates, Internal Standards)
Dite(i) Analyzed:
Samples Analyzed Within 12 Houn of
Tune? Vea No
Tune CMC? _Yes _No
Method Blank ID: .
Sample Identifier:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Hold Time
Out, days
AR
All
Stindinfi
s
SI
tlTPOffftt
S3.
*M
S3
: ซ.>1
ISTDt
IS1
B2
'
IS3
Date:
Time:
Compound: SPCC (I)
CCC(ป)
Aromatic (AR)
Chtomfmtfiiine ' (f\
BrramiK*ane
Vinvl Chloride f*>
ChlorMlhape
Methvlene Chloride
Acetone
Caibon Dinilfide
1.1-Dichloraethene f*t
1.1-Dichloroethane (fl
1.2-DichloroetheneYtotan
Chloroform <*>
1 2-Dichloroethane
2-Butflnone
1 . 1 . 1 -Trichloroethane
Carbon Tetrachloride
Bromodichloromethane
1 .2-Dichlorooronane (*\
cis-1 ,3-Dichloroorooene
Tnchloraelhene
Dibromochloromethane
1 . 1 .2-Trichloroethane
Benzene AR
trans- 1 .3-Dichlorooronene
Bromoform (If)
4-Methvl-2-Pentanone
2-Hexanone
Tetniihloroethene
1.1.2.2-Tetnchloroethane (ft
Toluene f*VA!H
Chlorobenzene (f)(AR)
Ethvlbenzene (*)(AR)
Stvrene fARI
Xvlenes ftotaH (AK\
Initial Gd.
RRF<.05
*RSD>30
Coatin^C*
RRF<.05
ซD>25
Blanks
Mett. Trio
,
- .,
OoaBfiers
<+/)
;
>i
s
f
i
i
s
i
2
I
S
1
3
TICs Reported In BUnk(i):
Reported as:
El
fog/kg. ug/Lt
-------
Case No.:_
SDG No.:.
Data Reviewer:
Site:
Procedure No.: M2-VOA
Revision: 1
Date: 06/30/1995
Page 6 of 34
Table MJ-VOAJ. VOA Surrogate and Matrix Spike Quality Control Summary
Sample Identifier
(Acceptance Ranee, %R):
1.
2.
3.
4.
5. .. ' " '
6.
7.
8.
9.
10.
11.
12.
13.
Aoueoui Sample Reeoveriet, %R
SI
88-110
-- .,
' t
1 - ,,
52
86-115
.
"
S3 '
76-114
(
1
Soil Sample Recovery. %R
SI
84-138
\
S2
59-113
S3
70-121
Qualifiers ซ/-)
. -
SI Tohwne-dS, S2 Bromofluorobeozeae,S3 l^-diehlofoe1faane-d4
MS/MSD Data Sdmmarv
SPCCd)
CCC(ซ)
Spike ComponndAromatk (AH)
Metric SiAe. ttttmirv %R
lUnge
Actual
Matrix Spike Dupfcate,
RecoTerv. %R
Range
Actual
MS/MSD Precision, RPD
Range
Actual
Qualifiers
<+/)
AQUEOUS SAMPLES
1,1-Dichloroethene (*)
Trichloroethene
Benzene AR
Toluene (*)(AR)
Chlorobenzene (WAR)
61-145
71-120
76-127
. 76-125
75-130
61-145
7M20
76-127
76-125
75-130
14
14
11
13
13
SOIL SAMPLES
1,1-DicWoroethene (*)
Trichloroethene
Benzene AR
Toluene (*)(AR)
Chlorobenzene (D(AR)
59-172
62-137
66-142
59-139
60-133
59-172
62-137
66-142
59-139
60-133
22
24
21
21
21
'
-------
Procedure No.: M2-VOA
Revision: 1
Date: 06/30/1995
Page 7 of 34
Codes Related to Quantitation (Can be used for both positive results and sample
quantitation limits):
J = Analyte present. Reported value may not be accurate or precise.
K = Analyte present Reported value may be biased high. Actual value
L = Analyte present. Reported value may be biasiedtow^Actual value is
expected to be higher. -", v^'v7%S:;:; V;
UJ = Not detected, quantitation limit may be inaccurate or imprecise.
*ฃf-*' '*'''' ;'. ,-:f^fi$^
UL = Not detected/ quantitation limit is probably higher.
. . " -<^'^
Other Codes
Q = No analytical result
" r '-. ,.
* = Results reported from diluted analysis.
3.1 Action Level Notification
The purpose behind action level notification is to make the EPA Remedial Project Officer
(RPM) or the Site Project Officer (SPO) aware of the potential human health risk at the
site. In accordance with the Region m Hazardous .Waste Division policy, the EPA RPM
or SPO must be promptly notified of any contaminant exceeding the established action level
or the 10-day health advisory limit. The data for contaminants exceeding the action levels
must be validated as a top priority and reported to the RPM or SPO. Validation of the rest
of the data may then be completed normally.
3.1.1 Acceptance Criteria
EPA's Office of Solid Waste and Emergency Response has established 10-day health
advisory limits or the action levels for several organic compounds and elements of special
health risk concern based on the Safe Drinking Water Act. The volatile organic
compounds and their 10-day health advisory limits are listed in Table M2-VOA-4. The
criteria for action level notification are as follows:
The contaminant concentration must be equal to or above the established 10-
day health advisory limits.
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Procedure No.: M2-VOA
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Date: 06/30/1995
Page 8 of 34
Data for contaminants exceeding the action levels must be validated as a top
priority.
The following EPA personnel must be notified of the action level
.
^^investigation (SI)
' --.i'''-' .' ''
EPA Section Toxicologists:
^ ':''"';' V;--^;;|^M;V\ '.'. "'
r- V Enforcement
Superfund
- RCRA
The remaining data validation should be completed per normal procedures.
' " '
Any special instructions from the Hazardous Waste Division should be
followed.
Records should be kept of the data review, action level notification and any
follow up instructions and actions.
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Procedure NOM M2-VOA
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Page 9 of 34
Table M2-VOA-4
VOLATILE ORGANIC ANALYTES AND ACTION LEVELS
Compound "..,". ...-.
Benzene ^ '
Chlorobenzene ; .'
1 , 1-Dichloroethylene
trans-1,2- . * ,
Dichloroethylene
1,2-Dichloropropane ' .
Methylethyl ketone ' .
(MEK, 2-butanone)
Tetrachloroethylene
1,1,1-Trichloroethane
Xylenes
Action
"gl*vel* v .
%^t;233. ';'
%4l;&0q'
1,000
v*'! . ป. ป ' "
, 2,720
' - / i
90
,^7,500;: v
f-.-f-f ',. . .;
'34,000
35,1)00
7,800
. ' :CompounbV"^j|ฃ^
Carbon tetrachloride l^^
1,2-Dichloroethane ^ 4v c-l
cis-l,2-Dichloroethylene
Dichloromethane>^>3^
f ^ i -ti ;-j A^-"?.^f^
(in^thylene chloride) ^ni
Ethylbenzene ;^^^
'Styrene. '.x,yV^^|^
-"-' v ' <'-v'ti*-i^i~/'
Toluene ' ^-W^ff?
Vinyl chloride
' '.. ""'-
Action
iatcyd*
K&o.-:
fl^wo:-;-'
|S-i,ooo .
!W**.--.r. ;-. '
sfSjS'?.* ซAA-~'
;
tfei'ioo'- ; '
^-5ft nnn
$*^?yw
W-^A-.: '.
f-Pe^oo" ;
i 2,600
-w.- .
*A11 units are ug/1.
3.1.2 Review Items
All data required to perform the complete Level M2 validation, as detailed in the following
sections are necessary for carrying out action level notification. The location of the data
and their retrieval procedures are also discussed below.
3.1.3 Evaluation Procedure
The evaluation process preceding action level notification will primarily consist of
comparing the results on Form I's with the action levels presented in Table M2-VOA-4.
Following the identification of the contaminants exceeding the action levels, focused data
validation should be performed using the criteria, and procedures described in the
appropriate sections below.
3.1.4 Action
The action resulting from focused data validation will be the notification of action level
exceedance to the personnel identified above in Section 3.1.1.
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Procedure No.: M2-VOA
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Page 10 of 34
3.L5 Reporting
Copies of Form I's can be used to highlight the contaminants above the action levels. The
findings of the focused validation can be summarized in a memorandum, and the data
qualifiers resulting from fojcn^^dation may be written on the Form I'S. The marked
up forms should be clarlfie^l^that- they represent validation of only the contaminants
* .-.-. v.- . ;:iiซ 'A- -Til **<:ป:-/>. '.* . -,.
exceeding the action
3.2 Technical Efo
.
The objective is tt>
from time of coUection tb^
,,. .-. '
3.2.1 Acceptance Crtie
- . f ... v:,;^fe
of results based on the holding time of the sample
ysis. - '
'
. ._, _______ w .. .
Technical requireme^vfi^^u^lpholding times have only been established for water
matrices. The holding time^^fOT^oils (and other non-aqueous matrices such as sediments,
oily wastes, and sludge) are^omn^tly^under investigation. In Region iti, a 14 day holding
time will be applied to all nim2aqueous samples. When soil holding time criteria are
established and. available, jfhe/j^rocedure'for qualifying soil samples will be re-evaluated.
The holding time criteria for water samples, as stated in the current 40 FR Part 136
(Clean Water Act) is as follows: .
For non-aromatic volatile compounds in cooled (@ 4ฐC) water samples, the
maximum holding time is 14 days from sample collection.
Maximum holding times for purgeable aromatic hydrocarbons in cooled (@ 4ฐC +.
2ฐC), acid-preserved (pH 2 or below) water samples are 14 days from sample
collection. .
'i . -
Water samples that have not been maintained at 4ฐC (ฑ 2ฐC) and/or preserved to a
pH of 2 or below should be analyzed within 7 days from sample collection. If
insufficient ice is used to ship samples, the laboratory may receive samples with no
ice left in the cooler. Under these circumstances, the temperature of the samples
may exceed 4*C.
It is further required that volatile compounds in properly preserved non-aqueous samples be
analyzed within 14 days of sample collection for all volatile compounds.
3.2.2 Review Items
Form I VOA, EPA Sample shipping log and/or chain-of-custody.
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Procedure No.: M2-VOA
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Page 11 of 34
3.2.3 Evaluation Procedure
Technical holding times are established by comparing the sampling dates on
the EPA Sample Traffic Report with dates of analysis on Form I VGA
Examine the sample records to determine if samples were preserved.' If it is
indicated that there were problems with the samples, then the ihtegiity of the
.. . ;'..'.-^'.t^rU -ir^&akc -! '.' . , '-: .. "". -;. ., --fcj|.^iJift*feSfeS*ฅ''ia' ซ-'
sample may have^be^^mpromised and professional judgmelKShould be
used to evalu^^e^effec^of the problem on flie sample
3.2.4 Action
If technical holding times are exceeded, qualify the sample tesiili
see Table M2-VOA-5).5- ; V : "i:"^
If there is no evidence that the samples were
technical holdmg times exceeded 7 days,
and sample quantitation limits with "UL" for ; s
professional judgment to determine if and how''*
compounds should also be qualified. Jp
ws. (Also
ฅ&?
and the
with "L"
Use
volatile
If the samples were properly preserved but the technical holding times
exceeded 14 days, qualify all positive results with 'lATiand all sample
quantitation limits with "UL."
Table M2-VOA-5
QUALIFICATION OF VOLATILE ANALYTES BASED ON TECHNICAL
HOLDING TIMES
Matrix
Water
Non-aqueous
Preserved
No
Yes
No/Yes
> 7 Days
All Aromatics*
None
None
14 Days
All Compounds
All Compounds
All Compounds
'"Reviewer should use professional judgment to determine if data for additional
compounds require qualification.
2. If technical holding times are grossly exceeded (e.g., by greater than two times the
required time for volatiles) either on the first analysis or upon re-analysis, the
reviewer must use professional judgment to determine the reliability of the data and
the effects of additional storage on the sample results. Should the reviewer
determine that qualification is necessary, non-detected volatile target compounds
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Procedure No.: M2-VOA
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Page 12 of 34
may be qualified unusable (R). Positive results are considered bias low and are
qualified with "L".
3. When there are other quality control problems in conjunction with' exceeded, holding
. times (such as suspected;laboratory contamination), the reviewer should follow the
hierarchy ofqualifim^^ particular, if for any reason me reviewer doubts the
presence of a cpmpo^ should display only tiie^'/B" or "R"
qiialifiet and i^^ is because no netjdirejc^cmx)f bias can be
inferred imder these^cbnditions. When results are reported by the laboratory as
below the CR^^thip^Lig qualifier is used over the "J" qualifier.
4. Customized;^ should be filled to show holding time
performance (oneTp^i|^H6ur period per instrument).
3.3 GC/MS InstrumentrPerformance Check
Gas chromatograpn/rnass spectrome^^ instrument performance checks (formerly.
referred to as tunmg) are performed to ensure mass resolution, identification, and to some"
. .. ^" ft. .+},$, f -'-trJi5'-',v '$ฃ' <.,-.'- r ;", t-v
degree, sensitivity. VTheป^tem:iire not "sample specific, Qmformance is determined
using standard materials, mereibre, these criteria should be met in all circumstances.
- '.';',:;':. ; ^ 'K-.! -'. ''.'.:' . ''
3.3.1 Acceptance Criteria :~-
The analysis of the instrument performance check solution must be performed at the
beginning of each 12-hour period during which samples or standards are analyzed. The
instrument performance check, bromofluorobenzene (BFB) for volatile analysis, must meet
the ion abundance criteria given below.
Bromofluorobenzene (BFB)
!
m/z Ion Abundance Criteria
50 8.0 - 40.0% of m/z 95
75 30.0 - 66.0% of m/z 95
95 Base peak, 100% relative abundance
96 5.0 - 9.0% of m/z 95
173 Less than 2.0% of m/z 174
174 50.0- 120.0% of m/z 95
175 4.0 - 9.0% of mass 174
176 93.0 - 101.0% of m/z 174
177 5.0 - 9.0% of m/z 176
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Procedure No.: M2-VOA
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Date: 06/30/1995
Page 13 of 34
NOTE: All ion abundances must be normalized to m/z 95, the nominal base peak,
even though the ion abundance of m/z 174 may be up to 120 percent that of
m/z 95.
3.3.2 Review Items
Form V VGA.
'"'". *?'> " :>i
3.3.3 Evaluation[tin^dK !^
1. Compare the data presented for each Instrument Performance Check (Form V
VGA) with each mass listing submitted to ensure the following: ''*|g;&;;;.':;_
Form V VOA is present and completed for each 12-hour period during
V. . ^>Y""ft'atf*'-'-' , ' 'j ' ' --.' ' .r.*-V*ti*-fซ^rV^.--.:. ฐ'
which samples were analyzed. ' \:^:v:5y.::^,rv
'..".-:.' 'A,^.'-'-; . :'.' -:.''; >?i*"i.1>KfS.J5'**'''??-'
The appropriate number of significant figures has teenreported (number of
significant, figures given for each ion in the ion abundance criteria column)
and that rounding is correct. (See SOW for requirements). 1;.
r
2. Verify that the mass assignment is correct and that the mass listing is normalized to
m/z 95. .
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Procedure No.: M2-VOA
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Page 14 of 34
3. If mass assignment is in error (such as m/z 96 is indicated as the base peak rather
than m/z 95), classify all associated data as unusable (R).
4. If ion abundance criteria are not met, professional judgment may be applied to
determine to what extent the data may be utilized. Guidelines to aid in the
application, of professional judgment to this topic are discussed as follows:
The most ^important factors to consider are the empikcal|j^ulte ; that .are
' . ;; v *' - . '< " . - ' '-^^ซ*^i<-^^^V>'?&t *-ป
relatively insensitive to location on the chromatographic|prqffl.e^and the type
of instrumentation. Therefore, the critical ion abimdaince^cn^a for BFB
are the m/?; 95^(5, 174/175, 174/176, and 17jS/177|^^5f|lie relative
abundances,of $t]JQ. and 75 are of lower importanoej:fe:^^fe^;: -
5. If the reviewer has reason to believe that instalment performance check criteria
. . . ..I-:',...:,.- . i, . ,.:";'.-. *:'.- ";4ป-frtf>'t.'-\"-\ ^ ,-
. . . ... . , . ,.. . .- ,
were achieved using techniques other than those described m n.p.4^then additional
information on the/instrument performance checks shouW b^^obtained. If the
techniques employed are found to be at variance with the contract requirements, the
performance and procedures of the laboratory may merit ey^^qaX^Qmcerns or
questions regarding laboratory performance should be noted for TPO action in the
ORDAS form. For example, if the reviewer has reason ^to believe that an
inappropriate technique was used to obtain background subtraction (such as
background subtracting from the solvent front or from anbther^region of the
chromatogram rather than the BFB peak), then this should be noted for TPO action
in the ORDAS form.
3.4 Initial Calibration
Compliance requirements for satisfactory instrument calibration are established to ensure
that the instrument is capable of producing acceptable qualitative and quantitative data for
compounds on the volatile target compound list (TCL). Initial calibration demonstrates that
the instrument is capable of acceptable performance in the beginning of the analytical run
and of producing a linear calibration curve.
r ' ,
3.4.1 Acceptance Criteria
'<: '
1. Initial calibration standards containing both volatile target .compounds and system
monitoring compounds are analyzed at concentrations of 10, 20, 50, 100, and 200
ug/L at the beginning of each analytical sequence or as necessary if the continuing
calibration acceptance criteria are not met. The initial calibration (and any
associated samples and blanks) must be analyzed within 12 hours of the associated
instrument performance check.
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Procedure No.: M2-VOA
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2. Separate initial calibrations must be performed for water samples (or medium level
soil samples) and for low level soil samples. The calibration for water samples and
medium level soil samples is performed with an uhheated purge and the calibration
for low level soil samples is performed with a heated purge; : /
'.- ' ' : .- ^^^^jy'. ' .'.-'' ' .'" '. ' .';':.- ;7S''V "'.'
3. Initial c^bration);standani Relative Response Factors (RRFs) for volatile target
compounds and:^^m^utoring compounds (surrogates) must ,be greater than or
equal to 0.05. ((^ntra^tual initial calibration RRF criteria are listed in Appendix
A\ \'^$&$*&3&'^-- . ' .-.- . ' ^,: ' ' '
.-*/ " . , .v'AV^Ci;''-'-;?.".' 'Y ' .-...._ .,.":.;
4. The Percent Relative Standard Deviation (%RSD) from the initial calibration must
be less than or equal to 30.0% for all compounds. (Contractual calibration %RSD
-ซป' ซ._."4ivi-H'ii''vfev,.j.-':.'... ' ' '. ' . ., .'-..". r-:.;;jv ' .
cntena are listed m Appendix A).
'- ~'
3.4.2 Re}
Form VI VGA and chromatbgrams.
3.4.3 Evaluation Procedures
1. Verify that the correct concentration of standards were used; for the initial
calibration (Le., 10, 20, 50, 100, and 200 ug/L for water). ^
2. Verify that the correct initial calibration was used for water and medium level soil
samples (i.e., unheated purge) and for low level soil samples (i.e., heated purge).
3. If any sample results were calculated using an initial calibration, verify that the
correct standard (i.e., the 50 ug/L standard) was used for calculating sample results
and that the samples were analyzed within 12 hours of the associated instrument
performance check.
4. Evaluate the initial calibration RRFs and RRFs for all volatile target compounds and
system monitoring compounds (surrogates):
Verify that for all volatile target compounds and system monitoring
compounds, the initial calibration RRFs are greater than or equal to 0.05.
NOTE: Because historical, performance data indicate poor response and/or erratic
behavior, the volatile compounds listed below have no contractual maximum
%RSD criteria. Contractually they must meet a minimum RRF criterion of
0.01; however, for data review purposes, the "greater than or equal to
0.05" criterion is applied to all volatile compounds.
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Procedure No.: M2-VQA
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Date: 06/30/1995
Page 16 of 34
Volatile Target Compounds Exhibiting Poor Response
Acetone
5 2-Butanone
Carbon disulfide
Methylene chloride
MM
.
NOTE: Compounds in bold are system monitoring compounds.
S. Evaluate the %RSD for all volatile target compounds and system monitoring
compounds: v; > V . . : ' ' '. '.'. '"." '^''.'.:''
!: 'v -\ . '". ' ' ' . ' ' ''-"''
a. Verity that all volatile target compounds have a %RSD of less than or equal
to 30.0%. The contractual criteria for an acceptable initial calibration
specifies that up to any 2 volatile target compounds may- fail to meet
minimum RRF or maximum %RSD as long as they have RRFs that are
greater than or equal to 0.010, and %RSD of less than or equal to 40.0%.
For data review purposes, however, all compounds must be considered for
qualification when the %RSD exceeds the +. 30.0% criterion.
/
b. If the %RSD is greater than 30.0%, then the reviewer should use
professional judgment to determine the need to check the points on the curve
for the cause of the non-linearity. This is checked by eliminating either the
high point or the low point and recalculating the %RSD.
3.4.4 Action
/ '
1. All volatile target compounds, including the "poor performers" listed above
(excluding the system monitoring compounds) will be qualified using the following
criteria:
a. If the %RSD is greater than 30.0% and all initial calibration RRFs greater
than or equal to 0.05, qualify positive results with "J". Non-detects are not
qualified. When the %RSD is grossly exceeded (i.e., > 50%) use
professional judgment for qualifying non-detects as "UJ".
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Procedure No.: M2-VOA
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b. If any initial calibration RRF is less than 0.05, qualify positive results that
have acceptable mass spectral identification with "L", and non-detected
analytes as unusable, "R".
2. At the reviewer's discretion, a more in-depth review to minimize the qualification of
data can be accomplished by considering the following: ^'-^y^??-.
a. If any of the required volatile compounds have a %RSD greater than 30.0%,
and if elimlnaiirig dther the high or the low pomt-bf the curve does not
restore the %RSD to less than or equal to 30.0%: ^ ^
i. : Quaiify;|X)sitive results for that opmpound(s) with ;**J". '
ii. No qualifiers are needed for volatile target compounds that were not
detected. J If the %RSD is grossly exceeded (U., >50%),
.-'-. professional judgment is used to qualify non-detects with *'UJ".
' '
b. If the Mgh point of the curve is outside of the linearity ^criteria (e.g., due to
. saturation):^ **%<-% '-.' .'_',.. ,."""'; "-"''
'\ ' , '
i. No qualifiers are required for positive results in the linear portion of
the curve. ' '.\--~-
ii. Qualify positive results outside of the linear portion of the curve with
a "J".
iii. No qualifiers are needed for volatile target compounds that were not
detected. If the %RSD is grossly exceeded (i.e., >50%,
professional judgment is used to qualify non-detects with "UJ".
c. If the low end of the curve is outside of the linearity criteria:
i. No qualifiers are required for positive results in the linear portion of
the curve.
ii. Qualify low level positive results in the area of non-linearity with
tซTปป
J ' X
iii. No qualifiers are needed for volatile target compounds that were not
detected. If the %RSD is grossly exceeded (i.e., >50%),
professional judgment is used to qualify non-detects with "UJ".
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Procedure No.: M2-VOA
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Page 18 of 34
NOTE: If a, b, or c options are used, a description of the process must be clearly
stated in the data review narrative.
3. If the laboratory has failed to provide adequate calibration information, the designated
representative should contact the laboratory and request the necessary information. If
the information is not available, the reviewer must use professional judgment to assess
the data. v;
. .. .,., .
4. The potent^ effl^ion^the data due to unacceptable calibration criteria should be
noted in the data review jnarrative. /
5.. If calibration criteria are exceeded, this should be noted on the ORDAS.
' . _; ' . v'iV&'ivi.W,.*'.": ' '
3.5 Continuing Calibration
-"._ !'...'-'-#^l?^-vV':'' '
Compliance requirement} for ^satisfactory instrument calibration are established to ensure
that the instrument is capable of producing acceptable qualitative and quantitative data.
Continuing calibration^establishes the 12-hour relative response factors on which the
quantitations are based and checks satisfactory performance of the instrument on a day-to-
day basis. ; "': -.'
3.5.1 Acceptance Criteria.
1. Continuing calibration standards containing both, target compounds and system
monitoring compounds are analyzed at the beginning of each 12-hour analysis period
following the analysis of the instrument performance check and prior to the analysis of
the method blank and samples. The continuing calibration may either be a part of the
initial calibration or run independently on another 12-hour analysis period. .
ป' i .
2. The continuing calibration RRF for volatile target compounds and system monitoring
compounds must be greater than or equal to 0.05. .
3. The percent difference (%D) between the initial calibration RRF and the continuing
calibration RRF must be within ฑ 25.0%.
3.5.2 Review Items
Review Items: Form Vn VOA and chromatograms.
ii
3.5.3 Evaluation Procedure
1. Verify that the continuing calibration was run at the required frequency and that the
continuing calibration was compared to the correct initial calibration.
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Procedure No.: M2-VOA
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Page 19 of 34
2. Evaluate the continuing calibration RRF for all volatile target compounds and system
monitoring compounds:
Verify that all volatile compounds and system monitoring compounds meet
the RRF specifications.
NOTE: Because nistpnc^ iperformance data indicate;:poor\r^ipoijse;and/or erratic
behavior,vthe compounds listed in Section 3.4.3, above, have no contractual
niaximum^D "criteria. (^ntractiiaUy mey must meet a mmimum RRF
. criterion bl^pipl^hbwever, for data review purposes^the' "greater than or
equal to 0.0^" criterion is applied to. all volatile compounds. .
3. Evaluate the^ %D;;J>e^^a|matial caUbratioiuRRF and continuing calibration RRF for
one or more r--^ii-'a/-v**:* '
within ฑ 25.0% for aU volatiletorget compounds and
system monitoring compounds. Note those compounds which have a %D
outside thejat 2^.0% criterion. The contractual OTteria for an acceptable
contmumg^calibration specifies that up to any 2 volatile target compounds
may foil to^ineet minimum RRF or maximum %D as long as they have
RRFs that are greater than or equal to 0.010, and %D of less than or equal
to 40.0%. For data review purposes, however, all compounds must be
considered for qualification when the %D exceeds 4he ฑ 2570% criterion.
3.5.4 Action
1. The reviewer should use professional judgment to determine if it is necessary to
qualify the data for any volatile target compound. If qualification of data is required,
it should be performed using the following guidelines:
a. If the %D is outside the ฑ 25.0% criterion and the continuing calibration
RRF is greater than or equal to 0.05, qualify positive results with "J".
b. If the %D is outside the ฑ, 25.0% criterion and the continuing calibration
RRF is greater than or equal to 0.05, no qualification of non-detected
volatile target compounds is necessary. If the %D is grossly exceeded
(>50%), professional judgment may be used to qualify non-detects with
"UJ".
c. If the continuing calibration RRF is less than 0.05, qualify positive results
that have acceptable mass spectral identifications with "L" or use
professional judgment and include justification for not qualifying the data in
the data review narrative.
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Procedure No.: M2-VOA
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Date: 06/30/1995
Page 20 of 34
d. If the continuing calibration RRF is less than 0.05, qualify non-detected
volatile target compounds as unusable, "R".
2. If the laboratory has failed to provide adequate calibration information, the designated
representative should 'contact the laboratory and request the necessary information. If
the information is jfot available, the reviewer must use professional judgment to assess
the data. -:-
3. The potential -effectsrion^the data due to unacceptable calibration criteria should be
'. ; '.'f'- ' ซ-". ';. "'' . .',.''".'
noted in the data review narrative. ,v
' ' ' ' '
4. If calibration criteria fareexceeded, this should be noted in the ORDAS.
3.6. Blanks
. i. i^"Yv>k<
. .-.,vJC".->.'
':\??i$$f^*$/'$?&:'' ' ' ' ''."'.'''
The purpose of -lalloio^^^^^cliS) blank analysis is to determine the existence and
magnitude of oohtaiqiinM^^esulting from laboratory (or field) activities. The criteria for.
evaluation of blanks apply,to;any blank associated with the samples (e.g., methods blanks,
instrument blanks,; trip blanks,rand equipment blanks). If problems with any blank exist,
all associated data must be carefully evaluated to determine whether or not there is an
inherent variability in the data, or if the problem is an isolated occurrence not affecting
other data.
3.6.1 Acceptance Criteria
1. No contaminants should be found in the blanks.
2. A method blank analysis must be performed after the calibration standards and once
for every 12-hour time period beginning with the injection of BFB.
3. The method blank must be analyzed on each GC/MS system used to analyze samples
for each type of analysis, i.e., unheated purge (water and medium level soil) and
heated purge (low level soil).
4. An instrument blank should be analyzed after any sample that has exceeded the initial
calibration range for any given compound to check that the blank is free of
interference and the system is not contaminated.
3.6.2 Review Items
Form I VOA, Form IV VOA and chromatograms.
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Procedure No.: M2-VOA
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Date: 06/30/1995
Page 21 of 34
3.6.3 Evaluation Procedures
1. Review the results of all associated blanks on the forms and chromatograms to evaluate
the presence of target and non-target compounds in the blanks.
2. Verify that a method blank analysis has been reported per matrix, per concentration
level for each 12-hour time period on each GC/MS system used to analyze volatile
samples. The reviewer can use the Method Blank Summary (FormTV VGA) to
identify the samples associated with each method blank. " :; :
3. Verify that the instrument blank analysis has been performed following any sample
analysis where a target analyte(s) is reported at high concentration^).:
3.6.4 Action ; : ;::/v
; . . '^^.' .".ฃ;,:" tiซV7'*\ : ' ' ".':-.';
' - .. v.--V:^'-fe;^;tfv ' '..-', ., ,';,:-i.- .
If the appropriate blanks were Jiot analyzed with the frequency described in Criteria 2, 3,
and 4, then me data reviewer should use professional judgment to determine if th&
associated sample data should be qualified. The reviewer may heed to obtain additional
information from the laboratory. The situation should be noted for TPO action on the
ORDAS form. ; !
Action regarding unsuitable blank results depends on the circumstances .and origin of the
blank. Positive sample results should be reported and qualified "B", if the concentration
of the compound in the sample is less than or equal to 10 times (lOx) the amount in any
blank for the common volatile laboratory contaminants (methylene chloride, acetone, and 2-
butanone), or 5 times (Sx) the amount for other volatile target compounds. In situations
where more than one blank is associated with a given sample, qualification should be based
upon a comparison with the blank having the highest concentration of a contaminant. The
results must not be corrected by subtracting any blank value.
For qualification purposes, consider all blanks in a case associated with all samples.
Field blanks measure contamination introduced not only in the field but also from the
laboratory. In general, evaluation of the impact on specific sample results is .handled the
same as with laboratory blanks. The reviewer should use caution in attributing
contamination to the field as opposed to laboratory sources. However, when field-
introduced contamination is suspected, it is helpful for the reviewer to consult the sampling
group to identify possible sources and prevent future reoccurrences. Verified field sources
of contamination should be noted in the data review narrative. If a field blank has the
highest concentration of a contaminant, then all samples in the associated case are qualified
"B", using the 5x and lOx rule. Other field blanks associated with the case are not
qualified.
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Specific actions are as follows:
1. If a volatile compound is found in a blank but not found in the sample, no action is
taken. If the contaminants found are volatile target compounds (or interfering non-
target compounds) at significant concentrations above the CRQL, men this should be
noted for TPO action in the ORDAS.
.... . i _
2. Any volatile compound detected in the sample (other than the common volatile
laboratory O)ntaminants)/4hat was also detected in any associated blank, is qualified
4 'B", when the sample concentration is less than five times (5x) the blank
concentration. For: common volatile laboratory contaminants, the results are qualified
"B", when the sample concentration is less than 10 times (lOx) the blank
concentration.-' .:^:^/soV;:. " " ' ^ . ' './"'' . -
3. The reviewer should note that blanks may not involve the same weights, volumes, or
dilution factors as the associated samples. These factors must be taken into
consideration when applying the "5x" and "lOx" criteria, such that a comparison of
the total amoimt of contamination is actually made.
Additionally, there may be instances where little or no contamination was present in
me associated blanks/ but qualification of the sample is deemed necessary. If the
reviewer determines that the contamination is from a source other than the sample,
he/she should qualify the data. Contamination introduced through dilution water is one
example. Although it is not always possible to determine, instances of this occurring
can be detected when contaminants are found in the diluted sample result but are
absent in the undiluted sample result. Since. both results are not routinely reported, it
' may be impossible to verify this source of contamination.
4. If gross contamination exists (i.e., saturated peaks by GC/MS), all affected compounds
in the associated samples should be qualified as unusable (R) due to interference. This
should be noted for TPO action in the ORDAS if the contamination is suspected of
having an effect on the sample results.
5. If inordinate numbers of other target compounds are found at low levels in the
blank(s), it may be indicative of a problem and should be noted for TPO action in the
ORDAS form.
6. The same consideration given to the target compounds should also be given to
Tentatively Identified Compounds (TICs), which are found in both the sample and
associated blank(s). (See VOA Section XHI for TIC guidance.)
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7. If an instrument blank was not analyzed following a sample analysis which contained
an analyte(s) at high concentration^), sample analysis results after the high
concentration sample must be evaluated for carryover. Professional judgment should
be used to determine if instrument cross-contamination has affected any positive
compound identification^). If instrument cross-contamination is suggested, then this
should be noted for TPO action if the cross-contamination is suspected of having an
effect on the sample results/Sample results which are pos^^a|tifects of carry-over
should be flagged as unusable (R).
8. When there is convincing evidence that contamination is restricted to a particular
instrument, matrix, or concentration level, the Sx/lOx rule will :only be applied to
compare contaminated blanks to certain associated samples T(as <|iposed to all samples
in the case). Some examples are as follows^ - '' '
' ''"'' '
Column bleed (siloxanes) may be localized to a particular instrument
' ' ' ' '
.
Methanbl extractions in the medium soil volatile analysis ^jrotocol can give rise to,
contaminants that are not seen in the low-level aqueous analyses. 'y
Common laboratory contaminants, such as methylene chloride, are generally too
unpredictable to safely assume contamination is restricted to a particular instrument,
matrix, or concentration leveU -x '-.--
9. For benzene and/or toluene, the reviewer may identify that the observed laboratory
contamination is attributable to a specific, regular, and predictable process (such as
trap bleed), which results in a constant 1 or 2 ppb instrument level concentration in all
runs (both samples and blanks). In this situation, the reviewer may want to consider
and flag certain results as tentatively identified, "N", as opposed to "B", if the
sample instrument level is clearly greater than the consistent level of contamination
detected in blanks and other samples. (This particular situation supersedes the Sx/lOx
rule.) ,
10. The following are examples of applying the blank qualification guidelines. Certain
circumstances may warrant deviations from these guidelines. Any deviations must be
clearly stated in the data review narrative.
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Example 1: Sample result is greater than the Contract Required Quantitation Limit
(CRQL), but is less than the 5x or lOx multiple of the blank result.
Rule
Blank Result
Sample Result 6Q ? v 30
:Final Sample Result 60B 30B
In the example for the "lOx" rule, sample results less than 70 (or 10 x 7)
would be qualified "B". In the case/of the "5x" rule, sample results less
than 35r(dr5 x;7)fwquld be qualified "B". .
Example 2: Sample result is less than the CRQL, and is also less than the 5x or lOx
multiple of the blank result. .
Rule .
Blank Result 6 .6
CRQL 5 :5
Sample Result 41 4J
Final Sample Result 4B 4B
Note that data are reported as 4B, indicating that the qualitative
presence is not confirmed.
Example 3: Sample result is greater than the 5x or lOx multiple of the blank result.
Rule
iP_x 5x
Blank Result 10 10
CRQL 5 5
Sample Results 120 60
Final Sample Result 120 60
For both the "10x".and "5x" rules, sample results exceeded the
adjusted blank result of 100 (or 10 x 10) and 50 (or 5 x 10),
respectively.
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3.7 System Monitoring Compounds (Surrogate Spikes)
Laboratory performance on individual samples is established by means of spiking activities.
All samples are spiked with system monitoring compounds (formerly referred to as
surrogates) prior to sample purging, the evaluation of the results of these system
monitoring compounds is not necessarily straightforward. The sample itself may produce
effects due to such factors as interferences and high conc^entratiohs of analytes. Since the
effects of the sample matrix are frequently outside the control Sfpe^wl^bry and may
present relatively unique problems, the evaluation and review of ^pPra^T'on specific
sample results is frequently subjective and demands analytical experience'and professional
judgment. Accordingly, this section consists primarily of guideUnes," in some cases with
several optional approaches suggested. -*>^s.,.,
3.7.7 Acceptance Criteria
1. Three system monitoring compounds (1,2^cMoroethane^4,'^rp^flubroyenieene, and
toluene-d8) are added to all samples and blanks to measure their recovery in
environmental samples and blank matrices. : ;^1^X*- '
2. Recoveries for system monitoring compounds in volatile samples and blanks must be
within the limits specified in Appendix A and the SOW.
3.7.2 Review Items
Form n VOA and chromatograms.
3.7.3 Evaluation Procedures
1. Check chromatograms to verify the recoveries on the System Monitoring Compound
Recovery FormForm n VOA.
2. The following should be determined from the System Monitoring Compound Recovery
form(s):
a. If any system monitoring compound(s) in the volatile fraction is out of
specification, there should be a reanalysis to confirm that the non-
compliance is due to sample matrix effects rather than laboratory
deficiencies. '
NOTE: When there are unacceptable system monitoring compound recoveries
followed by successful analyses, the laboratories are required to report only
the successful run.
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b. The laboratory failed to perform acceptably if system monitoring compounds
are outside criteria with no evidence of re-analysis. Medium soils must first
be re-extracted prior to, re-analysis when this occurs.
c. Verify that no blanks have system monitoring compounds outside the
3. Any time there'are^two or mpre analyses for a particular sample, the reviewer must
determine which a^ the best data to report Considerations should include but are not
limited to: . ?-xฃij&;&&^- '-' :. ' . .' .'.' Y'*.'
a. System monitoring compound recovery (marginal versus gross deviation).
b. Technical/holding times. ;_ ... ;
- ' .='.'&>-.'*;.:*"'"''<'' . ' ' ' . .-
- ' -fiS-^vJ-.:;.- -. ' . . . .'
c. Comparison of the values of the target compounds reported in each sample
* i -:;.\,.-^i , '.-ป.!;v-_' ซv.'ป' ... *^ . * * - . . *
d. Other QC information, such as performance of internal standards.
."."'." -v- ' *
3.7.4 Action
Data are qualified based on system monitoring compounds results if the recovery of any
volatile system monitoring compound is out of specification. For system monitoring
compound recoveries out of specification, the following approaches are suggested based on
a review of all data from the package, especially considering the apparent complexity of the
sample matrix. (Also, see Table M2-VQA-6, below).
1. If a system monitoring compound in the volatile sample has a recovery greater than the
upper acceptance limit: .
a. Detected volatile target compounds are qualified "J".
b. Results for non-detected volatile target compounds should be qualified "UJ"
2. If a system monitoring compound in the volatile sample has a recovery greater than or
equal to 10% but less than the lower acceptance limit:
a. Detected volatile target compounds are qualified "J".
b. , For non-detected volatile target compounds, the sample quantitation limit is
qualified as approximated, "UJ".
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3. If a system monitoring compound in a volatile sample shows less than 10% recovery:
a. Detected volatile compounds are qualified "L". ._-'
4.
5.
6.
4
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9. When both the initial analysis and the reanalysis have system monitoring compound
recoveries outside of criteria, the data summary form should normally contain the
highest concentration obtained for each, compound detected, provided that system
monitoring compound recoveries in the analysis being reported do not suggest a high
bias. However, if a demonstrated laboratory contaminant is detected in one analysis
but not in the other, the negative result, may be more appropriate to report
,-. ;.-'.i.-r'->j.^-'--::'-ซ.v-.-.- ' ' ' . .:'"/>&-.'-.S-"; -
When the reanalysis of a sample is within the system monitoring compound recovery
criteria, the laboratory is required to provide only data for the acceptable analysis. If
both sets of data are provided, and if a compound was detected in the initial analysis
but not in the reanalysis, then the positive result should be reported (provided the
compound is not a demonstrated laboratory contaminant). The reported result should
be flagged as estimated 0, due to possible sample inhomogeneity. .
3.8 Matrix Spike/Matrix Spike Duplicate
Data for matrix spike/matrix spike duplicates (MS/MSD) are generated to determine long-
term precision and accuracy of the analytical method oh various matrices and to
demonstrate acceptable compound recovery by the laboratory at the time of sample
analysis. These data alone cannot l>e used to evaluate the precision and accuracy of
individual samples. However, when exercising professional judgment, this data should be
used in conjunction with other available QC information. . - ^
3.8.1 Acceptance" Criteria
1. Matrix spike (MS) and matrix spike duplicate (MSD) samples are analyzed at a
frequency of one MS and MSD per 20 samples of similar matrix.
2. Spike recoveries should be within the advisory limits provided on Form m VOA-1 and
VOA-2. .
3. Relative percent difference (RPD) between MS and MSD recoveries must be within
the advisory limits provided on Form HI VOA-1 and VOA-2.
3.8.2 Review Items
Form III VOA-I and VOA-2, chromatograms.
3.8.3 Evaluation Procedures
1. Verify that MS and MSD samples were analyzed at the required frequency and that
results are provided for each sample matrix.
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2. Inspect results for the MS/MSD Recovery on Form m VOA-1 and VOA-2 and verify
that the results for recovery and RPD are within the advisory limits.
3. Check that the matrix spike recoveries and RPDs were calculated correctly.
4. Compare %RSD results of non-spiked compounds between the original result, MS, and
MSD. .
3.8.4 Action
1. No action is taken on MS/MSD data alone. However, using informed professional
judgment, the data reviewer may use the MS-and MSD results in conjunction with
other QC criteria to determine the need for some qualification of the data.
2. The data reviewer should first try to determine to what extent the results of the
MS/MSD affect the associated data. This determination should be made with regard to
the MS/MSD sample itself as well as specific analytes for all samples .associated with
the MS/MSD.
3. In those instances where it can be determined that the results of the MS/MSD affect
only the sample spiked, then qualification should be limited to this- sample alone.
However, it may be determined through the MS/MSD results that a laboratory is
having a systematic problem in the analysis of one or more analytes, which affects all
associated samples.
4. The reviewer must use professional judgment to determine the need for qualification of
positive results of non-spiked compounds.
5. When non-spiked compounds are present in either the MS or MSD results, a table in
the data review narrative is constructed showing original (unspiked) sample results for
non-spiked compounds, non-spiked compounds present in the MS and MSD and the
calculated %RSD.
NOTE: If a field blank was used for the MS/MSD, a statement to that effect must be
included on the ORDAS and noted for the TPO.
3.9 Internal Standards
Internal Standards (IS) performance criteria ensures that GC/MS sensitivity and response
are stable during each analysis.
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3.9.1 Acceptance Criteria
1. Internal standard area counts must not vary by more than a factor of two (-50% to
+100%) from the associated calibration standard.
2. The retention time of the internal standard must not vary more than ฑ30 seconds from
the retention time of the associated calibration standard.
;'''' i
3.9.2 Data Requirements and Data Retrieval
Form YE VOA and chromatograms.
3.9.3 Evaluation Procedures
1. Check the internal standard retention times and areas reported on the Internal Standard
Area Summary (Form vm VOA).
2. Verify that all retention times and IS areas are within criteria.
3. If there are two analyses for a particular fraction, the reviewer must determine which
are the best data to report. Considerations should include:
a. Magnitude and direction of the IS area shift.
b. Magnitude and direction of the IS retention time shift.
c. Technical holding times.
d. Comparison of the values of the target compounds reported in each fraction.
c. Other QC.
3.9.4 Action
1. If an IS area count for a sample or blank is outside -50% or +100% of the area for
associated standard, then:
a. Positive results for compounds quantitated using that IS should be qualified
with'T'. .
b. Non-detected compounds quantitated using an, IS area count greater than .+
100 % should be qualified ' 'UJ''.
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c. Non-detected compounds quantitated using an IS area count less than 50%
are reported as the associated sample quantitation limit and qualified with
"UJ". . ;
d. If extremely low area counts are reported, or if performance exhibits a
major abrupt drop-off then a severe loss of sensitivity is indicated. Non-
detected target compounds should then be qualified as unusable, "R".
2. If an IS retention time varies by more than 30 seconds:
The chromatographic profile for that sample must be examined to determine if any
false positives or negatives exist. For shifts of a large magnitude, the reviewer may
consider partial or total rejection of the datajor that sample fraction; Positive results
should not need to be qualified as "R", if the mass spectral criteria are met.
3. If the internal standards performance criteria are grossly exceeded, then this should be
noted for TPO action in the ORDAS. Potential affects on the data resulting from
unacceptable internal standard performance should be noted in the data review
narrative.
3.10 Reported CRQLs
The objective is to ensure that the Contract Required Quantitation Limits (CRQLs) are
accurate.
3.10.1 Acceptance Criteria
1. The adjustment of the CRQLs must be calculated according to the correct equation to
account for dilution and moisture content as appropriate.
3.10.2 Review Items
Form I VOA and chromatograms.
3.10.3 Evaluation Procedures
1. Verify that the CRQLs have been adjusted to reflect all sample dilutions and dry
weight factors that are not accounted for by the method.
3.10.4 Action
1, If any discrepancies are found, the laboratory may be contacted by the designated
representative to obtain additional information that could resolve any differences. If a
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discrepancy remains unresolved, the reviewer must use professional judgment to
decide which value is the best value. Under these circumstances, the reviewer may
determine qualification of data is warranted. A description of the reasons for data
qualification and the qualification that is applied to the data should be documented in
the data review narrative and in the document support. ,
' . ' ._.;'..' ' ,-";.- ;>;.^vjfe: ;'' '
2. The reviewer must assure that any .results in error by more ;timn ^1,0 percent are
identified and corrected on the sample data summary. If laborBo^ resuljmission is
not performed, the reviewer should document his/her changes to;the data in the
narrative and support; documentation. Calculation errors should also be noted on the
ORDAS.
3. Numerous or significant failures to properly^eyaluate and adju^MIJRQLs should be
noted for TPO action on the ORDAS.
3.11 Tentatively Identified Compounds
Chrpmatographic peaks in volatile fraction analyses that are not target analytes, system"
monitoring compounds or internal standards are potential tentatively/identified compounds
(TICs).
3.11.1 Acceptance Criteria
For each sample, the laboratory must conduct a mass spectral search of the NIST library
and report the possible identity for the 10 largest volatile fraction peaks which are not
system monitoring compounds, internal standards, or target compounds, but which have an
area or height greater than 10 percent of the area or height of the nearest internal standard.
TIC results are reported for each sample on the Organic Analyses Data Sheet (Form I
VOA-TIC).
NOTE: Since the SOW revision of October 1986, the CLP does not allow the
laboratory to report as tentatively identified compounds any target compound
which is properly reported in another fraction. For example, late eluting
volatile target compounds should not be reported as semivolatile TICs.
3.11.2 Review Items
Form I VOA-TIC chromatograms.
3.11.3 Evaluation Procedures
1. Blank chromatograms should be examined to verify that TIC peaks present in samples
are not found in blanks. When a low-level non-target compound that is a common
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artifact or laboratory contaminant is detected in a sample, a thorough check of blank
chromatograms may require looking for peaks which are less than 10 percent of the
internal standard height, but present in the blank chromatogram at a similar relative
retention time.
2. The reviewer should be aware of common laboratory artifacts/contaminants and their
sources (e.g., aldol -condensation products, solvent preservatives, and reagent
contaminants). These may be present in blanks and not reported 'as sample TICs.
Examples:
Common laboratory contaminants: COj (m/z 44), siloxanes (m/z 73),
diethyl ether, hexane, certain freonji (1, l,2-trichloro-l,2,2-trMuoroethaneor
fluorotrichloromethane), and phthalates at levels less than 100 ug/L or 4000
' "''
b. Solvent preservatives such as cyclohexene which is a methylene chloride
preservative. Related by-products include cyclohexanone, cyclohexenone,
cyclohexanol, cyclohexenol, chlorocyclohexene, and chlorocyclohexanol.
. \~
c. Aldol condensation reaction products of acetone include: 4-hydroxy-4-
methyl-2-pentanone, 4-methyl-2-penten-2-one, and 5,5rdimethyl-2(5H)-
furanone. ""-
3. Occasionally, a target compound may be identified in the proper analytical fraction by
non-target library search procedures, even though it was not found on the quantitation
list. If the total area quantitation method was used, the reviewer should request that
the laboratory recalculate the result using the proper quantitation ion. In addition, the
reviewer should evaluate other sample chromatograms and check library reference
retention times on quantitation lists to determine whether the false negative result is an
isolated occurrence or whether additional data may be affected.
4. Target compounds could be identified in more than one fraction. Verify that
quantitation is made from the proper fraction.
5. TIC concentration should be estimated assuming a RRF of 1.0.
3.11.4 Action
1. All TIC results should be qualified "J", estimated concentration, on the laboratory
Form I-TICs. '
2. General actions related to the review of TIC results are as follows:
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If all contractually required peaks were not library searched and quantitated, the
designated representative could request these data from the laboratory.
3. Blank Results
Form I-T1C which contains sample results that are questioned by laboratory results,
should be flagged "B" and a line drawn through these data for; emphasis (initialed and
dated), on the Form MIC that is included in the validation .iqpi^)ง^.;:',
To be considered questionable, a sample TIC concentration must bb~ within 10 times
the concentration of one of the blank results. If different volumes/weights are used,
the total amount of compound in the extract must be compared for sample versus
blank. For VGA data, an instrument level comparison! is ฃ -used unless the
contamination is. proven to originate during. sample ."storage (before
preparation/analysis). In general, blanks analyzed within the same case, by the same
lab, may be cross-applied to either soil or water samples extracted or analyzed on
other days. '...' .'.'' '
' j. '. *
To question a sample result, only presumptive evidence for the presence of the
compound in the blank is necessary. The presence of the TIC in the blank is
suggested in any of the following situations: ,
All blank results must be attached in the support documentation section of the data
review.
4. When a compound is not found in any blanks, but is a suspected artifact of common
laboratory contaminant, the result may be qualified as unusable, "R", and a line
drawn through the result (initialed and dated) on a copy of the Form I-TIC that is
included in the validation report. .
5. Physical constants, such as boiling point, may be factored into professional judgment
of TIC results.
6. Failure to properly evaluate and report TICs should be noted for TPO action on the
ORDAS form.
-------
Appendix B
Validation of Semivolatile X)rganic Analyte Data
Subappendix B-l covers Level Ml
Subappendix A-2 covers Level M2
WDCR565/03i52
-------
Appendix B
Validation of SemivolatUe t>rganic Analyte Data
'"'- " mj^&c&^:-<:-'V.-.--" -:-;:..?.*v-: "
j-=t^^^?^-C'--:-- -'; ' ' - v:.V- -
Subappendix B-l covers Level Ml
* Subappendix A-2 covers Level M2
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Appendix B-l
Validation of Semivolatile Organic Analyte Data
Manual Level Ml
1; Purpose and Applicability
if .- - - .
This procedure provides ^t^-byrstep instructions to manually validate the semivolatile
organic analyte (SVOAJ^iSati^usiiSg'ihe manual innovative data validation approach at Level
m' ' '" : "\ ' J '' '
' ''
. . ....
Hie procedure is appli^lejipithersyOA datax>btained using the Contract Laboratory
Program Statement of^ori^CILP^SOW). Harcfcopy data conforming to the CLP SOW
specifications :anฃessieirafi^
Data validated .(iusmg;^^l||re^edpte are considered usable for the following types of
purposes; however, ^tn^|;:^^;must decide on a case-by-case basis whether the
procedure is suitable for their intended data uses. The suggested data uses are:
Oversight of activities led by other parties
Comparison to action levels
, Initial site investigation
Contamination sources
2. Quality Control Measures Checked
Table Ml-SVOA-1 highlights the quality control (QC) indicators evaluated under this data
validation procedure.
3. Procedure
The following subsections describe for each of the QC indicators the acceptance criteria,
location and retrieval of QC data, evaluation of the QC data, actions taken in the event the
QC acceptance criteria are exceeded, and documentation of the QC violations in a
standardized report form.
U.S. EPA Headquarters Library
Mail code 3201
1200 Pennsylvania Avenue NW
Washington DC 20460
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Table Ml-SVOA-1
QC CHECKLIST FOR LEVEL Ml
CLP RAS SEMIVOLATILE ORGANICS
QC MEASURES
. Action Level. Notification
Instnunent Tune
Manual
Initial Calibration (RRF)
Initial Calibration (%RSD)
Continuing Calibration (RRF)
Continuing-Calibration (%D)
Laboratory Blank
Surrogate Recovery
Dilution Factor
Moisture Content
Mass Spectra
Chromatograms
Raw Data
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Reporting requirements for Level Ml are:
Hand annotate the Form I's, including
Data validation qualifiers
- Sample identification number
Sampling location
Provide a narrative that includes
A statement that defines the level of the data review, i.e., Ml
Major problems associated with analysis
- **- . -
Include the following attachments
- list of data validation qualifiers
Support documentation including forms that support assigning data
qualifiers - "
Chain of custody form
3.1 Action Level Notification
The purpose behind action level notification is to make the EPA Remedial Project Officer
(RPM) or the Site Project Officer (SPO) aware of the potential human health risk at the
site. Li accordance with the Region m Hazardous waste division policy, the EPA RPM or
SPO must be promptly notified of any contaminant exceeding the established action level or
the 10-day health advisory limit. The data for contaminants exceeding the action levels
must be validated as a top priority and reported to the RPM or SPO. Validation of the rest
of the data may then be completed normally.
3.1.1 Acceptance Criteria
EPA's Office of Solid Waste and Emergency Response has established 10-day advisory
limits or the action levels for several organic compounds and elements of special health risk
concerns based on the Safe Drinking Water Act. The semivolatile organic compounds and
their 10-day health advisory limits apply only to aqueous samples and are listed in Table
Ml-SVOA-2. The criteria for action level notification are as follows:
' The contaminant concentration must be equal to or above the established 10-
day health advisory limits.
Data for contaminants exceeding the action levels must be validated as a top
priority.
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The following EPA personnel must be notified of the action level
exceedances:
EPARPMorSPO
EPA Section Chiefs:
- Site Investigation (SI)
- Remedial
Enforcement
- RCRA
EPA Section lexicologists:
Enforcement
Superfund
RCRA
The remaining data validation should be completed per normal procedures.
Any special instructions from the Hazardous Waste Division should be
followed.
Records should be kept of the data review, action level notification and any
follow up instructions and actions.
Table Ml-SVOA-2
SEMIVOLATILE ORGANIC ANALYTES AND ACTION LEVELS
Compound
1 ,3-Dichlorobenzene
Pentachlorophenol
Action
Level*
8,930
300
Compound
1 ,4-Dichlorobenzene
Action
Level*
10,700
.
*A11 units are ug/1.
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3.1.2 Review Items
All data required to perform Level Ml validation, as detailed in the following sections are
necessary for carrying out action level notification. The location of the data and their
retrieval procedures are also discussed below.
3.1.3 Evaluation Procedure
The evaluation process preceding action 'level notification will primarily consist of
comparing the results on Form I's with the action levels presented in Table Ml-SVOA-2.
Following the identification of the contaminants exceeding the action levels, focused data
validation should1 be performed1 using the criteria, and procedures described in the
appropriate se(jtionsi>elow; ' ff H *."--
3.L4 Action - ; " . " ' ;
The action resulting from focused: data validation will be the notification of action level
exceedance to the personnel identified above in Section 3.1.1. '
3.1.5 Reporting .
Copies of Form I's can be used to highlight the contaminants above the action levels. The
findings of the focused validation can be summarized in a memorandum, and the data
qualifiers resulting from focused validation may be written on the Form I's. The marked
up forms should be clarified that they represent validation of only the contaminants
exceeding the action levels, and not all data.
3.2 Evaluation of Mass Spectra for the Detected Compounds
The primary QC indicator checked in Level Ml is the mass spectra for the detected
compounds. This indicator pertains to evaluating a compound's presence by matching its
mass spectrum with a standard (known) mass spectrum for the compound. No assessment
is made of the reported quantity of the compound or any quantitative quality control
indicators that could lend some uncertainty to the reported value.
3.2.7 Acceptance Criteria
The acceptance criteria for mass spectral matching are given in the CLP Functional
Guidelines and are as follows:
All ions present in the standard (known) spectrum at a relative intensity
; greater than 10 percent must be present in the sample mass spectrum
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Procedure No.: Ml-SVOA
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Page 6 of 19
The relative intensities of the qualifying ions (those above 10 percent relative
intensity) must .be within +/-20 percent between the standard and sample
spectra, for example, an ion with a relative abundance of SO percent in the
standard spectrum must be present between a relative abundance of 30 and
70 percent in the sample spectrum) ;
Ions, present in the sample above 10 percent relative abundance must be
* * * . .ป " ?-.*^ '-t-'X'^'--,- ''.
accounted for. - ' .;.-.- . : ':'.:!:..- ' :
3.2.2 Review Items
.
Form I's for each field sample, field blanks, and laboratory blanks mduded in a Sample
Delivery Group (SDG) are necessary to compiled list of the detected compounds. Mass
spectra are then necessary, for each of the detected compounds in a sample.-The required
mass spectra include both the sample spectra as well as the standard spectra, r
With respect to the blanks, it may be beneficial to evaluate the blanks before, the sample
mass spectra are evaluated, If a compound is found to be a common contaminant, i.e., it *
is present in any one of the blanks and also in the sample, the concentration in the sample
should be evaluated -with respect to the highest blank contamination using the 5 (or 10)
times criteria before proceeding with the elaborate mass spectral evaluations. .The effort
required for the sample mass spectral evaluation may be significantly-, reduced by
performing the blank evaluation first. The mass spectra for the blanks; however, should be
evaluated to ensure that the contaminants were identified properly.
All sample Form I's are generally located together in front of the data package. Copies of
the Form I's can also be found in the .detailed sample data package organized by sample;
i.e., the Form I and its substantiating raw data for a sample are placed together. The raw
data include a quantitation report and mass spectra for each detected compounds in that
sample are. A standard (known) mass spectrum, and two sample mass spectra (one
unaltered and another background-subtracted) are generally provided. The presentation of
the mass spectra differs for different instrument manufacturers, but information necessary
for evaluating mass spectra is always provided in some form. Hands-on experience with
different brands of mass spectrometers, although not essential, can be helpful in
interpreting the information.
Copies should be made of the Form I's, preferably from the summary data package, if
included. Otherwise, the forms can be pulled out from the raw sample data package. All
detects should then be highlighted with a marker or other convenient means. The raw data
should then be tagged for every sample for evaluating the mass spectra and the
chromatograms (reconstructed ion current profiles).
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Procedure No.: Ml-SVOA
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3.2.3 Evaluation of Mass Spectra
Compare the highlighted Form I's with the tagged raw sample data. Verify that raw data
are provided for every sample, and a Form I exists for every sample represented by raw
data. Verify on a sample-by-sample basis that mass spectra are provided for every detected
(highlighted) compound reported on the Form I's. A cross verification should then be
performed that all target compounds for which mass spectra are provided are also reported
as detected on Form I's. ^; .?&&' ' " ' , :.-.'< v''
Mass spectral comparison routines based on the evaluation criteria presented earlier
(presence of major ions and their relative intensities) are built into the instrument software;
therefore, performed automatically? A listing of ions and their relative intensities is not
produced; rather a score based on the extent of^the fit of all criteria is produced. Hie
score is based on a basis of 100 or 1000 for a perfect match of the presence of major ions
and thek relative abundances^ f^e score is printed on the quantitation report as a "q"
value, a score upward of 60 percent of the maximum (upward of 60 or 600) is generally
considered acceptable for positive identification for a compound. < . :
Visual comparison of a mass spectrum involves looking for the base ion (the mass fragment
with the highest intensity), the parent ion (mass fragment equal to the molecular weight of
the compound) and other characteristic ions representing removal of one or more functional
groups (such as -CH3, -CH2-, -Cl, -OH, or a combination thereof) from the-parent ion, the
base ion or other ions. The removal of functional groups is often successive and produces
a fingerprint pattern for a type of compound; i.e., straight-chain hydrocarbons produce a
characteristic envelope of mass fragments separated by 14 mass units. Similarly, aromatic
compounds produce a peculiar fingerprint. The base ion represents the most stable mass
fragment; therefore, it is always present. However, a parent ion often is unstable and may
not exist at all or may exist at a low abundance or relative intensity.
Compare the standard (known) mass spectrum with the . background-subtracted sample
spectrum for the presence of the base, parent and other characteristic ions. Although
background-subtracted and unaltered mass spectra are generally provided, the former type
of spectra are much cleaner looking due to the subtraction of column bleed or other broad-
based interferences; therefore, better suited for comparison. Generally, the presence of
major ions and overall matching of the fingerprint pattern between the standard and the
sample. spectra can be considered satisfactory. The comparison is rather subjectivcj and
requires a trained-eye to deduce the information.
\
Interference still may be present in a background-subtracted mass spectrum due to coeluting
compounds (as compared to column bleed or broad-based interferences). Unless the
interfering compound is an isomer or an analog of the target compound in question, the
fingerprints produced by the target compound and the interfering compounds can be quite
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Procedure No.: Ml-SVOA
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Page 8 of 19
different. Inseparable isomers reflect a limitation of the gas chromatpgraphy without any
recourse. Concentrations for such isomers may be reported either as all contribution from
one isomer or the value may be divided equally between the two isomers. For example,
difficulties are often seen in separating benzo(b)fluoranthene and benzo(k)fluoranthene by
gas chromatography.. These compounds also produce similar mass spectra; therefore, it is
quite difficult to; tell -them apart Homologous compounds generally have different
retention times; therefore, may not be of much concern. Thus, coeluting .compounds do
not pose significant jirpblems .when evaluating the mass spectra.
' ' '
Sddom does a CH^ laboratory incorrectly interpret a mass spectrum, but there is a
subjective element to mass spectral interpretation. While working within the CLP
guidelines, the laboratories ^do have their own reporting practices at the limit of the
mstmment's senativity.^Most of the mass spectral identification problems occur near the
limit of detecticravwhere;the differences in the relative intensities are not easily discernible.
Special attenticm should be paid in evaluating mass spectra for compounds detected at low
9ฐnCentrat^ -:'. . ' "''.''..-'. '
Rearrangements and, other side-reactions often occur inside a mass spectrometer. These'
phenomena produce rnass fragments that are not easily accountable from the structure of
the parent compound; WhUe it is desirable that a data validator possess the knowledge to
interpret complex mass spectra, . for the routine CLP analyses, such expertise is
unnecessary.
3.2.4 Action
In the event the mass spectrum of a detected compound does not at all resemble the
Standard spectrum or has extremely poor matching, the compound should be considered
undetected. In this case the detected value should be changed to the CRDL for that sample
and flagged as undetected, "U." (NOTE: This action is in contrast to the EPA
Functional Guidelines which recommend rejection of data. It is felt that an outright
rejection of data is not justified. If the mass spectrum produced at a target compound's
retention time does not match the standard spectrum, a conclusion can be drawn that the
target compound is not present and the mass spectrum may be due to something else. In
such a case the target compound should be considered as undetected and data should not be
rejected. Make sure that the target compound in question does produce a good mass
spectrum by inspecting the standard mass spectrum from the calibration and the fit score on
the quantitation report for the daily or continuing calibration. Data for undetected
compounds are usable for many purposes such as risk assessment; therefore, rejection of
data is not beneficial to a project. The conflict of improper characterization should be
brought up and rectified with the laboratory.)
If there is some evidence of the compound's presence (as determined by visual matching of
the base ion, parent ion and fingerprint pattern despite a poor fit score), the compound
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Procedure No.: Ml-SVOA
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Page 9 of 19
should be considered tentatively identified. The reported value should not be altered in this
case; however, a data qualifier code, "N", should be appended to the data point to denote
tentative identification.
In both of the above cases, evaluation of additional information such as the retention time
and frequency of detection in other field samples is warranted. Previous site history is also
an important evaluation; .however," information essential to perform such an evaluation (in
contrast to 'validation') may not be easily available to a data validator. Nonetheless, it is
incumbent uppn a data.validator-to make appropriate recommendations to 4he project
manager or the; remedial^/officer.^
3.2,5 R&orfag i^ฑ^~:f: /;'' ; '".;.'. ';J-':;:~;.?' ;" ;' ,
The most convenient fonn of reporting the mass spectral evaluation is through a brief
memorandum to appropriate authorities.. The highlighted Forms Is and the mass spectra in
question should be appOTd6d tb/me memorandum in support of tiie conclusions. Also fill
out and attach the Mass Spectral Evaluation Form, as depicted in Table Ml-SVOA-3, to
the report as a record of v what was done. Record the date(s) of analyses. Field sample
numbers should be transcdbed from the chain-of-custody in the Sample Identifier column.
Notations-may be placed under the "MS" column for each sample to describe the mass
spectral evaluation. The following notations are suggested:
XAcceptable mass spectrum.
NTentative identification. Partial proof of a compound's presence, but all
identification criteria not met.
UNo mass spectral match. Using professional judgment, the compound is
considered undetected.
R^-No mass spectral match. Using professional judgment, the compound
data are rejected from further use..
3.3 Evaluation of Chromatograms
The purpose behind .evaluating the chromatograms is to get an idea regarding potential false
negatives, and gross analytical errors. Checking for positive data as described under mass
spectral evaluation does not offer any insight into data that are not reported (i.e., reported
as nondetects). Laboratory error or gross interference from other compounds could be the
reasons for erroneous reporting. The gas. chromatograms or the reconstructed ion current
(RIC) profiles are the primary too! used for the false negative evaluation under Level Ml.
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Case No.:.
SDG No.:.
Data Reviewer:
Site:
Procedure No.: Ml-SVOA
Revision: 1
Date: 06/30/1995
Table Ml-SVOA-3,
SVGA Mass Spectral Eraloation
Summar
Dates Analyzed:
lot. ID:
Sample Identifier
1. "
2. ' :
3.
4. ' '."'. ': '
s.-1 -' '' ' ' ' '' ' '.''
6. '' '' "-.'.' ' ' -"
1. ''" . '-' -:' ' '";' ' ' "
'ซ.' ' ' "-
9. ' '' S :''
10. ;
SPCC <*) CCC(*|
"
Addk(A)
Compound: ' Bam/Neutral (BN)
Phenol - f*VA'
bUO-CUnoedivnedier VfiN)
2-CMoraohenol ' fAI
1.3-Diehlorooenzeoe ' fBNl
1. 4-Diehlorobenzene fMBN)
1.2-Diehlurabeuuiie fBN
2-MetfivlDhenol . fAI
2 r-oxvfaiifl-CMonปRmama fBJfl
4-Metbvbhenol fAI
N Nhroio-di-o-DroovUnune fBNVft
HexacbJoroethane fBNl
Nitrobenzene fBW
Isrmhorone fBNl
2-NitroDhenol fAV*1
2.4-DimethvIohenol CA1
bis(2-Chloroethoxv>methane (BN)
2.4-DichloroohenoI fAI
1.2.4-Trichlorobenzene (BN)
Naohthalene CBN}
4-OhloroaniIine fBN)
Hexachlorobutadiene fBN)f*)
4-Chloro-3-methvlDhenol (M(*)
Hexachlorocvclooentadiene CBNXtf)
2 4 6-Trichloroohenol f AV*
2 4 5-TrichloroohenoI f A)
2-Chloronaohthalene fBN*
2-Nitroaniline (BNV
Dimethvlohthalate fBN)
Acenaohthvlene fBhO
2.6-Dinitrotoluene fBN)
3-Nitroaniline fBN)
' Acenaohthene f*1fBN)
2 4-DinitroohenoI (M(fT>
4-Nilrophenol (AW/SO
Commenta on Chromatognmi
1.
2. '
3. ' ' :
4. .....' -
5.' .'-; . ' ' . -'"' ' '.-:'.: . -, . ' ' . .
*v : ; '' '.".' . " ' '' . -.. _
7. ' V- . " . . ' . .
8. '"' ' ; " ' .' ' "' .. -:'::. ' . >
9. ''' .. ' ' ' ''': '
10.. . -. :'' .'.':':"..' .'' ' .
.'.. .' -..'.-..,-'-. , - .
ir-.'.
MS
RT
- ' 2 :'
MS
RT
.',: 3 " '
MS
".
^
RT
' ^ 'Samnte Identifier ",..' "':'. .^: ' '; ".'":"
--. -4
MS
i
RT
. =
;.; V .
'MS
ฐ
- . '
RT
6
MS
RT
":**
MS
RT
.-
' '%:'
MS
t '
/
--,
-o
RT
.
'' ' 9 ' '
MS
RT
I
id ;
MS
RT
-. ..
- .
ซ'
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Procedure No.: Ml-SVOA
Revision: 1
Date: 06/30/1995
srcc an ccc(*
Acidic (A)
Compound: Base/Neutral (BN
DiethvbihthiUtfi fBNl
' 4-ChkHnnlienvl-ohenvIedier (tttf\
FhlOfNID " (tttt
4-Ntonanttliwt (BN1
. 4.6-D5nhro-2-mdhvtehenol (A1
N-NKrotod'roheflvlmnine V fBNSf*)
4-BrornoohenvJ-ohenvleflier ^(Bffi
RefltocUoroohenol . f AV*I
CWnzale "'"'' '" nhdปlate ' fBNI
Chraene fBNI
DMKOctVปnปi*ii1irte /BfnC*1
PcinofbVfliioBMithenfl ' (Eti
Bcmofldfluorafitfaen& fBN^
BefnofB^DVKfw ffihnr''
. IndenoH .2.3-crfhjvrene fBNI
Dibcnz^A fi^anthracene ^BN
Benzofe.h.rh)ervlene fBN)
Sample Identifier
1
MS
.. .' .:
iS"?t****
' -: ':--
.'^-;7
'* -X;
RT
<&Ki:.
.-'if-.
.(,.;
. .ซ.:
'':'
' ?~'.:~t '
~ -
1
MS
'
V;-
,~ .'"*-'*'
.-.'T-..'
..:.',:.
..-. .
*.- -
-, 1-
RT
..-,--*
:' :- "
.' y
.-.
' .-
N'-
3
"MS
' -
'
RT
4
MS
RT
" .
""
MS
IT "
5
RT
6
MS
RT
MS
.
1
RT
' -,
'
MS
~~-~
--.
8
RT
9
MS
RT
10
MS
ป
*
RT
-r
;
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Procedure No.: Ml-SVOA
. Revision: 1
Date: 06/30/1995
Page 12 of 19
3.3.1 Acceptance Criteria
There are no EPA-established criteria for evaluating chromatograms for false negatives.
The criteria used for evaluating chromatograms are based on good laboratory and scientific
practices, and these are not hard and fast requirements. The suggested evaluation criteria
are: ' ' '. ",... . ,...:-. 'i.., . ' . ' -, . .ซ. .-. . .'ฃ'' .''
There should not be any significant peaks in me (Aroin^grams th^ are not
accounted for as TCLs or TICs. Significant peaks are. those with a
minimum peak height of 10 percent of the (dosest internal standard.
The chromatograms should ' ideally have.. base-line resolution between
adjacent peaks. Also, mere should nobbe broad (unresolved) envelops in the
chromatograms. ' -:- -:'/r ""' ......
'- ; - , :-. '.:;,- - . . '.-' :."-.-' '.:->.<-; K!
There should not be abrupt shifts in the baseline.
There should not be peak tailing or sharp rise in the peak fronts.
3.3.2 Review Items
Chromatograms, or the RIG profiles for each sample are necessary for the evaluation. The
RIC profiles can be found in the front of the raw data package for each sample. The
quantitation report for each sample is also necessary to retrieve either the retention times or
information regarding scan numbers to compare with the peaks on the chromatograms.
3.3.3 Evaluation of Chromatograms
Visually inspect the chromatograms for all peaks that appear to be at least 10 percent
height of the nearest internal standard. Compare that the scan number or the retention time
that appears on the x-axis of the RIC profile with that listed on the quantitation report for
the TCLs or the library search record for the TICs. Make sure that all significant peaks
are accounted for.
Also observe the RIC profile for peak resolution between adjacent peaks. Poor peak-to-
peak resolution is indicative of degrading performance of the gas chromatographic column.
The values obtained from a degrading system are prone to be inaccurate. Obviously
certain isomeric or homologous compounds are difficult to separate. But generally, there
should be at least 90 percent valley between the neighboring peaks.
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Procedure No.: Ml-SVOA
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Inspect the RIC profile for broad, unresolved envelops. These are generally indicative of
outside interference from a series of homologous compounds such as straight-chain
hydrocarbons. Especially, assess the interference with the internal standards and surrogates
under the envelop using the expected area counts. The standard values that are far from
the expected values may be indicative of potential problems with the TCL detection or
quantification. "
Inspect the RIC profile for abrupt shifts in the baseline. /Such shifts >are indicative of
problems with'instrument sensitivity or leakage in the system. The area counts obtained
from shifted baseline are inaccurate, or even the detection of a TCL at low concentration
may be missed/ ;
V . :. . . .. , ' ' .,._.. - '- ' ' ' -' ,-
'. .' "."." A ..- "'"''>t ' , ' - - ' . ' . * '-."..
Rapid peak rising or peak tailing indicate problems* with the gas chromatographic column,
such as depleted stationary phase on the column, decomposition of the stationary, phase or
creation of active sites. Again, a visual inspection of the RIC profile will yield information
on the shape ofthepeafc;^ .'<' ' '. ' '/v-';.-^--^''/'--... " '.:"' -. '>
3.3.4 Action vv';'"- .'. . .. . : . --^ :':--> ":; ;/,;.;' -. *
Professional discretion must be. used when evaluating and qualifying data based on the
chromatographic evaluations. An experienced chemist can generally infer the magnitude
and the frequency of the problem from the RIC profile. If the probleitr appears to be
systematic, then it should be brought to the laboratories attention and resolved.
Intermittent problems may or may not require any action. The following guidelines are
suggested when acting on RIC profile observations: -
Any unaccounted TCL peak with area equivalent to or greater than the
lowest reportable limit for the sample must be brought to the laboratory's
attention and resolved. Any unaccounted non-TCL (i.e., TIC) peak with an
area equal to or greater than 10'percent area of the nearest internal standard
must also be resolved with the laboratory. TICs with less than 10 percent
area are not required to be reported according to the CLP-RAS protocols.
In the event, the discrepancy cannot be resolved with the laboratory, the
problems should be documented and brought to the attention of the CLP-
TPO, the RPM and the SM. The data for unreported TCL or TICs may be
considered unusable until the problems are resolved.
If a peak resolution problem is evident for the samples, and appears to be
systematic (i.e., present in all calibration samples, QC samples, and field
samples and increasing as the run progresses, additional QC measures such
as the continuing calibration percent difference (%D), and internal and
surrogate standard recoveries in the vicinity of the affected peaks should be
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Procedure No.: Ml-SVOA
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Date: 06/30/1995
Page 14 of 19
evaluated to determine if the peak resolution problem could affect detection
or quantification. If determined so, the positive data may be qualified as
estimated, "J." Negative data may also be qualified as estimated, "UJ" if
the ability to detect at low concentrations is also deemed to be jeopardized
by poor resolution of adjacent peaks. -
Broad envelops of homologous .compounds could: interfere with
quantification ,or;even detection. If the mteaference is evident from the
recoveries of the internal and surrogate standards in the .vicinity of the
envelop, associated.compounds may also be interfered,with. Using
professional discretion, the positive arid negative data may ^considered as
estimated, 'T'^and^W', respectively. If the project objectives cannot be
met with the estimated data, alternative sample preparation \and cleanup
procedures-may: need to be developed and specified. ';. v
Discrete; shifts'in'the:: baseline in the rmddle of a nm are m^ of
intermittent problems. If the shift is due to leakage or change in the system
pressure, me positive as well as negative data' may .be; considered estimated
("J" and "UJ, respectively). The problem could be also due to some
fluctuation in the instrument electronics which may lead to drastic changes in
the sensitivity of the instrument to defect the compounds. As a note,
professional judgment should be exercised in determining the severity of the
problem. For example, the magnitude of a drop in the baseline below the
zero line may not be estimated and could be very significant. On the other
hand, a drop that yields a baseline still above zero can be put in a
perspective with the original baseline and a general appearance of the entire
RIC profile.
The problems with peak symmetry are indicative of system degradation, and
should be brought to the attention of the laboratory for a corrective action.
Professional judgment should be used when and if qualifying any data due to
unsymmetrical peaks. First the problem should be defined in terms of
persistence throughout the chromatogram and also from sample to sample.
Additionally, the shapes and area counts for the internal and surrogate
standards should be evaluated to see if the problem could have affected
compound detection and/or quantification. Data qualification may be
uncalled for if the standard area counts are acceptable.
3.3.5 Reporting
The Mass Spectral Evaluation Form (Table Ml-SVOA-3) may be used to note any brief
comments on the chromatographic evaluations. The comments may be noted against each
sample identifier. For more descriptive comments, a separate sheet may be used.
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Procedure No.: Ml-SVOA
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3.4 Evaluation of Retention Times
While not unequivocal in identifying a compound, the retention times are quite helpful in
confirming the presence of a detected compound. Matching of mass spectrum and
retention time of sample with those of a standard yields higher credibility and confidence
level to the detection m the sample. On the other hand, not matching the retention time
may or may not invalidate tiie: detection. If a mass spectral match is made beyond any
doubt, poor matchirig of the retention time may not have adverse impact on the detection.
If mass spectral matching; is unacceptable or only partial, and the retention times do not
match, then a strong doubt can be cast on a compound's presence.
3.4.1 Acceptance Criteria *-.,.-
" ! ' >;'.;-: '">::''ป:'' '' . " ''.
The criteria for retention tim^ the EPA's functional guidelines as follows:
The relative retention times (RRTs) must be within +/-0.06 RRT units of , ;
the appUcable internal standard RRT. -
" .' ' ' -.
3.4.2 Review Items
Quantitation reports for the sample and continuing calibration are required for the
evaluation. These are located in the raw data for samples and standards. A copy of the
continuing calibration quantitation reports may be made or the reports pulled out from the
raw data to facilitate a comparison with the sample quantitation reports.
3.4.3 Evaluation of Retention Times
For the detected compounds, determine the relative retention time for the compounds by
dividing their retention times with the retention time of their associated internal standard in
the samples as well as in the applicable continuing (or initial) calibrations. The sample
RRTs must fall in range of standard RRT +/- 0.06 units.
3.4.4 Action
Action for retention time evaluation requires professional discretion. Action taken must be
based on other data such as mass spectra and not on retention times alone. The following
actions are suggested for several potential situations.
Acceptable matching of the mass spectra and the RRTs~No action
suggested.
WDCR656/027JI
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Procedure No.:- Ml-SVOA
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Acceptable matching of the mass spectra but poor matching of the RRTs-No
action suggested, but the cause of retention time shift may be investigated.
Check to,see if similar discrepancies are observed in other parts of the
chromatogram. Often high concentration of a compound will cause shifts in
the retention times for other compounds in the nearby eluting region, but
shifts in retention times in other areas may not be observed. Shifts all
through the chromatogram may be indicative of an erratic system, such as
flow rate fluctuations, poor temperature regulation, restriction or leakage in
the system. . There are likely chances that the sample values in such
conditions may be inaccurate. Positive data may be qualified as estimated,
"J", if deemed essential. ' ; I
3.4.5 Reporting ^-: _.
The form presented earlier in Table Ml-SVOA-3 may be used to record any problems in
the RRT matching. For the detected compounds in each sample, the calculated RRTs inay
be recorded under the "RT" column. A data qualifier code may be added to the values.
exceeding 0.06 RRT and requiring qualification, such as "0.15J", for a compound with a
difference of 0.15 RRT units and where a professional.judgment to estimate the data is
'exercised. -.. I -,'.. .'.''..'"','"'.'' .
3.5 Evaluation of Blanks : :
Laboratory blanks and field blanks have a profound impact on false positives reported in
samples; i.e., compounds reported as positive detects but not originating from the samples
themselves. Cross contamination from the sampling equipment, incidental contamination
from the field conditions or contamination from the laboratory equipment or general
environmental are likely sources of false positives in the samples.
3.5.1 Acceptance Criteria
Criteria for blank evaluation are specified in the EPA's Functional Guidelines. In addition,
Region m has some additional requirements modifying the guidance. The .acceptance
criteria for blanks apply equally to any type of blanks associated with either sampling or
analysis, such as trip blanks, rinsate blanks, field or bottle blanks, laboratory method
blanks. While there are several criteria for evaluating the blanks, the only criterion
applicable to Level Ml is the comparison of the blank and sample concentrations. This
criterion is as follows:
For common contaminants, such as the phthalate esters, the sample
concentration must be minimally 10 times the blank concentration to be
considered a positive detect. Other contaminants must be present in the
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Procedure No.: Ml-SVOA
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sample at or above 5 times the blank concentration before they can be
considered significant detects. The blank with the highest concentration
must be used (this is, if the laboratory blank has the highest concentration of
naphthalene, and the equipment rinsate blank has the highest concentration
of 2-nitroaniline, both of these blanks must be used to qualify the respective
contaminants).
3.5.2 Review Items
Data requirements and data retrieval procedures for blanks are the same as those for the
field samples because the blanks as well as field samples are validated similarly.. Form I's,
mass spectra, chjomatograms, quantitationreports, etc., are essential for performing a
validation of the blanks first. > . "* " .'
3.5.3 Blai& Evaluation Procedure
Validate the blanks same as the field samples. Detailed validation procedures are described
above under appropriate'sections. Use the validated blank' results for a comparison with
the sample results. Make certain that the samples and blanks are evaluated oh the same
basis of sample .weight or volume, dilution factors, moisture, content, etc. Use the 5 (or
10) times the highest blank concentrations for qualifying the sample data.
3.5.4 Action
If the sample concentrations do not meet the criteria of 5 (or 10). times the blank
concentration, the sample results should be considered essentially undetected (or as not
detected substantially above the levels reported in the blanks); therefore, flagged "B" in
accordance with the Region HI data validation guidelines.
3.5.5 Reporting
Form.I's may be used to write the "B" data qualifier for the data not meeting the blank
criteria.
3.6 Sample Paperwork
The purpose for evaluating the sample paperwork is to determine that the samples being
validated are indeed the ones taken from the site, and have not been tampered with.
Accurate sample identity is of paramount importance in substantiating the sample data.
Without unequivocal sample identity and chain-of-custody procedures, the sample data may
not be defensible or enforceable.
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Procedure No.: Ml-SVOA
Revision: 1
Date: 06/30/1995
Page 18 of 19
Under the current GLP contracts, the original paperwork (i.e., the purge package or the
administrative record) is .included in the data package from the laboratory. It is assumed
that the data validator is not privy to the original paperwork; therefore, the evaluation
criteria and procedures described below apply only to the documents that are generally
included in the data validation package. These documents are the chain-of-custody forms
and Region HI Shipping Record. .
3.6.1 Acceptance Criteria
i . ' \ '
Criteria for acceptability or authenticity of the sampling paperwork, document control and
chain-of-custody have been established by the National Enforcement Investigations Center
(NEIQ, in support of the CLP. Overall criteria are too numerous and subjective to be
discussed here, but the criteria that apply to data validation are:
The chain-of-custody form should be properly and completely filleti out
including the sampler signatures, date and time of sampling, sampling station
identification, analyses requested, traffic numbers, tag numbers, etc. These
data are minimally required to confirm the authenticity of the sample and its
data; ''. ' ' ' '."'"''. ' '.
The chain-of-custody must be maintained at all.times. The custody transfers
between different parties must be signed and dated.
'3.6.2 Review Items
A copy of the chain-of-custody form originated in the field and that returned from the
laboratory with the data are essential to confirm the identity of the samples. In addition,
the Region HI Shipping Record is essential to identify the field QC samples. The chain-of-
custody and Shipping Record are generally located in front of the data package.
3.6.3 Evaluation Procedure
Ensure that the chain-of-custody form was signed and dated by the samplers, and a time
and date were entered for sample collection. The laboratory copy of the chain-of-custody
must have the signature of the laboratory sample custodian. Any errors on the form should
have been crossed out with a single line through the entry. Verify that all collected
samples have unique station identification, traffic numbers and sample tag numbers.
Ensure that the Region :in Shipping Record correctly reflects the information on the chain-
of-custody.
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Procedure No.: Ml-SVOA
Revision: 1
Date: 06/30/1995
Page 19 of 19
3.6.4 Action
The action to be taken in qualifying the data is highly dependent on the nature of the
problem. Some errors in paperwork are practically unavoidable in real situations. An
effort should be made to reconcile the differences by cross checking the field notebooks
against the sampling paperwork. Occasionally, the samplers may forget to sign the chain-
of-custody; however, the field notebooks may amply describe the sampling event.
Problems are also'inevitable in noting or cross-referencing sample tag numbers and traffic
numbers. Generally, there are several alternate sources of information to substantiate or
refute the problem.
3.6.5. Reporting:
.. ' ' ' .' ' ป-. *..
Any discrepancies found in the paperwork must be immediately brought to the attention of
the EPA RPM. Clearly define the problems in a memorandum to the responsible parties.
Attach marked copies of the chain-of-custody forms to substantiate,the findings.
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Procedure No.: M2-SVOA
Revision: 1
Date: 06/30/1995
Page 1 of 39
Appendix B-2
Validation of Semivolatile Organic Analyte Data
Manual Level M2
1. Purpose and Applicability
This procedure provides step-by-step instructions to manually Validate the semivolatile
organic analyte (SVOA) data using the manual innovative data validation approach-at Level
M2.. This approach focuses on the use of information contained on the CLP forms and a
review of chromatograms as summarized in Table M2-SVOA-1. The procedures are based
on modifications to Regions Hi's National Functional Guidelines for Organic Data Review.
The procedure is applicable to the SVOA data'pbtaihed using the Contract Laboratory
Program Statement of Work (CLP SOW). Hard copy data conforming to the 1990 CLP
SOW specifications are essential in order to cany outthe procedure.
Data validated using this .procedure are considered usable for the following types of
purposes; however, the data users must decide on a case-by-case basis whether the
procedure is suitable, for their intended data uses. The suggested data uses are:
Oversight of activities led by other parties
Comparison to action levels
Initial site investigation
Contamination sources
Nature and extent of contamination
Preliminary risk assessment
Risk assessment with known high, levels of toxics
Feasibility study
Preliminary design
Treatability study
Initial cleanup verification
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Procedure No.: M2-SVOA
Revision:, i
Date: 06/30/1995
Page 2 of 39
Table M2-SVOA-1
QC CHECKLIST FOR LEVEL M2
CLP RAS SEMIVOLATILE ORGANICS
QC MEASURES
Action Level Notification
Instrument Tune
Initial Calibration (RRF)
Initial Calibration (96RSD)
Continuing Calibration (RRF)
Continuing Calibration (%D)
Laboratory Blank
MS/MSD (%R, RPD)
Internal'Standard Area
Field Blank
Sample Paperwork
Holding Time
Retention Time
Surrogate Recovery
Dilution Factor
Moisture Content
Mass Spectra
Chromatograms
Raw Data
X
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Procedure No.: M2-SVOA
Revision: 1
Date: 06/30/1995
Page 3 of 39
2. Quality Control Measures Checked
Table M2-SVOA-1 highlights the quality control (QC) indicators evaluated under this data
validation procedure. '
3. Procedure
The following subsections describe for each of the QC indicators the acceptance criteria,
location and retrieval of QC data, evaluation of the QC data, actions taken in the event the
QC acceptance criteria are exceeded, and documentation of the QC violations ini a
standardised report form.
The semivolatile data requirements to be checked-are listed below:
3.1 Action Level Notification
3.2 Technical Holding Times (CCS - Contractual holding times only)
3.3 GC/MS Instrument Performance Check (CCS)
3.4 Initial Calibration (CCS)
3.5 Continuing Calibration (CCS)
3.6 Blanks (CCS)
3.7 Surrogate Spikes (CCS)
3.8 Matrix Spikes/Matrix Spike Duplicates
3.9 Internal Standards (CCS)
3.10 Reported Contract Required Quantitation Limits (CRQLs)
3.11 Tentatively Identified Compounds
Two forms have been developed to assist in the performance and documentation of
implementing Level M2. The first form, M2-SVOA-QUAL, summarizes holding time,
calibrations, blanks, surrogates, and internal standards. The second form, M2-SVOA-SPK,
summarizes surrogate and matrix spike quality control checks. These forms appear on the
following pages as Table M2-SVOA-2 and Table M2-SVOA-3.
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Procedure No.: M2-SVOA
Revision: 1
Date: 06/30/1995
Page 4 of 39
Reporting requirements for Level M2 are as follows:
1 ii
Hand annotate the Form I's, including
Data validation qualifiers
Sample identification number
Sampling location
Provide, a narrative that includes
- A statement that defines the level of the data review, i.e., M2
, Major and minor problems associated with the analysis
Highlight issues that may have affected detection limits
* Include the following attachments v
List,of data validation qualifiers , .-. :' ,/
- Support documentation including forms that support assigning data
'qualifiers .. \--.. '' '' .. : ,';_,,'',-,-..;;.. '._/' - ': ' '
Chain of custody form
Samples affected fay calibration should be listed on the appropriate
:. calibration forms /';';.'. .
The data qualifiers assigned in this review are as follows: . v, :
Codes Relating To Identification (Confidence concerning presence-or absence of
compounds) .''.. ' . : --
U = Not detected. The associated number indicates approximate sample
concentration necessary to be detected.
(NO CODE) = Confirmed identification.
B = Not detected substantially above the level reported in laboratory or field
blanks.
R = Unreliable result. Analyte may or may not be present in the sample.
Supporting data necessary to confirm result.
N = Tentative identification. Consider present. Special methods may be
needed to confirm its presence or absence in future sampling efforts'.
Codes Related To Quantitation (can be used for both positive results and sample
quantitation limits):
J = Analyte present. Reported value may not be accurate or precise.
-------
Case No.:_
SDG No.:ฃ
Data Reviewer
Site:
Procedure No.: M2-SVOA
Revision: 1
Date: 06/30/1995
Table M2-SVOA-2. SVGA Qualifier Summary (Calibrations, Blanks, Holding Time, Surrogates, Internal Standards)
Analysts
Date(s):
Analyzed Within
12 Hours of
nine?
_Yeป__No
IntUlD:
Tune OK?
_i.Yei_No
MBlnkpi
Ext. Dates:
Sample .
Identifier:
l'.
2. ^
3. ' . . " ""
4;.- -*-$ ;";<
5."'" ^ - :'^^-',-
6 ' -".'' '-''" V
7. - ' '"-'
g., ' ' ;.'.:'
9. '"'. " -"''' :-
10.' . ; : :: -.
Hold
Time
Out, days
Ex
..-;-..,-
>
. ,
.
'!:''
'.. :-'-
An
:-
Standards: (<>>)
Surrogate
1
. ' .
.--. . ..
:.'' '..'". -
..,.-
' "'
2
. ; .-.
3
4
5
.*".'
6
. - .
"' ''
7
-.-:
.'"'* '"^
.' -'
-- :
;_...,. -
8
';.. .
,,:!_' '
> '.'.- '
.' ^
- y . '
:". '
"*"
1
?t'.-'-
?'
...i-;. ..
Internal (IS)
2
-'
,;.<-.-,;
' . '
3
.,
>:,,
- ~
4
5
',
-''
6
Time:
Compound; Y SPCC roDane) ' fBN)
4-Methvlohenol fA)
N-Nitroso-di-n-oroovlamine fBN)f#>
Hexachloroethane fBN)
Nitrobenzene ' fBN)
Isoohorone fBN)
2-Nitroohenol fA)f*V
2.4-Dimethvlohenol fAt
bis(2-Chloroethoxv1methane fBN)
2.4-Dichloroohenol fA)
1.2.4-Trichlorobenzene ' fBN)
Naphthalene fBN)
4-Chloroaniline fBN)
Hexachlorobutadiene fBN)f*)
4-Chloro-3-methvlnhenol - f A)f*)
2-Methvlnaohlhalene fB^f)
HexachlorocvcloDcntadiene fBN)(lf)
2.4.6-Trichloroohenol ' fA)f*)
2.4.5-Trichloroohenol fA)
''-Chloronaohthalene fBN)
2-Nitroaniline fBN)
Dimethvlohthalate " fBN)
Acenaohthvlene fBN)
2.6-Dinitrotoluene fBhf)
3-Nitroaniline fBN)
Acenaohthene f*)fBN)
2.4-Dinitronhenol fA)f#)
4-Nitronhenol fA)(iO
-.->:! r,'--'-
RRF30
.
' rnnfiimi
RRF<.05
nztaL"
%bvi
"
v--'vi:v-:-::;
''-is* -^
1
'
nks ' " '" ' ' "'
FSeM
ป.
---~.-
"~
OoaEfiers
'(+AJ ^
I
S
#
1
I
S
H
2
I
S
tt
3
-------
Case No.:_
SDG No.:
Data Reviewer:
Site:
Procedure Noi: M2-SVOA
Revision: 1
Date: 06/30/1995
Table M2-SVOA-2
(contd.)
Analytu Date:
Inftnuneni ID:
Date:
Time:
Compound: ' '". v^Vr-^SPCC-ttl':
' ..':-.; ;-:v-^;^^Add!c-(A)T
. B*M/Ntiitnl(BN)
DibcfBiOflf fl *' ' " v' " -' " ""' fBN^
2.4-binhrotohieae ' ' - -';'' -.'-: -'"YUM)
Dietiivfohthalite ' ' .~- 7BNV
X-Chloroohenvtohenvleflier (BNV
Fluorene -' .- '- ''"'""'''''-' "(tttn.'
4-Nhraanfline ~ ' \>'->F-"'--'fv:^(Btn!>
4.^ปPinltftv^"ttielhvlphciiol * -~ *'v".^~- ^-''YA^
N-KhfOioJrohenvlamme ;' v :--' ~~.'< YBN)TT":
4-BromouheBvl-aheiwledier '' ' YBNl
RenttehlomohetMtl '-. ' ''' '(Mft
Phenanihrene ' '" ' '"."" (Btfl
-ArttjrปcetiB ' ''" ' '.'"" '" ; ""'. -JBr^i
Ca'rbazole :''.'.' ':' ' ' IBN>
Dt-n-Butvlnhthalate ' : ' (Btt\
Fhiofซnthene ' ' ' (BrDfl
Pvrene " ' fBN\
_ _. _ .
3 J '-Diehlorab'enndene ' (Btft
BenzoCttanthracene . (Brfl
bij(7-cthvfheTvrtohthal8te flttft
Chrvtene iBN>
Di-n-Oetvlohthalate (BN1(*1
Benzofblfluoranthene fBNI
BenTortrlfluoranthene fBH>
Benzofa^Dvrene ' fBKIf*1)
Indenod .2.3-c Jlovrene (BN)
Dibenzfa.h^anthracene fBN)
Benzofe.h.nDervlene (BN)
^. r; Initial CซI.
>RKr<.05
' . .-. ' ' .
-- A '.- ' .
'-^ /'
. . .
-v. . -.-. ;
'.:-.;: ':'. '. .'
'.'.'. '. '-. '
-:.: ..' .' "
'..' ;' '
-
%RSD>30
- ... . -
'--.
. '
*
. CoulimnDjE Cu*
RRF<.05
.
- .
~j*- "
ซD>25
.
Blanks .
Ub
, 'i
. : " ' :",
"
:
.
Field
\
~-~..,
- 7;- '
Qualifiers
(+/-)'
(
%
I
S
I
4
I
S
-------
Case No.:.
SDG No.:_
Data Reviewer:
Site:
Procedure No.: M2-SVOA
- Revision: 1
_ Date: 06/30/1995
Table M2-SVOA-3. SVGA Soil Surrogate and Matrix Spike Quality Control Summary
Surrogate Data Summary
Sample Identifier:
(Acceptance Ranee, XR):
, '-'!. ' ' : .
''..- i
Soil Sample Recoveries, %R
SI
23-120
...
S2
30-115
"
-' -
S3
18-137
S4 '
24-113
S5
25-121
' .'
ป *
S6
19-122
S7
20-130
.
'- .
S8
20-130
: " -
Qualifiers (+/-)
.. . - .
.. . , ..
SI - Nhrobenzene-dS;S2 = 2-fluorobiphenyl, S3 = teiphenyWU. S4 ซ= phenol-d5, S5 = 2-fluorophenol, S6 ซ= 2,4.6-lribromophenol, S7 ซ= 2-
chloropheiiol-d4,S8 - U-dichlotobenzeae-d4,
MS/MSP Pate Summary
SPCC4T)
CCC(ป)
Spike Compound: Aromatic (AR)
SOIL SAMPLES
Phenol
2-Chlorophenol
1 ,4-Dichlorobenzene
N-Nitroso-di-n-propylamine
1 ,2,4-Trichlorobenzene
4-Chloro-3-methylphenol
Acenaphthene
4-Nitrophenol
2.4-Dtnitrotoluene
Penlachlorophenol
Pyrene
Matrix Spike, Recovery.
%R
Range
26-90
25-102
28-104
41-126
38-107
26-103
3M37
11-114
28-89
17-109
35-142
Actual
Matrix Spike Duplicate,
Recovery* %R
Range
26-90
25-102
. 28-104
41-126
38-107
26-103
31-137
11-114
28-89
17-109
35-142
Actual
MS/MSD
Precision, RPD
Range
35
50
27 .
38
23 .
33
19
50
47
47
36
Actual
Qualifiers
(+/-)
-------
Case No.:.
. SDG No.:.
Data Reviewer:
Site:
Procedure No.: M2-SVOA
Revision: 1
_ Date: 06/30/1995
Table M2-SVOA-3. SVGA Aqueous Surrogate and Matrix Spike Quality Control Summary
^Surrogate Data Sfimmarv
Sample Identifier:
(Acceptance Ranee. XR):
1. . ' .- '
2. "' ' . ' '
3. .. . "
4. '
5.
6.
7.
s. ' : . ..
9."'" ' .'-'
10.
Aquebui Sample Recoveries
Si
35-114
S2
43-116
.' -,:-
--.'
S3
33-141
-
.<; .
S4
10-110
,
S5
21-110
;-.':
ป *" .
*R
S6
10-123
. - ' '.
S7
33-110
i
i
S8
16-110
-. ' ..
Qualifier* (+/-)
\
^ ^ '
-..'.. ;
-".""' ' ' -
SI > Nhrobenzene-
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Procedure No.: M2-SVOA
Revision: 1
Date: 06/30/1995
Page 9 of 39
K = Analyte present./Reported value may be biased high. Actual value is
expected lower.
L = Analyte present. Reported-value may be biased low. Actual value is
expected to be higher. ' . ' ; .
UJ = Not detected, quantitation limit may be inaccurate or imprecise.
UL = Not detected, quantitation limit is probably higher.
Other Codes
Q = No analytical result .
* = Results reported from diluted analysis.
' " ' . '
3.1 Action Level Notification
The purpose behind action level,notification is to make the EPA Remedial Project Officer
(RPM) or the Site Project Officer (SPO) aware of the potential human health risk at the
site. In accordance with the Region HI Hazardous waste division policy, the EPA RPM or
SPO must be promptly notified of any contaminant exceeding the established action level or
the 10-day health advisory limit. The data for contaminants exceeding tte action levels
must be validated as a top priority and reported to the RPM or SPO, Validation of the rest
of the data may then be completed normally.
3.1.1 Acceptance Criteria
EPA's Office of Solid Waste and Emergency Response has established 10-day advisory
limits or the action levels for several organic compounds and elements of special health risk
concerns based on the Safe Drinking Water Act. The semivolatile organic compounds and
their 10-day health advisory limits apply only to aqueous samples and are listed in Table
M2-SVOA-4. The criteria for action level notification are as follows:
The contaminant concentration must be equal to or above the established 10-
day health advisory limits.
Data for contaminants exceeding the action levels must be validated as a top
priority.
The following EPA personnel must be notified of the action level
exceedances:
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Procedure No.: M2-SVGA
Revision: 1
Date: 06/30/1995
Page 10 of 39
EPA RPM or SPO
EPA Section Chiefs:
- Site Investigation (SI)
r- . Remedial
:*-; ; ; Enforcement
-T RCRA
EPA Section Toxicologists:
T- .v Enforcement
Superfund
r RCRA
The remaining data validation should be completed per normal procedures.
Any special instructions from the Hazardous Waste Division should be
followed. .
Records should be kept of the data review, action level notification and any
follow up instructions and actions.
Table M2-SVOA-4
SEMIVOLATILE ORGANIC ANALYTES AND ACTION LEVELS
Compound
1 ,3-Dichlorobenzene
Pentachlorophenol
Action
Level*
8,930
300
Compound
. 1,4-Dicnlorobenzene
Action
Level*
10,700
*A11 units are ug/1.
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Procedure No.: M2-SVOA
Revision: 1
Date: 06/30/1995
Page 11 of 39
3.1.2 Review Items
All data required to perform Level M2 validation, as detailed in the following sections, are
necessary for carrying out action level notification. The location of. the data and their
retrieval procedures are also discussed below.
3.1.3 Evaluation Procedure
The evaluation process preceding action level notification will primarily consist of
comparing the results on Form I's with the action levels presented in Table M2-SVOA-4.
Following the identification of the contaminants exceeding the action levels, focused data
validation should be performed using the criteria and procedures described in the
appropriate sections below.
3.1.4 Action
The action resulting from focused data validation will be the notification of action level
exceedance to the personnel identified above in Section 3.1.1.
3.1.5 Reporting
Copies of Form I's can be used to highlight the contaminants above the action levels. The
findings of the focused validation can be summarized in a memorandum," and the data
qualifiers resulting from focused validation may be written on the Form I's. The marked
up forms should be clarified that they represent validation of only the contaminants
exceeding the action levels, and not all data;
3.2 Technical Holding Times
The objective is to ascertain the validity of results based on the holding time of the sample
from time of collection to time of sample extraction and analysis.
3.2.1 Acceptance Criteria
Technical requirements for sample holding times have only been established for water
matrices. The holding times for soils (and "other non-aqueous matrices such as sediments,
oily wastes, and sludge) are currently under investigation. When the results are available
they will be incorporated into the data evaluation process. Additionally, results of holding
time studies will be incorporated into the data review criteria as the studies are conducted
and approved.
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Procedure No.: M2-SVOA
Revision: 1
Date: 06/30/1995
Page 12 of 39
The holding time criteria for water samples, as stated in the current 40 CFR Part 136
(Clean Water Act) is as follows:
For semivolatile compounds in cooled (@ 4ฐQ water samples the maximum
holding time is 7 days from sample collection to extraction and 40 days from
sample extraction to analysis.
It is further required that semivolatile compounds k properly preserved non-aqueous
samples be extracted within 7 days from sample collection and the .extracts analyzed within
40 days from sample extraction.
3.2.2 Review Items
Form I SV-1 and SV-2, EPA Sample Shipping Log -and/or chain-of-custody.
3.2.3 Evaluation Procedures
Technical holding times for sample extraction are established by comparing the sampling -
date on the EPA Sample Traffic Report with the dates of extraction on Form I SV-1 and/
SV-2. To determine if the samples were analyzed within the holding time after extraction,
compare the dates of extraction on the sample extraction sheets with the dates of analysis
on Form I SV-1 and SV-2.
Verify that the C.O.C. indicates that the samples were received intact and iced. If the
samples were not iced or there were any problems with the samples upon receipt, then
discrepancies in the sample condition could affect the data.
3.2.4 Action
1. If technical Holding times are exceeded, flag all positive results as estimated "J"
and sample quantitation limits as estimated "UJ" and document that holding times
were exceeded. However, please note that some extractable compounds are
extremely persistent in the environment (e.g., PAHs) in non-aqueous matrices and
would not be expected to- degrade significantly during sample storage. The
reviewer must use professional judgment in the application of data qualifiers to
those compounds in non-aqueous matrices.
2. If in the professional judgment of the data reviewer a loss of semivolatile
compound(s) is evident due to exceeding the holding time criteria, the affected
positive results or the associated quantitation limits may be qualified as biased low,
"L" or "UL" respectively. The narrative must contain the reviewer's justification
- for qualification of the compound results as biased low.
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Procedure No.:- M2-SVOA
Revision: 1
Date: 06/30/1995
Page 13 of 39.
3. If technical holding times are grossly exceeded (greater than 2 times the required
technical holding time), either on the first analysis or upon re-analysis, the reviewer
must use professional judgment to determine the reliability of the data and the
effects of additional storage on the sample results. The reviewer may determine
that positive results or the associated quantitation limits are approximates and should
be qualified with "J" or "UJ", respectively. The reviewer may determine that
non-detect data are unusable (R). ,
4. Because of limited information concerning holding times for non-aqueous samples,
it is recommended, that a comment in the data review narrative be included to state
that aqueous holding times were applied.
5. Whenever possible, the reviewer should comment on the effect of exceeding the
holding time oh the resulting data in the data review narrative.
' ''.-" V' ''*;' " -.'. - "
6. When contractual and/or technical holding times are exceeded, this should be noted
on me ORDAS form. 7
7. The reviewer should also be aware of the scenario in which the laboratory has
exceeded the technical holding times, but met contractual holding times. In this
case, the data .reviewer should notify the Regional TPO (where samples were
collected) and/or RSCG that shipment delays may have occurred so that the field
problem can be corrected. The reviewer may pass this information on to the
Regional TPO on the ORDAs, but should explain that contractually the laboratory
met the requirements.
8. When there are other quality control problems in conjunction with exceeded holding
times (such as suspected laboratory contamination), the reviewer should follow the
hierarchy of qualifiers. In particular, if for any reason the reviewer doubts the
presence of a compound, the data summary should display only the "B" or "R"
qualifier, and not the "L" qualifier. This is because no net direction of bias can be
inferred under these conditions.
3.3 GC/MS Instrument Performance Check
Gjas chromatograph/mass spectrometer (GC/MS) instrument performance checks (formerly
referred to as tuning) are performed to ensure mass resolution, identification and, to some
degree, sensitivity. These criteria are not sample specific. Conformance is determined
using standard materials, therefore, these criteria should be met in all circumstances.
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Procedure No.: M2-SVOA
Revision: 1
Date: 06/30/1995
. Page 14 of 39
3.3.1 Acceptance Criteria
The analysis of the instrument performance check solution must be performed at the
beginning of each 12-hour period during which samples or standards are analyzed. The
instrument performance check, decafluorotriphenylphosphine (DFTPP) for semivolatile
analysis, must meet the ion abundance criteria given below. ,
Decafluorotriphenylphosphine (DFTPP)
m/z ION ABUNDANCE CRITERIA
51 30.0-80.0% of m/z 198
68 Less than 2.0% of m/z 69
69 ' Present *".':/
70 Less than 2.0% of m/z 69
127 25.0-75.0% of m/z 198
197 Less than 1JO% of m/z 198 ,
198 Base peak, 100% relative abundance
199 5.0-9.0% of m/z 198
275 10.0-30.0% of m/z 198
365 Greater than 0.75% of m/z 198
441 Present, but less than m/z 443
442 40.0 -110.0% of m/z 198
443 15.0-24.0% of m/z 442
NOTE: All ion abundances must be normalized to m/z 198, the nominal base peak,
even though the ion abundances of m/z 442 may be up to 110 percent that of
m/z 198.
3.3.2 Review Items
FormVSV.
3.3.3 Evaluation Procedures
1. Compare the data presented on each GC/MS Instrument Performance Check (Form
V SV) with each mass listing submitted and ensure the following:
a. Form V SV is present and completed fgr each. 12-hour period during which
samples were analyzed.
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Procedure No.: M2-SVOA
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b. The appropriate number of significant figures has been reported (number of
significant figures given for each ion in the ion abundance criteria column)
and that rounding is correct.
c. The laboratory has not made any calculation errors.
' *"'".' ' ' " .'''-'.
2. Verify that the ion abundance criteria were met. The criteria for m/z 68, 70, 441,
and 443 are calculated by normalizing to the specified m/z.
." '" ? > ' '', ,'.'"' "' - """ r":'_ 'V1.',' :"" *'.'. ' ;
. ' - ""'.''.."_- - . \ . i" .''
3. If possible, verify that spectra were generated using appropriate background
subtraction techniques. Since the DFTPP spectrum is obtained from
chromatographic peaks that should be free from coelutioh problems, background
- subtraction should be done in accordance with the following procedure; Three
scans (the peak apex scan and the scans .immediately preceding and following the
apex) are acquired and averaged and background subtraction must be accomplished
using a single/scan prior to the elution of DFTPP. v . ?
NOTE: ' All instrument conditions must be identical to those used in the
? sample analysis. Background subtraction actions resulting in spectral
distortions for the sole purpose of meeting the contract specifications
are contrary to the quality assurance objectives and are therefore
unacceptable.
3.3.4 Action
1. If the laboratory has made minor transcription errors which do not significantly
affect the data, the data reviewer should make the necessary corrections on a copy
of the form. .
2. If the laboratory has failed to provide the correct forms or has made significant
transcription or calculation errors, the Region's designated representative should
contact the laboratory and request corrected data. If the information is not
available, then the reviewer must use professional judgment to assess the data. The
Regional TPO should be notified by noting the problem(s) on the ORDAS.
3. If mass assignment is in error (such as m/z 199 is indicated as the base peak rather
than m/z 198), classify all associated data as unusable, (R).
4. If ion abundance criteria are not met, professional judgment may be applied to
determine to what extent the data may be utilized. Guidelines to aid in the
application of professional judgment in evaluating ion abundance criteria are
discussed as follows:
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a. Some of the most critical factors in the DFTPP criteria are the
non-instrument specific requirements that are also not unduly affected by the
location of the spectrum on the chromatographic profile. The m/z ratios for
198/199 and 442/443 are critical. These ratios are based on the natural
abundances of carbon 12 and carbon 13 and, should always be met.
Similarly, the relative abundances for m/z 68, 70,197, and 441 indicate the
condition of the instrument and the suitability of the resolution adjustment
and are very important Note that all of the foregoing abundances relate to
adjacent ions; they are relatively insensitive to differences in instrument
design: and position of the spectrum on the chromatographic profile. .
b. For the ions at m/z 51,127, and 275, the actual relative abundance is not as
critical. For instance, if m/z 275 has 40% relative abundance (criteria:
10.0-30.0%) and other criteria arejnet, then the deficiency is minor.
c. .The relative abundance of m/z 365 is an indicator of suitable instrument zero
adjustment. If relative abundance for m/z 365 is zero, minimum detection
limits may be affected. On the other hand, if m/z 365 is present, but less
than the 0.75% minimum abundance criteria, the deficiency is not as-
.serious/ . . '. . . ' -.'- '.':.' ':
5. Decisions to use analytical data associated with DFTPP instrument performance
checks not meeting contract requirements should be clearly noted in the data review
narrative. \ . , ' ~-
6. If the reviewer has reason to believe that instrument performance check criteria
were achieved using techniques other than those specified in the SOW and in
subparagraph a. above, additional information on the DFTPP instrument
performance checks should be obtained. If the techniques employed are found to be
at variance with contract requirements, the procedures of the laboratory may merit
evaluation. Concerns or questions regarding laboratory performance should be
noted for TPO action on the ORDAS. For example, if the reviewer has reason to
believe that an inappropriate technique was used to obtain background subtraction
(such as background subtracting from the solvent front or from another region of
the chromatogram rather than the DFTPP peak), then this should be noted for TPO
action on the ORDAS. ,
3.4 Initial Calibration
Compliance requirements for satisfactory instrument calibration are established to ensure
that the instrument is capable of producing acceptable qualitative and quantitative data for
compounds on the semivolatile Target Compound List (TCL). Initial calibration
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Procedure No.: M2-SVOA
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demonstrates that the instrument is-capable of acceptable performance in the beginning of
the analytical run and of producing a linear calibration curve.
3.4.1 Acceptance Criteria .;.
1. Initial calibration standards containing both semivolatile target compounds and
surrogates are analyzed at concentrations of 20, SO, 80, 120, and 160 ug/L at the
beginning of each analytical sequence or as necessary if the continuing calibration
acceptance criteria are not met. The initial calibration (and any associated samples
and blanks) must be analyzed within 12 hours of the associated instrument
performance check.
2. Minimum Relative Response Factor (RRF) criteria must be greater than or equal to
0.05. Contractual RRF criteria are Iisted4ir Appendix A.
3. The Percent Relative Standard Deviations (%RSD) for the RRFs in the initial
calibration must be less than or equal to 30%.
3.4.2 Review Items
Form VI SV-1 and SV-2 and chromatograms.
3.4.3 Evaluation Procedures
1. Verify that the correct concentration of standards were used for the initial
calibration (i.e., 20, 50,. 80, 120, and 160 ug/L)* For the eight compounds with
higher CRQLs, only a four-point initial calibration is required (i.e., 50, 80, 120,
and 160 ug/L). '
2. If any sample results were calculated using an initial calibration, verify that the
correct standard (i.e., the 50 ppb standard) was used for calculating sample results
and that the samples were analyzed within 12 hours of the associated instrument
performance check.
3. Evaluate the RRFs for all semivolatile target compounds and surrogates:
Verify that all semivolatile target compounds and surrogates have RRFs that
are greater than or equal to 0.05. If problems are suspected with low
response factor or compound identification, also check elution order.
NOTE: Because historical performance data indicate poor response and/or
erratic behavior, the semivolatile compounds listed above have no
U.S. EPA Headquarters Library
Mail code 3201
1200 Pennsylvania Avenue NW
Washington DC 20460
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contractual maximum %RSD criteria. Contractually they must meet
a minimum RRF criteria of 0.01; however, for data review
purposes, the "greater than or equal to 0.05" criterion, is applied
to aU semivolatile compounds.
Semivolatile Target Compounds Exhibiting Poor Response
' : ' ' ' ' . ' '
i^'-oxybis^-Chlorppropane)
, 4-Chloroaniline
Hexachlorobutadiene ,
Hexachlorocyclopentadiene
2-Nitroaniline
Dimethylphthalate
3-Nitroaniline
2,4-Dinitrophenol
4-Nitrophenol
Carbazole
Diethylphthalate
4-Nitroaniline ^
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
Di-n-butylphthalate
Butylbenzylphthalate
3-3'-Dichlorobenzidine
bis(2-Ethylhexyl)phthalate
Di-n-octylphthalate
4. Evaluate the %RSD for all semivolatile target compounds and surrogates.
a. Verify that all semivolatile target compounds have a %RSD of less than or
equal to 30%. The contractual criteria for an acceptable initial calibration
specifies that up to any 4 semivolatile target compounds may fail to meet
minimum RRF or maximum %RSD as long as they have RRFs that are
greater than or equal to 0.010, and %RSD of less than or equal to 40.0%.
For data review purposes, however, all compounds must be considered for
qualification when the %RSD exceeds the ฑ 30.0% criterion.
b. If the %RSD is greater than 30.0%, then the reviewer should use
professional judgment to determine the need to check the points on the curve
for the cause of the non-linearity. This is checked by eliminating either the
high point or the low point and recalculating the %RSD.
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Procedure No.: M2-SVOA
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. Page 19 of 39
3.4.4 Action
1. All semivolatile target compounds, including the 19 "poor performers," listed
above, will be qualified using the following criteria:
a. If the %RSD is greater than 30.0% and the RRF is greater than or equal to
0.05, qualify positive results with "J", and non-detected semivolatile target
compounds using professional judgment
b. If the'RRF is less than 0.05, qualify positive results that have acceptable
mass spectral identification with "J" using professional judgment, and non-
detects as unusable.(R). '.
2. At the reviewer's discretion, a more in-depth review to minimize the qualification
of data can be accomplished by considering the following:
a. If any of the required semivolatile compounds have a %RSD greater than
30.0%, and if eliminating either the high or the low point of the curve does,
hot restore the %RSD to less than or equal to 30.0%: .
i. Qualify positive results for that compound(s) with "J".
ii. Qualify non-detected semivolatile target compounds based on
professional judgment. /--'-
b. If the high point of the curve is outside of the linearity criteria (e.g. due to
saturation):
i. No qualifiers are required for positive results in the linear portion of
the curve.
ii. Qualify positive results outside of the linear portion of the curve with
ซซTป> . '
J .
iii. No qualifiers are needed for non-detected target compounds.
c. If the low end of the curve is outside of the linearity criteria:
i. No qualifiers are required for positive results in the linear portion of
the curve.
t
ii. Qualify low level positive results in the area of non-linearity with
"J".
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ill. Qualify non-detected semivolatile target compounds using
professional judgment.
3. If the laboratory has failed to provide adequate calibration information, the
designated representative should contact the laboratory and request the necessary
information. If the information is not available, the reviewer must use professional
judgment to assess the data.
4. Whenever possible, the potential effects on the data resulting from a failure to meet
calibration criteria should be noted in the data review narrative.
5. If calibration criteria are grossly exceeded, this should be noted for TPO action on
the ORDAS.
'6. When it is suspected that relative response factors were incorrectly generated from
misidentified peaks or incorrect area measurements, the laboratory should be
contacted to requantitate these RRFs and associated sample results. .The ORDAS
.should identify affected results and document the cause of the reviewer's suspicions.
In addition, a CLP telephone log must be completed.
7. Positive results for compounds flagged for blank contamination (B) will not need a
separate flag (J) in the data summary form for minimum RRF, %RSD, or %D
outside criteria. However, these situations should be addressed UL the data review
narrative and issues pertaining to noncompliance should be documented on the
ORDAS.
3.5 Continuing Calibration
Compliance requirements for satisfactory instrument calibration are established to ensure
that the instrument is capable of producing acceptable qualitative and quantitative data for
semivolatile target compounds. Continuing .calibration establishes the 12-hour relative
response factors on which the quantisations are based and checks satisfactory performance
of the instrument on a day-to-day basis.
3.5.1 Acceptance Criteria
1. Continuing calibration standards containing both target compounds and surrogates
are analyzed at the beginning of each 12-hour analysis period following the analysis
of the instrument performance check and prior to the analysis of blanks and
samples.
2. The minimum Relative Response Factors (RRF) for semivolatile target compounds
and surrogates must be greater than or equal to 0.05.
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3. The percent difference (%D) between the initial calibration RRF and the continuing
calibration RRF must be within +.25.0% for all target compounds.
3.5.2 Review Items
Form VH SV-1 and SV-2 and chromatograms.
3.5.3 Evaluation Procedures
1. Verify that the continuing calibration was run at the required frequency and that the
continuing calibration was compared to the correct initial calibration.
2. Evaluate the continuing calibration RRF for all semivolatile target compounds and
surrogates. . *"'' :
Verify that all semivolatile target compounds and surrogates have RRFs
within specifications.
NOTE: Because .historical performance data indicate poor response and/or erratic
behavior, the compounds listed in Section 3.4.3 have no contractual
maximum %D criteria. Contractually they must meet a minimum RRF
criterion of 0.01; however, for data review purposes, the "greater than
or equal to 0.05" criterion is applied to all semivolatile: compounds.
3. Evaluate the %D between initial calibration RRF and continuing calibration RRF
for one or more semivolatile compounds.
Verify that the %D is within the +_ 25.0% criterion, for all semivolatile
target compounds and surrogates. Note those compounds which have a %D
outside the +.25.0% criterion. The contractual criteria for an acceptable
continuing calibration specifies that up to any 4 semivolatile target
compounds may fail to meet minimum RRF or maximum %D as long as
they have RRFs that are greater than or equal to 0.010, and %D of less than
or equal to 40.0%. For data review purposes, however, all compounds must
be considered for qualification when the %D exceeds the ฑ25.0%
criterion.
3.5.4 Action
1. The reviewer should use professional judgment to determine if it is necessary to
qualify the data for any semivolatile target compound. If qualification of data is
required, it should be performed using the following guidelines:
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a.
Procedure No.: M2-SVOA
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If the %D is outside the ฑ 25.0% criterion and the continuing calibration
RRF is greater than or equal to 0.05, qualify positive results "J".
b. If the %D is outside the ฑ 25,0% criterion and the continuing calibration
RRF is greater than or equal to 0.05, qualify non-detected semivolatile target
compounds based on professional judgment .
c. If the continuing calibration RRF is less than 0.05, qualify positive results
. that have acceptable mass spectral identification with "J" or use
professional judgment., -
d. If the continuing calibration RRF is less than 0.05, qualify non-detected
semivolatile target compounds as unusable (R).
2. If the laboratory has failed to provide adequate calibration information, the
designated representative should contact the laboratory and request the necessary
information. If the information is not available, the reviewer must use professional
judgment to assess'the data.
3. Whenever possible, the potential effects on the data resulting from a failure to meet
calibration criteria should be noted in the data review narrative.
4. If calibration criteria are grossly exceeded, this should be noted for TPO action on
theORDAS. c
5. When it is suspected that relative response factors were incorrectly generated from
misidentified peaks or incorrect area measurements, the laboratory should be
contacted to requantitate these RRFs and associated sample results. The ORDAS
should identify, affected results and document the cause of the reviewer's suspicions.
In addition, a CLP telephone log must be completed.
6. Positive results for compounds flagged for blank contamination (B) will not need a
separate flag (J) in the data summary form for minimum RRF, %RSD, or %D
outside criteria. However, these situations should be addressed in the data review
narrative and issues pertaining to noncompliance should be documented on the
ORDAS.
3.6 Blanks
The purpose of laboratory (or field) blank analyses is to determine the existence and
magnitude of contamination problems resulting from laboratory (or field) activities. The
criteria for evaluation of blanks apply to any blank associated with the samples (e.g.,
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Procedure No.: M2-SVOA
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method blanks, instrument blanks, trip blanks, and equipment blanks). If problems with
any blank exist, all associated data must be carefully evaluated to determine whether or not
there is an inherent variability in the data, or if the problem is an isolated occurrence not
affecting other data.
3.6.1 Acceptance Criteria
1. No contaminants should be found in the blanks.
2. The method blank must be analyzed on each GC/MS system used to analyze that
specific group or set of samples.
3.6.2 Review Items
' ' ' .. . . - ' * " . '
Form I SV-1 and SV-2, Form IV SV and chromatograms.
, . -, . .
3.6.3 Evaluation Procedures
1. Review the results of all associated blanks, Form I SV-1 and SV-2, and
chromatograms to evaluate the presence of target and non-target compounds in the
blanks.
2. Verify that a method blank analysis has been reported per matrix, per concentration
level, for each extraction batch and for each GC/MS system used to analyze
semivolatile samples. The reviewer can use the Method Blank Summary (Form IV
SV) to assist in identifying samples associated with each method blank.
3.6.4 Action
If the appropriate blanks were not analyzed with the frequency described above, then the
data reviewer should use professional judgment to determine if the associated sample data
should be qualified. The reviewer may need to obtain additional information from the
laboratory. The situation should be noted for TPO action on the ORDAS.
Action in the case of unsuitable blank results depends on the circumstances and origin of
the blank. Positive sample results should be reported unless the concentration of the
compound in the sample is less than or equal to 10 times (lOx) the amount in any blank for
the common phthalate contaminants, or 5 times the amount for other compounds. In
instances where more than one blank is associated with a given sample, qualification should
be based upon a comparison with the associated blank* having the highest concentration of
a contaminant. The results must not be corrected by subtracting any blank value.
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For qualification purposes, to determine the highest concentration of a
contaminant, consider 'all blanks in a case associated with all samples.
Field blanks measure contamination introduced not only in the field but also from the
laboratory. In general, evaluation of the impact on specific sample results, is handled as
with laboratory blanks. The reviewer should use caution in attributing contamination to the
field as opposed to laboratory sources. However, when field-introduced contamination is
suspected, it is helpful for the reviewer to consult the sampling group to identify possible
sources and prevent future reoccurrences. Verified field sources of contamination should
be noted in the data review narrative. If a field blank has a highest concentration of a
contaminant, then'all samples in the associated case are qualified "B", using the Sx and
lOx rule. Other field blanks associated with the case are not qualified.
Specific actions are as follows:
1. If a semivolatile compound is found in a blank but not found in the sample, no
action is taken. If the contaminants found are volatile target compounds (or
interfering non-target compounds) at significant concentrations above the CRQL,
then this should be noted for TPO action on the ORDAS.
2. Any semivolatile compound detected in the sample (other than the common
phthalate contaminants), that was also detected in any associated blank, is qualified
"B" if the sample concentration is less than five times (Sx) the blank concentration.
For phthalate contaminants, the results are qualified "B" when the sample result is
less than lOx the blank concentration.
In using the 5x/10x rule to compare blank results to sample results which were
calculated using different weights, volumes, or dilution factors, the reviewer must
choose between comparing the levels detected with the instrument, the total amount
of compound (ug of contamination) present in the extracts, or the final concentration
of the contaminant in the sample aliquots. Often, more than one approach will be
acceptable and will yield the equivalent flagging of sample results.
a. Comparisons involving sample dry weight correction factors, but with all
other calculation factors the same for sample versus blank:
In this case, the reviewer can compare the wet weight
concentrations, instrument levels, or the total amount
of compound (ug of contaminant) in the extracts. All
of these approaches will be acceptable and will yield
equivalent flagging of sample results.
b. When the sample has a smaller initial aliquot size than the blank (purge or
extraction weight/volume), but all other calculation factors beyond this
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Procedure No.: M2-SVOA
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analytical step are .identical (Le., same final extract volumes, injection
volumes, and extract dilution factors for sample versus blank):
In this case, it is acceptable and equivalent to compare either
instrument levels, the total amount of compound (ug of contaminant)
in the extracts, or the concentration of contaminant in the extracts.
'';. Final concentrations of sample versus blank should not be compared.
c. When the sample has a larger final extract volume or a greater dilution
factor than the blank: . ' >; .
'::*(--^ If the laboratory contaminant;may have been introduced after or
during the sample dilution-' step, then a direct comparison of
, instrument levels is appropriate. OFor 'example, comparing the
: instrument level result for a water sample that was diluted 1:100
prior to injection would'_ take into account possible laboratory
contamination of the syringe, instrument, or dilution solvent
On the other hand, if it is highly probable that the contamination
originated before the dilution step, then it is more appropriate to
calculate and compare the total amount of compound (ug of
contaminant) present in the undiluted extract of the sample versus the
blank. For example, a SNA extract diluted 1:100 prior to injection
may only be subject to phthalate contamination prior to the dilution
step (i.e., during extraction/concentration).
If the results of a dilution run are to be flagged (B) because of blank
contamination, the reviewer should attempt to determine whether an
undiluted run was also performed. If so, the undiluted run may be
used to verify the presence of a compound detected at levels too high
to be questioned or, conversely, to prove that a compound was
actually not present at levels multiplied by a dilution factor.
The reviewer should note that blanks may hot involve the same weights, volumes,
or dilution factors as the associated samples. These factors must be taken into
consideration when applying the "5x" and "10x" criteria, such that a comparison
of the total amount of contamination is actually made.
Additionally, there may be instances where little or no contamination was present in
the associated blanks, but qualification of the sample was deemed necessary.
Contamination introduced through dilution is one example. Although it is not
always possible to determine, instances of this occurring can be detected when
contaminants are found in the diluted sample result, but are absent in the undiluted
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sample result. Since both results are not routinely reported, it may be impossible to
verify this source of contamination. However, if the reviewer determines that the
contamination is from a source other than the sample, he/she should qualify the
data. An explanation of the rationale used for this determination should be provided
in the narrative accompanying the Regional Data Assessment Summary.
3. If gross contamination exists (i.e., saturated peaks by GC/MS), all affected
compounds in the associated samples should be qualified as unusable (R), due to
interference. This should be noted for TPO action if the contamination is suspected
of having an effect on the sample results. .-'.';. . ( . ,
4. If inordinate amounts of other target compounds are found at low levels in the
blank(s), it may be indicative of a problem and should be noted for TPO action.
'.'" ':-'-".^-'" ^>;:T'^v^^.r-:jW^-4'^^^:-:.'^';3:^-";'-'''' ' ' . '
5. The same consideration given to the target compounds should .also be given to
Tentatively Identified Compounds (TICs) which are found in both the sample and
associated Wank(s^
6. If an instrument blank was not analyzed following a sample analysis which-
' contained an anaiyte(s) at high concentrations), sample analysis results after the
high concentration sample must be evaluated for carryover. Professional
judgment should be used to determine if instrument cross-contamination has
affected any positive compound identifications). If instrument cross-
contamination is suggested, then this should be noted for TPO action if the
cross-contamination is suspected of having an effect on the sample results.
7. Blanks or samples run after a-matrix spike or standard should be carefully examined
to determine the occurrence of instrument or syringe carry-over. Since the
efficiency of sample transfer can vary dramatically according to apparatus and
operator techniques, professional judgment should be used in each case to determine
whether sample or blank results are .attributable to carry-over. Some common
examples are as follows: ,
Zero to one percent syringe carry-over occasionally in BNA runs.
Higher percentages of carry-over following BNA runs that are saturated.
Sample results which are possible artifacts of carry-over should be flagged as
unreliable (R).
8. When there is convincing evidence that contamination is restricted to a particular
instrument, matrix, or concentration level, the 5X/1QX rule will only be applied to
compare contaminated blanks to certain associated samples (as opposed to all
samples in the case). Some examples are as follows:
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Procedure No.: M2-SVOA
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Column bleed (siloxanes) may be localized to a particular instrument.
Common laboratory contaminants, such as methylene chloride and
phthalates, are generally too unpredictable to safely assume contamination is
restricted to a particular instrument, matrix, or concentration level.
The following are examples of: applying the blank qualification guidelines. Certain
circumstances may warrant deviations from these guidelines. " . :. ,
Example 1: Sample result is greater than the Contract Required Quantitation
Limit (CRQL), but is less than the 5x or lOx multiple of the blank
result. -'- '' .. : . '',- ' . .. " - ';';. -'-....'v:'-''. :-.'- '.-'.'
Rule
Blank Result
CRQL
Sample Result
Qualified Sample Result
5x
'5, 5'
60 30
60S 30B
In the example for the "lOx" rule, sample results less than 70 (or 10
x 7) would be qualified "B". In the case of me "5x" rule, sample
results less than 35 (or 5 x 7) would be qualified "B".
Example 2: Sample result is less than CRQL, and is also less than the 5x or lOx
multiple of the blank result.
Blank Result
CRQL
Sample Result
Qualified Sample Result
Rule
IQx 5jc
66
5 5
4J 4J
4B 4B
Note that data are reported as 4B, indicating that the qualitative
presence is not confirmed.
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Example 3: Sample result. is greater than the 5x or lOx multiple of the blank
result.
Rule
Blank Result 10 10-
Sample Result - 120 60
QuaUfied.Sample Result 12(te 60
For both the "lOx" and "5x" rules, sample results exceeded the
adjusted blank results of -100 (or 10x10) and SO (or 5x10),
respectively. ^ .': "-' .: :- -.' : . -;-.'..;'" :' ''''-.'
3.7 Surrogate Spikes
Laboratory performance on individual samples is established by means of spiking activities.
All samples are spiked with surrogate compounds prior to sample preparation. The
evaluation of the results of these surrogate spikes is not necessarily straightforward. The
sample itself may produce effects because of such factors as interferences and high
concentrations of analytes. Since the effects of the sample matrix are frequently outside the
control of the laboratory and may present relatively unique problems, the evaluation and
review of data based on specific sample results is frequently subjective and demands
analytical experience and professional judgment. Accordingly, this section consists
primarily of guidelines, in some cases with several optional approaches suggested.
3.7.1 Acceptance Criteria
1. Surrogate spikes, 4 acid compounds (3 required and 1 advisory) and 4 base/neutral
compounds (3 required and 1 advisory) are added to all samples and blanks to
measure their recovery in sample and blank matrices.
2. Surrogate spike recoveries for semivolatile samples and blanks must be within the
limits specified on Form n SV-1 and SV-2.
3.7.2 Review Items
Form II SV-1 and SV-2 and chromatograms.
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3.7.3 Evaluation Procedures
1. Review chromatograms to check the surrogate spike recoveries on the Surrogate
Recovery Form n SV-1 and SV-2.
2. The following should be determined from the Surrogate Recovery form(s):
a. If any two base/neutral 01 acid surrogates are out of specification, or if any
one base/neutral or aad extractable surrogate has a recovery of less than
10%, then there should be a reanalysis to confirm that die non-compliance is
because of sample matrix effects rather than laboratory deficiencies.
NOTE: When meie are followed by successful re-
^1he : laboratories are required to report only ;fhe successful run.
D. The laboratory has failed to perform satisfactorily if surrogate recoveries are
. . .; out of specification and there is no evidence of reinjection of the extract, or
: reextraction and reanalysis (if reinjection fails to resolve the problem).
c. Verify mat no blanks have surrogates recoveries outside the criteria.
'.-'". ; ' * . . ' '
3. Any time there are two or more analyses for a particular fraction the reviewer must
determine which are the best data to report. Considerations should include but are
not limited to:
a. Surrogate recovery (marginal versus gross deviation).
b. Technical holding times.
c. Comparison of the values of the target compounds reported in each fraction.
d. Other QC information, such as performance of internal standards.
4. When both the initial analysis and the reanalysis have surrogate recoveries outside
of criteria, the data summary should normally contain the highest concentration
obtained for each compound detected, provided that surrogate recoveries in the
analysis being reported do not suggest a high bias. However, if a demonstrated
laboratory contaminant is detected in one analysis but not the other, the negative
result may be more appropriate to report.
When the reanalysis of a fraction is within surrogate recovery criteria, the
laboratory is required to provide only data for the acceptable analysis. If both sets
of data are provided, and if a compound was detected in the initial analysis but not
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Procedure No- M2-SVOA
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Page 30 of 39
the reanalysis, then the positive result should be reported (provided the compound is
not a demonstrated laboratory contaminant). The reported result should be flagged
as estimated (J), due to possible sample inhomogeneity.
5. If advisory surrogates are outside established criteria, professional judgment will be
used in qualifying the sample results. If the results are outside the criteria, then
qualification would only affect similar target compounds.. '
3.7.4 Action
Data are not qualified with respect to surrogate recovery unless two or more semivolatile
surrogates, within the same fraction (base/neutral or acid fraction), are out-bf specification.
For surrogate spike recoveries out of specification, the following approaches are suggested
based on a review of all data from the case, especially considering the apparent complexity
of the sample matrix. ;
NOTE: These actions apply to all surrogates, except for "advisory" surrogates.
Professional judgment should be used in qualifying sample results based on.
advisory surrogate recoveries. Qualification based on advisory surrogate"
recoveries should be applied to similar compounds in the sample only.
Specify in the .narrative any actions taken based on advisory surrogate
recovery. .
1. If two or more surrogates in either semivolatile fraction (base/neutral or acid
fraction) have a recovery greater than the upper acceptance limit (UL):
a. Specify the fraction that is being qualified; i.e. acid, base/neutral, or both.
b. Detected semivolatile target compounds are qualified biased high, "K".
c. Results .for non-detected semivolatile target compounds should not be
qualified.
2. If two or more surrogates in either semivolatile fraction have a recovery greater
than or equal to 10% but less than the lower acceptance limit (LL):
a. Specify the fraction that is being qualified, i.e. acid, base/neutral, or both.
b. Detected semivolatile target compounds are qualified biased low, "L".
c. For non-detected semivolatile target compounds, the sample quantitation
limit is qualified as biased low, "UL".
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Procedure No.: M2-SVOA
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3. If any surrogate in either semivolatile fraction show less than 10% recovery:
a. Specify the fraction that is being qualified, i.e. acid, base/neutral, or both.
b. Detected semivolatile target compounds are qualified biased low, "L".
c. Non-detected semivolatile target compounds may be qualified as unusable
(R). (If advisory surrogate limits are not met, use professional judgment to
qualify non-detected compounds). : :'-':'>'-.'' , ,
... ::'. --". ..-,">... ;-;. tabl
QUALIFICATION OF SEMI
SURROG;
. '.'.. '. '
Detected analytes
Non-detected analytes
2 or 3
All High
K
;None
CM2-SVOA
[VOLATJLE
ITE.BBCO1
2or3
All Low
L
UL
-5 '-:>'' ;/.:. . '
V ANALYTES BASED ON
SERIES ::c,:-,-;>-\,.:.. ^%V '-'V '
2 or 3
Mixed High/Low
-. :,J "--;:. ;".;: '
ui
1 or More
< 10%Rec.
L
R
4. If two or more surrogate recoveries in either semivolatile fraction (base/neutral or
. acid fraction) are outside surrogate recovery limits, 'and one of the recoveries is
below the lower limit (but > 10%) and the other recovery is above the upper limit:
a. Specify the fraction that is being qualified, i.e., acid, base/neutral, or both.
b. Detected semivolatile target compounds are qualified as estimated, "J".
c. Non-detected semivolatile target compounds are qualified as estimated,
"UJ".
5. In the special case of a blank analysis with surrogates out of specification, the
reviewer must give special consideration to the validity of associated sample data.
The basic concern is whether the blank problems represent an isolated problem with
the blank alone, .or whether there is a fundamental problem with the analytical
process. For example, if one or more samples in the batch show acceptable
surrogate recoveries, the reviewer may choose to consider the blank problem to be
an isolated occurrence. However, even if this judgment allows some use of the
affected data, analytical problems should be noted for TPO action. Also note if
there are potential contractual problems associated with the lack of re-analysis of
samples that were out of specification.
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Procedure No.: M2-SVOA
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6. Whenever possible, the potential effects of the data resulting from surrogate
recoveries not meeting the advisory limits should be noted in the data review
narrative.
7. Positive results for compounds already flagged for blank contamination will not
need a separate flag for surrogate recoveries. However, these situations should be
addressed in the narrative or the support documentation.
8. When dilutions are performed which prevent -detection of BNA surrogate
.. compounds;-the narrative or support documentation should indicate.that extraction
efficiency/methodaccuracy cannot be verified.
' :.;'-;;.:-:;-::r;';'\- ; " "... ;- ' ''. --: '' ' ' ...''.- . " ' '/-. /
9., Although semivolatile surrogate recoveries cannot usually be correlated with
specific analytes, m the followmg cases s
a particular suro?g^:A;r';\ :.;;;; ..-.'" ' .. '";!:'. '; ' "' ' '.'.' r
a^ When a semivolatile surrogate is the deuterated analog of a TCL analyte (for
exmple]r^phen6l;and pheiibi), a low recovery for the surrogate can be
: used to; flag positive results and quantitation limits as biased low for the ^
undeuterated analog: (This applies even if no other surrogates are outside
criteria .or if omer surrogates are biased high mstead of low.)
b. When dij-ierphenyl is biased low, positive results and quantitation limits for
me heavier polyaromatic hydrocarbons (those which eliite starting with
fluorathene) can be considered as biased low. (This applies even if no other
surrogates are outside criteria or if other surrogates are biased high instead
of low.)
c. When 2,4,6-tribromophenol is biased, low,positive results and quantitation
limits for trichlorophenols and pentachlorophenol can be considered as
biased low. (this applies even if no other surrogates are outside criteria or if
other surrogates are biased high instead of low.)
3.8 Matrix Spikes/Matrix Spike Duplicates
Data for matrix spikes/matrix spike duplicates (MS/MSD) are generated to determine long-
term precision and accuracy of the analytical method on various matrices and to
demonstrate acceptable compound recovery by the laboratory at the time of sample
analysis. These data alone cannot be used to evaluate the precision and accuracy of
individual samples. However, when exercising professional judgment, this data should be
used in conjunction with other available QC information.
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Procedure No.: M2-SVOA
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3.8.1 Acceptance Criteria
1. Matrix spike and matrix spike duplicate samples are analyzed at frequency of one
MS and MSD per 20 samples of similar matrix.
j
2. Matrix spike and matrix spike duplicate recoveries should be within the advisory
limits established on Form m SV-1 and SV-2.
' ' ..'. '':- ' ' '-..-. -. I.-''- ;
3. The Relative Percent Differences (RPDs) between matrix spike and matrix spike
duplicate recoveries should be within the advisory limits listed on Form HI SV-1
and SV-2. ' / ..';' '-... ' " ' ' -." "'- -.. ''.''
3.8.2 Data Requirements and Data Retrieval
Forai IE SV-1 and SV-2 and chromatograms.
3.8.3 Evaluation Procedures
1. Verify that MS and MSP samples were analyzed at the required frequency and that
results are provided for each sample matrix.
2. Inspect results for the MS/MSD Recovery on Form ffl SV-1 and SV-2 and verify
that the results for recovery and RPD are within the advisory limits'.?
3. Compare results (%RSD) of non-spiked compounds'between the original result,
MS, and MSD,
3.8.4 Action
1. No action is taken on MS/MSD data alone. However, using informed professional
judgment the data reviewer may use the matrix spike and matrix spike duplicate
results in conjunction with other QC criteria and determine the need for some
qualification of the data.
2. The data reviewer should first try to determine to what extent the results of the
MS/MSD affect the associated data. This determination should be made with
regard to the MS/MSD sample itself as well as specific analytes for all samples
associated with the MS/MSD.
3. In those instances where it can be determined that the results of the MS/MSD affect
only the sample spiked, then qualification should be limited to this sample alone.
However, it may be determined through the MS/MSD results that a laboratory is
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Procedure No.: M2-SVOA
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having a systematic problem in the analysis of one or more analytes, which affects
all associated samples. : .
4; The reviewer must use professional judgment to determine the need for qualification
of positive results of non-spiked compounds.
NOTE: If a field blank was used for the MS/MSD, a statement to that effect must be
included for TPO action on the ORDAS. ;, -
5. When extremely low % recoveries are noted, qualify data for all affected
compounds using professional judgment
6. When non-spiked compounds are present in either.the MS or MSD results, a table
in the data review narrative is constructed.- showing original' (unspiked) sample
results for non-spiked compounds, non-spiked compounds present in the MS and
MSD and the calculated %RSD.
3.9 Internal Standards .-. .";'*'
" " \" ,
Internal Standards (IS) performance criteria ensure that GC/MS sensitivity and response are
stable during every analytical run.
3.9.1 Acceptance Criteria ;^.
1. Internal standard area counts for samples and blanks must not vary by more than a
factor of two' (- 50% to + 100%) from the associated calibration standard.
2. The retention time of the internal standards in samples and blanks must not vary by
more than +. 30 seconds from the retention time of the associated calibration
standard.
3.9.2 Review Items
Form Vin SV-1 and SV-2 and chromatograms.
3.9.3 Evaluation Procedures
1. Check raw data (e.g., chromatograms and quantitation lists) for samples and blanks
to verify the internal standard retention times and areas reported on the Internal
Standard Area Summary (Forms Vm SV-1, VHI SV-2).
2. Verify that all retention times and IS areas are within the required criteria.
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Procedure No.-: M2-SVOA
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3. If there are two analyses for a particular fraction, .the reviewer must determine
which are the best data to report. Considerations should include:
a. Magnitude and direction of the IS area shift
b. Magnitude and direction of the IS retention time shift.
c. Technical holding times.
d. Comparison of the values of the target compounds reported in each fraction.
3.9.4 Action
, ' ' . \ ' .
' ' . . ' . .''.'-.' '*
1. If an IS area count for a sample or blank4s*outside 50% or + 100% of the area
for the associated standard: ' .-,.,..
a. Positive results for compounds quantitated using that IS should be qualified'
.'' with'TV. ... '-' ; '.-'. -;. -' ' -.'. .';." --..'.... V;
b. Non-detected compounds quantitated using ah IS area count greater than
+100% should be qualified with "UJ".
c. Non-detected compounds quantitated using an IS area count less than 50%
are reported as the associated sample quantitation limit and qualified with
"UJ".
d. If extremely low area counts are reported, or if performance exhibits a
major abrupt drop-off, then a severe loss of sensitivity is indicated. Non-
detected target compounds should then be qualified as unusable (R).
2. If an IS retention time varies by more than 30 seconds:
The chromatographic profile for that sample must be examined to determine if any
false positives or negatives exist. For shifts of a large magnitude, the reviewer may
consider partial or total rejection (R) of the data for that sample fraction. Positive
results should not need to be qualified with "R" if the mass spectral criteria are
met.
3. If the internal standards performance criteria are grossly exceeded, then this should
be noted for TPO action. Potential effects on the data resulting from unacceptable
internal standard performance should be noted in the data review narrative.
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Procedure No.: M2-SVOA
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3.10 Reported CRQLS
The objective is to ensure that the reported quantitation results and Contract Required
Quantitation Limits (CRQLs) for semivolatile target compounds are accurate.
3.10.1 Acceptance Criteria
1. The CRQL must be calculated according to the correct equation and account for
moisture content and dilution factor as appropriate. -
3.10.2 Review Items \
Form ISV-1 and SV-2 and chromatograms.
3.10.3 Evaluation Procedures
1. Verify that the CRQLs have been adjusted to reflect all sample dilutions,
concentrations, splits, clean-up activities, and dry weight factors that are not;
accounted for by the method; . ; '
.'". --..-'' r.' .'.-.
3.10.4 Action \
1. If there are any discrepancies found, the laboratory may be contacted by the
designated representative to obtain additional information that could resolve any
differences. If a discrepancy remains unresolved, the reviewer must use
professional judgment to decide which value is the best value. Under these
circumstances, the reviewer may determine qualification of data is warranted.
Decisions made on data quality should be included in the data review narrative. A
description of the reasons for data qualification and the qualification that is applied
to the data should be documented in the data review narrative.
2. Numerous or significant failures to properly evaluate and adjust CRQLs should be
noted for TPO action.
3. The reviewer must assure that any results in error by more than 10 percent are
identified and corrected on the sample data summary. If laboratory resubmission is
not performed, the reviewer should document his/her changes to the data in the
narrative or support documentation. Calculation errors should also be noted on the
ORDA.
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Procedure No.: M2-SVOA
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3.11 Tentatively Identified .Compounds
Chromatographic peaks in semivolatile fraction analyses that are not target analytes,
surrogates, or internal standards are potential tentatively identified compounds (TICs).
TICs must be qualitatively identified by a National Institute of Standards and Technology
(NIST) mass spectral library search and the identifications assessed by the data reviewer.
3.11.1
For each sample, the laboratory must conduct a mass spectral search of the NIST library
and report the possible identity for the 20 largest semivolatile fraction peaks which are not
surrogate, internal standard, or target compounds, but which have area or height greater
than 10 percent of the area or height of the nearest internal standard. TIC results are
reported for each sample-oS'liie^rganic Analyses Data Sheet (Form I SV-TIC).
"~'' ' " ' ''
NOTE: ;Smce abn of October 1986, the CLP does not allow the
laboratory tb'reporf is tentatively identified compounds any target compound
1 .-- . '^ ;.-.'.ป-"*" '"*4ปl'-ป.Vป.t, p ' * ^^ ' ' ~
which /is pro^^ly^r^rted in anomer fraction^ For example, late eluting
volatile target compounds should not be reported as semivolatile TICs.
.' '..)'.- '".: '': '-.-'. ' ' '
. - ' x ' ' ' *
'3.11.2 Review Items <:-
','" " '"'"
Form I SV-TIC, chromatograms.
3.11.3 Evaluation Procedures
1. Guidelines for tentative identification are as follows:
Ensure that TIC results are reported on Form Fs.
2. Blank chromatograms should be examined to verify that TIC peaks present in
samples are not found in blanks. When a low-level non-target compound that is a
common artifact or laboratory contaminant is detected in a sample, a thorough
check of blank chromatograms may require looking for peaks which are less than 10
percent of the internal standard height, but present in the blank chromatogram at a
similar relative retention time.
3. The reviewer should be aware of common laboratory artifacts/contaminants and
their sources (e.g., aldol condensation products, solvent preservatives, and reagent
contaminants). These may be present in blanks and not reported as sample TICs.
Examples:
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Procedure No,: M2-SVOA
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Page38of39
a. Common laboratory contaminants: CO2 (m/z 44), siloxanes (m/z 73),
diethyl ether, hexane, certain freons (l,l,2-trichloro-l,2,2-trifluoroethaneor
fluoro-trichloromethane), and phthalates at levels less than 100 ug/L or 4000
ug/Kg.
b. Solvent preservatives, such as cyclohexene which is a methylene chloride
preservative. Related by-products include cyclohexanone, cyclohexenone,
cyclohexanol, cyclohexenol, chlorocyclohexene, and chlorocyclohexanol.
c. Aldol reaction products of acetone include: 4-hydroxy-4-methyl-2-
pentanone, 4-methyl-2-penten-2-one, and 5,5-dimemyi-2(5H)-furanone.
4. Occasionally, a target compound may be identified as a TIC in the proper .analytical
fraction by non-target library search procedures, even though it was not found on
the .quantitation list If the total area quantitation method was used, the reviewer
should request that the laboratory recalculate the result using the proper quantitation
ion. In addition, the reviewer should evaluate other sample chromatograms and
check library reference retention times on quantitation lists to determine whether the
raise negative result is an isolated occurrence or whether additional data may be
affected.
5. Target compounds may be identified in more than one fraction. Verify that
quantitation is made from the proper fraction.
3.11.4 Action
1. All TIC results should be qualified "J", estimated concentration on the Laboratory
Forml-TICs.
2. Blank Results
/
Form I-TIC which contain sample results that are questioned by blank results,
should be flagged "B" and a line drawn through these data for emphasis (initialed
and dated).
',:
To be considered questionable, a sample TIC concentration must be within 10 times
the concentration of one of the blank results. If different volumes/weights are used,
the total amount of compound in the extract must be compared for sample versus
blank. In general, blanks analyzed within the same case, by the same lab, may be
cross-applied to either soil or water samples extracted or analyzed on other days.
All blank results must be attached in the support documentation section of the data
review.
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Procedure No.: M2-SVOA
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Page 39 of 39-
3. When a compound is not found in any blanks, but is a suspected artifact of common
laboratory contamination, the reviewer should cross off the reported TIC result on
the copy of the Form I-TIC and note the reason(s) in the narrative.
4. Physical constants, such as boiling point, may be factored into professional
judgment of TIC results.
5. Failure to properly evaluate and report TICs should be noted for TPO action.
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Procedure No.: MI-PEST
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Page 1 of 20:
Appendix C-l
Validation of Pesticides and PCB Analyte Data
Manual Level Ml
1. Purpose and Applicability
This procedure provides step-by-step instructions to manually validate pesticide and ploly-
chlorinated biphenyl (pest/PCBs) data using the manual innovative data validation approach
atLevelMl.
The procedure is applicable to the Pesticide/PCB xlata obtained using the Conract
Laboratory Program Statement of Work (CLP SOW). Hard copy data conforming to the
applicable CLP'SOW specifications are essentialin order to carry out .the procedure. |
Data validated using this procedure are considered usable for the following types of
purposes; however, the data users must decide on a case-by-case basis whether the
procedure is suitable for their intended data uses. The suggested data uses are:
Oversight of activities led by other parties
Action level comparison
Initial site investigation
Contamination sources
2. Quality Control Measures Checked
Table MI-PEST-1 highlights the quality control (QC) indicators evaluated under this data
validation procedure.
3. Procedure
The following subsections describe for each of the QC indicators the acceptance criteria,
location and retrieval of QC data, evaluation of the QC data, actions taken in the event the
QC acceptance criteria are exceeded, and documentation of the QC violations in a
standardized report form.
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Procedure No.: Ml-PEST
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Page2o'f20
Table Ml-PEST-1
QC CHECKLIST FOR LEVEL Ml
CLP RAS PESTICIDES/POLYCHLORINATED BIPHENYLS
QC MEASURES
Action Level Notification
GC/ECD Performance Check '
Initial Calibration (CF) .
Initial Calibration (%RSD)
Continuing Calibration (RPD)
Laboratory Blank .
MS/MSD(%R,JRPD)
Field Quality Control (dup., blnk., PE samp.)
Sample Paperwork ; .
Holding Time
Retention Time
Surrogate Recovery
Dilution Factor '
Moisture Content
Pesticide Cleanup Checks
Chromatograms
"
Raw Data
-'.. ./;../;'. .- r Mamial;'/;:-
| Ml | ป0 W
r^!^
*?.'. .' ' "'
t ป *.
i
1 . x |
i 1
1 ^
1 '
1 : ' :..'-
p :^v-
..v':-.-x--V-"'ir
- ' ..ฃV) ;:*.
.. :.. '*.?.-v: .-.:
'.-''.x;r '
''.'X'": '';-.'
/."x-'-V
1- : '.'
1 .'x .
x ^
\". x."
1 - 'X .
X
x
X
X
X
I
/'". ' / =
:;-.-;;M3 ;
x
' ' . i-
';':'." x r '
,.-:-.X "
s-;-.-x '
::-.' -X ';
' X
!
X
X
X
X
X
X .
X .
X
x
X
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Procedure No.: Ml-PEST
Revision: 1
Date: 06/30/1995
Page 3 of 20
Reporting requirements for Level Ml are:
Hand annotate the Form Fs, including
Data validation qualifiers
Sample identification number
Sampling location
Provide a narrative that includes
- A statement that defines the level of the data review, i.e., Ml
Major problems associated with analysis
Include the following attachments
List of data validation qualifiers
' - Support documentation including forms that support assigning data
qualifiers
- Chain of custody form
- . ~ " f . m
3.1 Action Level Notification
The purpose behind action level notification is to make the EPA Remedial Project Officer
(RPM) or the Site Project Officer (SPO) aware of the potential human health risk at the
site. In accordance with the Region HI Hazardous Waste Division policy, the EPA IJJPM
or SPO must be promptly notified of any contaminant exceeding the established action ijevel
or the 10-day health advisory limit. The data for contaminants exceeding the action levels
must be validated as a top priority and reported to the RPM or SPO. Validation of the: rest
of the data may then be completed normally.
3.1.1 Acceptance Criteria
Region HI Hazardous Waste Division has established 10-day advisory limits or the action
levels for several organic compounds and elements of special health risk concern. The
pesticide organic compounds and their 10-day health advisory limits apply only to aqueous
samples and are listed in Table Ml-PEST-2. The criteria for action level notification are
as follows:
The contaminant concentration must be equal to or above the established 10-
day health advisory limits.
Data for contaminants exceeding the action levels must be validated as a top
priority.
The following EPA personnel must be notified of the action level
exceedances:
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Procedure No.: MI-PEST
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Date: 06/30/1995
Page 4 of 20
EPA RPM or SPO
EPA Section Chiefs:
- Site Investigation (SI)
Remedial
- Enforcement
RCRA
(
EPA Section Toxicologists:^ .
- Enforcement
Superfund
-. RCRA
The remaining data validation should be completed per normal procedures.
Any special instructions from the Hazardous Waste Division should be
followed.
Records should be kept of the data review, action level notification and any
follow-up instructions and actions.
Table Ml-PEST-2
PESTICIDES AND POLYCHLORINATED BIPHENYLS AND ACTION
LEVELS
Compound
Chlordane
Heptachlor
Methoxychlor
Action
Level*
63
10
2,000
Compound
Endrin
Lindane
Toxaphene
Action
Level*
5
1,200
80
*A11 units are ug/1.
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Procedure No.: Ml -PEST
Revision: 1
Date: 06/30/1995
Page 5 of 20
3.1.2 Review Items
All data required to perform the complete Level Ml validation, as detailed in the following
sections are necessary for carrying out action level notification. The location of the data
.and their retrieval procedures are also discussed below.
3.1.3 Evaluation Procedure
The evaluation process preceding action level notification will primarily consist of
comparing the results on Form I*s with the action levels presented in Table Ml-PEST-2.
Following the identification of the contaminants exceeding the action levels, focused data
validation 'should be performed using the criteria, and procedures described in 1 the
appropriate sections below. : *"
3.1.4 Action
The action resulting from focused data validation will be the notification of action level
exceedance to the personnel identified above in Section 3.1.1. : \
\ . ' ,
3.1.5 Reporting
Copies of Form I's can be used to highlight the contaminants above the action levels. The
findings of the focused validation can be summarized in a memorandum, and the data
qualifiers resulting from focused validation may be written on the Form I's. The marked
up forms should be clarified that they represent validation of only the contaminants
exceeding the action levels, and not all data.
3.2 Evaluation of Retention Times
Retention times are the only tool (in the event that a mass spectral analysis was not
required) that allow for the identification of the pesticides and PCBs. While a retention
time from a single column is not an unequivocal proof of a compound's presence, if the
retention time of the suspected compound on a second column also matches that. of a
standard, then the compound's presence is deemed confirmed. There is reasonable
probability that a non-target compound may have the same retention time as a target
compound on one gas chromatographic column, but the probability of the two compounds
having same retention times also on a second column is indeed very remote. For this
reason, the methods utilizing non-specific detectors require that the analyses be performed
under two separate sets of chromatographic conditions
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Procedure No.: MI-PEST
Revision: 1
Date: 06/30/1995
Page 6 of 20
3t.2.1 Acceptance Criteria
Tjhe retention time acceptance criteria have been established by the EPA and Region m as
follows:
The retention times of both of the surrogates, matrix spikes, and reported
compounds in each sample must be within the calculated .retention time
windows on both columns. The acceptable windows are ฑ0.05 minutes for
compounds eluting before heptachlor epoxide and ฑ0.07 minutes for
compounds eluting after and including heptachlor epoxide.. The retention;
time for the surrogate tetrachloro-m-xylene (TCX) must be within ฑ0.05
minutes of the mean retention time determined from the initial calibration
and that for decachlorobiphenyl (DCB) must be within ฑ0.10 minutes of the
mean retention time determined from the initial calibration.
3.2.2 Review Items
The instrument level printouts or the quantitation reports are required to obtain the
retention times for the detected compounds. These are included in the raw data sections of
the data package for the calibrations as well as the samples. Additionally, Forms Vm and
X would be helpful in substantiating and documenting any discrepancies. It also may be
helpful to use a copy of the necessary calibration quantitation reports for a .comparison with
the sample retention times.
3|.2.3 Evaluation Procedures
Note: It is important to emphasize that the evaluation of the retention times goes hand-in-
hand with the chromatographic evaluations. During the evaluation of any one of these QC
measures, a substantial use of the other QC measure is involved. Therefore, it may be
beneficial to carry out these two evaluations together.
Review the quantitation reports and chromatograms for retention times in the
standards and samples. Use Forms I, VIII and X as additional tools for
documenting and confirming the accuracy of the reported data. Confirm
reported detected analytes by comparing the sample chromatograms to the
tabulated results and verifying peak measurements and retention times.
Acceptable ranges for the pesticides and PCBs are presented in Table Ml-
PEST-3. Ensure that the sample retention times are within these ranges for
the compounds reported as detected and confirmed by the second column
analysis. Perform a similar evaluation of the associated blank data for a
confirmation of the reported laboratory contaminants, if any.
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Procedure Nq.: MI-PEST
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Date: 06/30/1995
Page 7 of 20:
For multi-component target compounds (Toxaphene and Aroclors), the
retention times and relative peak height ratios of major component peaks
should be compared against the'appropriate standard chromatograms.
3.2.4 Action
If the qualitative criteria for both columns were not met, all: target compounds that' are
reported detected should be considered riondetected. The reviewer may need to use the
qualifiers that are specific to pesticides. The reviewer should use professional judgment to
assign an appropriate quantitation; limit using the following guidance.. ;
. .- ' - .''.' ':.-''"''. . j
If the misidentified peak was sufficiently outside the target pesticide
retention time'window, then the repotted values may, .be a false positive; and
should be replaced with the sample CRQL value. V . . ; :
If the misidentified peak poses an interference with potential detection of a
target peak, the reported value should be considered and qualified as
unusable (R). . -. '", . :
" . . \
If the data reviewer identifies a peak in both GC column .analyses that falls
within the appropriate retention time window, but was reported as a
nondetect, then the compound may be a false negatives- Professional
judgment should be used to decide if the compound should be included.
All conclusions made regarding target compound; identification should be
included in the data review narrative.
i
3.2.5 Reporting
Include one or more Forms Ml-PEST-WNDW (example provided by Table Ml-PEST-4)
to represent the acceptance windows for the retention times based on the calibrations.
Record any deviations of the retention times on the Form Ml-PEST-RT for the detected
compounds in each sample. Include these documents in the report for Level Ml data
validation results. If the data need qualification, enter appropriate qualifier code on the
sample Form I's, and attach these to the report.
3.3 Evaluation of Chromatograms For Detected Compounds
The purpose behind evaluating the chromatograms is to get an idea regarding potential false
negatives, and gross analytical errors. Some idea as to the false positives may also be
derived by checking the chromatograms. Evaluation of the positive data as.described under
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Case No.:_
SDG No.:.
Data Reviewer:
Site:
Procedure No.: Ml-PEST
Revision: 1
Date: 06/30/1995
Page 8 of 20
Oatei Analyzed:
Instalment ID:
Table Ml-PEST-3
. Pesticides/Polycblorinated BipUenyls Retention time Windows
Compound
Iplu-BHC . ,. " '.:.-.
beta-BHC . -
deb-BBC
gammt-BHC (Liodane)
Heptichlor . .
Heptachlorepoxtde '- -'<
ftiiitaftflfin I :'.-. * -
lyifffflpH _ " ' ^ ",-'.'
4,4'-DDB . ':-. . - .;
Emfriii ' - ' . ''''- '
VnAft**ttfm9* If ' ' " ' - ' . '
4,4*-DDD : '
findbtul&n fulftte . . -
4,4'-DOT
Methoxyehlor
Eodrio ketone. .
Eodrin aldehyde
alpha-CUordane
gamma-Chlordane
Toxaphene
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Tetrachloro-m-xylene (Surr.)
Decachlorobiphenyl (Surr.)
Retention Time
Window in
, Mianttt
ฑ0.05
ฑ(WJ5
:ฑOM
ฑ0.05 .
. ฑ0.05
ฑ0.07
. ฑ0.07
:ฑd.0ฃ:
^"tWito"'.-
. ฑo:o7
" J.Aft7
ฑ0.07
ฑ0.07-
ฑ0.07
ฑ0.07.
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.05
ฑ0.10
Primary Column
Sid. Ret. Time
/ . -
':
-
-
'
Range
* . ;
"
,
Secondary f"i^"""
SUJ. Ret. Time
.
' .-.'':.'
. - ^_
. . ...
Range
, ' 1 '
i
i
\.
\
1
!
' '
I
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Case No.:_
SDG No.:.
Data Reviewer:
Site:
Procedure No.: MI-PEST
Revision: 1
Date: 06/30/1995
Page 9 of 20
-Table Ml-PEST-4
PEST/PCB Retention Time Evaluation Summary
Dates Analyzed:
/'
i
Inftn'uiftn1 IDs
. ' Column (1): '
. . Column (2):
Compound: . -
alpha-BHC
beU-BHC
delta-BHC
gunma-BHC (lindane) .
Hepuehlor
Heptaehlor epoxide
EndosulfanI
Dieldrin
4,4'-DDE
Endrin
EndosulfanJI
4.4MJDD
Endosulfan sulfate
4,4'-DDT
Methoxychlor
Endrin ketone
Endrin aldehyde
alpha-chlordane
gamma -chlordane
Toxaphene Peak 1
Peak!
Peak 3
Aroclor 1016 Peak 1
Peak 2
Peak 3
Aroclor 1221 Peak 1
Peak 2
Peak3
Aroclor 1232 Peak 1
Peak 2
Peak 3
Aroclor 1242 Peak 1
Peak 2
Peak 3
Aroclor 1248 Peak 1
Peak 2
Peak 3
Aroclor 1254 Peak 1
Peak 2
. Peak 3
Aroclor 1260 Peak I
Peak 2
Peak3
Sample Identifier:
1.
2.
3.
4.. ' - :
5. . '
6. ..'.;.'
7, ; : '
8. " . '''..
9. - ' '
10.
Comments :
ป
2.
3. . . . .,..-
4. . ' '
5. ' . ' ,
ซ . - ,- . . i-
7; ' ' ' ' ' ._.''>
-*. . ' . . ' ' .' ...
9. ' . ...-.-...-.
10.
Sample Identifier & Retention Times for Primary Column (1) and Secondary Column (2)
1
a)
.
a)
..
2
0)
C)
, ..
3
tt)
>
0)
4
a)
w
5 .
av
"
10 .
tt)
0)
.
%
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Procedure No.: Ml -PEST
Revision: 1
Date: 06/30/1995
Page 10 of 20
mass spectral evaluation does not offer any insight into data that are not reported (i.e.,
reported as nondetects). Laboratory error or gross interference from other compounds
cbuld be the reasons for erroneous reporting. The gas chromatographic profiles are the
primary tool used for the false negative evaluation under Level Ml.
$.3.1 Acceptance Criteria
TJhere are no EPA.-established quantitative criteria for evaluating chromatograms for false
negatives. The criteria used for evaluating chromatograms are based on good laboratory
and scientific practices, and these are not hard and fast requirements. The suggested.
evaluation criteria are as follows:
':''.*..'''-.'' " . '
Chrpmatpgrams must displaysingle component pesticides detected in the
sample and the largest peak of any multi-component analyte detected in the
sample at less than full scale, '.'-.'
If an extract must be diluted, chromatograms must display single component
pesticides between 10 and 100 percent of full scale, and multicomponent
analytes between 25 arid 1(X) percent of full scale.
'' "ซ.''-- . - _ f
For any sample, the baseline of the chromatogram must return to below 50
percent of full scale before the elution time of alpha-BHC, and;also return to
below 25 percent of full scale after the elution time of alpha-BHC and
before the elution time of decachlorobiphenyl,
If a chromatogram is replotted electronically to meet these requirements, the
scaling factor used must be displayed on the chromatogram,and both the
initial chromatogram and the replotted chromatogram must be submitted in
the data package.
There should not be any significant peaks in the chromatograms that are
accounted for as TCLs. Significant peaks are those with a minimum peak
height of 10 percent of the full scale deflection.
The chromatograms should ideally have base-line .resolution between
adjacent peaks. Also, there should not be broad (unresolved) envelops in the
chromatograms.
There should not be abrupt shifts in the baseline.
There should .not be peak tailing or sharp rise in the peak fronts.
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Procedure No.: MI-PEST
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3.3.2 Review Items
Chromatograms for each sample and standard calibrations are necessary for the evaluation.
These can be found in the front of the raw data package for each sample. The quantisation
report for each sample is also necessary to retrieve the retention times since I the
chromatographic profile from a single column can be inconclusive. A copy of the standard
chromatograms from both chromatographic columns may be very helpful in visually
comparing the sample: traces for fingerprint features. . . !
3.3.3 Evaluation Procedures
Note: It is important to emphasize that the evaluation of the chromatograms goes hancl-in-
hand with the retention time evaluations. Duritlg the evaluation of any one of these
measures, a substantial use of the other QC measure is involved. Therefore, it ma
beneficial to carry out these two evaluations together.
Visually inspect the primary and the secondary column chromatograms
QC
be
for
all peaks that appear to be at least .10 percent of the full scale deflection.
Compare the retention time of the suspect compound on the primary column
with that of the standard. If the retention time is close to the acceptance
range, then check the retention time on the secondary column. If there is
clear disagreement in the retention time the compound is likely not a target
compound and should not have been reported.
If multicomponent. target, compounds, exhibit marginal pattern-matching '
quality, professional judgment should be used to establish whether the
differences are due to environmental "weathering" (i.e., degradation of the
earlier eluting peaks relative to the later eluting peaks). If the presence of a
multicomponent pesticide is strongly suggested, results should be reported as
presumptively present (N).
If an observed pattern closely matches more than one Aroclor, professional
judgment should be used to decide whether the neighboring Aroclor is a
better match, or if multiple Aroclors are present.
If GC/MS confirmation was required but not performed, the reviewer should
report this for TPO action.
Also observe the chromatogram traces for peak resolution between the
adjacent single component peaks. Poor peak-to-peak resolution is indicative
of degrading performance of the gas chromatographic column. The values
obtained from a degrading system are prone to be inaccurate. Generally,
U.S. EPA Headquarters Library
Mail code 3201
1200 Pennsylvania Avenue NW
Washington DC 20460
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Procedure NOJ MI-PEST
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there should be at least 90 percent valley between the neighboring peaks.
This criteria is important for detectors such as the electron capture detector
(BCD) that do not allow for unequivocal identification. Poor peak resolution
between the adjacent peaks may results .in estimated quantisation of both for
both compounds.
Inspect the BCD .profile for broad, unresolved envelops. These are
generally indicative of outside interference from homologous compounds.
Such envelops .can mask the target peaks or interfere, with accurate
quantitation of the peaks. >;.
Inspect the BCD profile for abrupt shifts in the baseline. Such shifts are
indicative of problems with instrument sensitivity or leakage in the system.
The area counts obtained from shifted baseline are inaccurate, or even the
detection of a TCL at low concentration may be missed.
"'.-'.' i .-\ ' "' ' ''' . .
Rapid peak rising or peak tailing indicate problems with, the gas
chromatographic column, such as depleted stationary phase on the column,
decomposition of the stationary phase or creation of active sites. Again, a
visual inspection, of the BCD profile will yield information on the shape of
the peak. ; . '
3.3.4 Action ^
professional discretion must be used when evaluating and qualifying data based on the
chromatographic evaluations. An experienced chemist can generally infer the magnitude
and the frequency of the problem from the ECD profile and fingerprints. If the problem
appears to be systematic, then it should be brought to the laboratory's attention and
resolved. Intermittent problems may or may not require any action. The following
guidelines are suggested when acting on ECD. profile observations:
Any unaccounted TCL peak (as confirmed by the retention times on both
columns) with area equivalent to or greater than the lowest reportable limit
for the sample must be brought to the laboratory's attention and resolved.
In the event, the discrepancy cannot be resolved with the laboratory, the
problems should be documented and brought to the attention of the CLP-
TPO, the RPM and the SM. The data for unreported TCLs may be
considered unusable until the problems are resolved.
If a peak resolution problem is evident for the samples, and appears to be
systematic (i.e., present in all calibration samples, QC samples, and field
samples and increasing as the run progresses, additional QC measures such
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Procedure No.: MI-PEST
Revision: 1
Date: 06/30/1995
Page 13 of 20
as the continuing calibration percent difference (%D), and surrogate standard
recoveries in the vicinity of the affected peaks should be evaluated to
determine if the peak resolution problem could affect detection! or
quantitation. If determined so, the positive data may be qualified as
estimated, "J." Negative data may also be qualified as estimated, "UJ
if
the ability to detect at low concentrations is also deemed to be jeopardized
by poor resolution of adjacent peaks. . .
Broad envelopes of homologous compounds could interfere with quantitation
or even detection. If the interference is evident from the recoveries of the
surrogate standards in the vicinity of the envelop, associated compounds may
also be interfered with. Using professional discretion, the positive iand
negative data may be considered as estimated, "J-? and "UJ", respectively.
If the project objectives cannot be met with the estimated data, alternative
sample preparation and cleanup procedures may need to be developed land
specified. The recommended solution should be brought to the attention of
the RPM, the SM and the TPO. j
Discrete shifts in the baseline in the middle of a run are indicative of
intermittent problems. If the shift is due to leakage or change in the system
pressure, the positive as well as negative data may be considered estimated
("J" and "UJ, respectively). The problem could be also due to sbme
fluctuation in the instrument electronics which may lead to drastic changes in
the sensitivity of the instrument to detect the compounds. As a note,
professional judgment should be exercised in determining the severity of the
problem. For example, the magnitude of a drop in the baseline below! the
zero line may not be estimated and could be very significant. On the other
hand, a drop that yields a baseline still above zero can be put in a
perspective with the original baseline and a general appearance of the entire
RIC profile. . ' ' .
The problems with peak symmetry are indicative,of system degradation, and
should be brought to the attention of the laboratory for a corrective action.
.Professional judgment should be used when and if qualifying any data due to
unsymmetrical peaks. First the problem should be defined in terms of
persistence throughout the chromatogram and also from sample to sample.
Additionally, the shapes and area counts for the surrogate standards should
be evaluated to see if the problem could have affected compound detection
and/or quantitation. Data qualification may: be uncalled for if the standard
area counts are acceptable.
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Procedure No,: MI-PEST
Revision: 1
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Page 14 of 20
3.3.5 Reporting
Keeps notes of the problems and substantiate them with copies of both cnromatograms and
ojther pertinent laboratory paperwork. . Include these items in the overall report for Level
Ml data validation. For more descriptive comments, a separate sheet may be used.
3.4 Evaluation of Blanks
"the purpose of laboratory (or field) blank analyses is to determine the existence and
magnitude of contamination problems resulting from laboratory (or field) activities. The
criteria for evaluation of laboratory blanks apply to any blank associated with the samples
(e.g., method blanks, instrument blanks, and sulfur cleanup blanks). If problems exist with
a ly type of blank, all associated data must be carefully evaluated to determine whether or
not there is an inherent variability in the data, or if the problem is an isolated occurrence
not affecting other data. '.,' ',
laboratory blanks and field blanks have a profound impact on false positives reported in
samples; i.e.,.compounds reported as positive detects but not originating from the samples
themselves. Cross contamination from the sampling equipment, incidental contamination
from the field conditions or contamination from the laboratory equipment or general
environmental are likely sources of false positives in the samples.
3.4.1 Acceptance Criteria "''..
Criteria for blank evaluation are specified in the EPA's functional guidelines. In addition,
Region HI has some additional requirements modifying the guidance. The acceptance
criteria for blanks apply equally to any type of blanks associated with either sampling or
analysis, such as trip blanks, rinsate blanks, field or bottle blanks, laboratory method
blanks. While there are several criteria for evaluating the blanks, the only criteria
applicable to Level Ml is the comparison of the blank and .sample concentrations. These
criteria are as follows:
No contaminants should be present in the blanks.
Frequency of Blank analyses:
Method BlanksA method blank analysis must be performed for
each 20 samples of similar matrix in each sample delivery group
(SDG) or whenever a sample extraction procedure is performed.
Instrument BlanksAn acceptable instrument blank must be run at
; least once every 12 hours and immediately prior to the analysis of
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Procedure No.: MI-PEST
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Date: 06/30/1995
Page 15 of 20
i
either the performance evaluation mixture or Individual Standard
Mixtures A and B, depending on the place in the analysis sequence.
Sulfur Cleanup BlanksA sulfur cleanup' blank must be analyzed
whenever part of a set of samples extracted together requires sulfur
cleanup. If the entire set of samples associated with a method blank
requires sulfur cleanup, then the method blank also serves: the
purpose of a sulfur blank and no separate sulfur blank is required.
3.4.2 Review Items
Data requirements and data retrieval procedures for blanks are the same as those for the
field samples because the blanks as well as field samples are validated similarly. Form! I's,
mass spectra, chromatograms, quantitation reports, etc., are essential for performing a
validation of the blanks first. ' .
3.4.3 Evaluation Procedure
Validate the blanks same as the field samples. Detailed validation procedures are described
above under appropriate sections. Use the validated blank results for a comparison with
the sample results. Make certain that the samples and blanks are evaluated on the same
basis of sample weight or volume, dilution factors, moisture content, eUC"~Use the 5 (or
10) times the highest blank concentrations for qualifying the sample data. More
specifically, the blank data evaluation procedures are as follows:
Review the results of all associated blanks, Form I PEST, and Form IV
PEST, and chromatograms to evaluate the presence of TCL pesticides.
Verify that method blank analysis has been reported per SDG, per matrix,
per concentration level, for each GC system used to analyze samples, and
for each extraction batch.
Verify that the method blank analyses do not contain any target pesticide or
Aroclor/Toxaphene at greater than its Contract Required Quantitation Limits
(CRQL). -
. For the surrogates in each method blar\k, verify that the observed retention
times'are within the appropriate retention time windows calculated from the
initial calibration.
Verify that the instrument blank analysis has been performed every 12 hours
as part of the continuing calibration and following a sample analysis which
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Procedure No.: MI-PEST
Revision: 1
Date: 06/30/1995
Page 16 of 20
contains an analyte(s) at high concentration(s), and that the instrument blanks
do not contain any target analytes above one-half the CRQL, assuming that
the material in the instrument-resulted from the extraction of a 1-L water
sample;
\ / . " /* .
Verify that the sulfur cleanup blanks were analyzed at the required frequency
and that they do not contain any target compound above the CRQL,
assuming that the material in the instrument resulted from the extraction of a
1-L water sample. If a separate sulfur cleanup blank was prepared, one
version of Form TV PEST should be completed associating^ the samples
with the method blank, and a second version of Form IV PEST should be
completed listing only those samples associated with the separate sulfur
cleanup blank.
3,.4.4 Action
If the appropriate blanks were not analyzed with the frequency described in Criteria 3, 4,
and 5, then the data reviewer should use professional judgment to determine if the
associated sample data should be qualified. The reviewer may need to obtain additional
information from the laboratory. The situation should be brought to'the attention of the
TPO. . ,
Action in the case of unsuitable blank results depends on the circumstances and the origin
of the blank. Detected compound results should be reported unless the concentration of the
compound in the sample is less than or equal to 5 times (5x) the amount in the blank. In
instances where more than one blank is associated with a given sample, qualification should
be based on a comparison with the associated blank having the highest concentration of a
contaminant. The results must not be corrected by subtracting the blank value.
Specific actions are as follows:
If a target pesticide or Aroclor/Toxaphene is found in the blank but not
found in the sample(s), no qualification is required. If the contaminant(s) is
found at level(s) significantly greater than the CRQL, then this should be
noted in the data review narrative.
Any pesticide or Aroclor/Toxaphene detected in the sample, that was also
detected in any associated blank, is qualified if the sample concentration is
less than five times (5x) the blank concentration. The quantisation limit may
also be elevated. Typically, the sample CRQL is elevated to the
concentration found in the sample. The reviewer should use professional
judgment to determine if further elevation of the CRQL is required.
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Procedure No.: Ml -PEST
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Date: 06/30/1995
Page 17 of 20
The reviewer should note that analyte concentrations calculated for method
blank may not involve the same weights, volumes, or dilution factors as the
associated samples. These factors must be taken into consideration when
applying the "5x" criteria, such that a comparison of the total amount of
contamination is actually made.
In addition, there may be instances when little or no contamination |was
present in the associated blanks, but qualification of the sample was deemed
necessary. Contamination introduced through dilution is one example.
Although it is not always possible to determine, instances of this occurring
can be detected when contaminants are found in the diluted sample re ;ult,
but absent in the undiluted sample result. Since both results are not
routinely reported, it may be possible' to verify this source of contamination.
However, if the reviewer determines that the contamination is from a so irce
other than the sample, he/she should qualify the data. In this case, the
"5x" rule does not apply; the sample value should be reported as a.
nondetected target compound, "U." ซ
If gross contamination exists (i.e., saturated peaks), all affected compounds
in the associated samples should be qualified as unusable (R), due to
interference. This should be noted in the data review narrative if the
contamination is suspected of having an effect on the sample results.
If inordinate amounts of other target pesticides or Aroclors/Toxaphene are
found at low levels in the blank(s),, it may be indicative of a problem at the
laboratory and should be noted in the data review narrative.
If an instrument blank was not analyzed following a sample analysis which
contained an analyte(s) at high concentration(s), sample analysis results after
the high concentration sample must be evaluated for carryover. Professional
judgment should be used to determine if instrument cross-contamination1 has
effected any positive compound identification(s), and if so, detected
compound results should be qualified. If instrument cross-contamination is
suggested, then this should be noted in the data review narrative if the cross-
contamination is suspected of having an effect on the sample results.
The following are examples of applying the blank qualification guidelines. Certain
circumstances may warrant deviations from these guidelines:
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Procedure No.; MI-PEST
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Date: 06/30/1995
Page 18 of 20
Example 1: Sample result is greater than the CRQL, but is less than the 5x
multiple of the blank result.
Blank Result 1.0
CRQL 0.5
Sample Result 4.0
Qualified Sample Result 4.0B
In this case, sample results less than 5.0 (or 5 x 1.0) would be
qualified as nondetected target compounds.
Example 2: Sample result. is less than the CRQL, and is also less than the 5x
multiple of the blank result. '
Blank Result LO
CRQL 0.5
Sample Result 0.4J
Qualified Sample Result 0.4B
Example 3: Sample result is greater than the 5x multiple of the blank result.
5jc
Blank Result 1.0
CRQL .0.5
Sample Result 10.0
Qualified Sample Result 10.0
In this case, the sample result exceeded the adjusted blank result (5x
1.0) and the sample result is not qualified.
Record blank contaminants on QSFs.
If the sample concentration do not meet the criteria of 5 (or 10) times the blank
concentration, the sample results should be considered essentially undetected (or as not
detected substantially above the levels reported in the blanks); therefore, flagged "B" in
accordance with the Region III data validation guidelines.
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Procedure No.: MI-PEST
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Date: 06/30/1995
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3.4.5 Reporting
Form I's may be used to write the "B" data'qualifier for the data not meeting the blank
criteria. Additional discrepancies may be included in the overall report for the Level Ml
validation.
3.5 Sample Paperwork
The purpose for evaluating the sample paperwork is to determine that the samples being
validated are indeed the ones taken from the site, and have not been tampered with.
Accurate sample identity is of. paramount importance in substantiating the sample data.
Without unequivocal sample identity and chain-of-custody procedures, the sample data may
hot be defensible or enforceable. * - . . .'.":
''. ' ' . ' ' ' -.:'-..'!
Under the current CLP contracts, the original paperwork (i.e., the purge package or the
administrative record) is included in the data package from the laboratory. It is assumed
that the data validator is not privy to the original paperwork; therefore, the evaluation"
criteria and procedures described below apply only to the documents that are generally
included in the data validation package. These documents are the chain-of-custody fqrms
and Region m Shipping Record.
3.5.1 Acceptance Criteria . C
Criteria for acceptability or authenticity of the sampling paperwork, document control! and
chain-of-custpdy have been established by the National Enforcement Investigations Center
(NEIC), in support of the CLP. Overall criteria are too numerous and subjective to be
discussed here, but the criteria that apply to data validation are:
The chain-of-custody form should be properly and completely filled out
including the sampler signatures, date and time of sampling, sampling station
identification, analyses requested, traffic numbers, tag numbers, etc. These
data are minimally required to confirm the authenticity of the sample and its
data.
The chain-of-custody must be maintained at all times. The custody transfers
. between different parties must be signed and dated.
3.5.2 Review Items.
A copy of the chain-of-custody form originated in the field and that returned from the
laboratory with the data are essential to confirm the identity of the samples. In addition,
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Procedure No.: MI-PEST
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Date: 06/30/1995
Page 20 of 20
the Region ni Shipping Record is essential to identify the field QC samples. The chain-of-,
custody and Shipping Record are generally located in front of the data package.
3.5.3 Evaluation Procedure
Ensure that the chain-of-custody form was signed and dated by the samplers, and a time
and date were entered for sample collection. The laboratory copy of the cham-of-custody
must have the signature of the laboratory sample custodian.' Any errors on the form should
have been crossed out with a single line through the entry. Verify mat all collected
samples have unique station identification, traffic numbers and sample tag numbers.
Ensure that the Region m Shipping Record correctly reflects the information on the chain-
of-custody. . :..'.
3.5.4 Action :
The action to be taken in qualifying the data is highly dependent on the nature of the
problem: Some errors in paperwork are practically unavoidable in real situations. An
effort should be made to reconcile the differences by cross checking.the field notebooks
a ;ainst the sampling paperwork. Occasionally, the samplers may forget to sign the chain-
ojf-custody; however, the field notebooks may amply describe the sampling event.
Problems are also inevitable in noting or cross-referencing sample tag numbers and traffic
numbers. Generally, there are several alternate sources of information to .substantiate or
refute the problem. , ,
3.5.5 Reporting
Any discrepancies found in the paperwork must be immediately brought to the attention of
the EPA RPM or SPCX Clearly define the problems in a memorandum to the responsible
parties. Attach marked copies of the chain-of-custody forms to substantiate the findings.
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/J995
Pagel of 31-
Appendix C-2
Validation of Pesticide/PCB Organic Analyte Data
Manual Level M2
1. Purpose and Applicability
This procedure provides step-by-step instructions to manually validate the pesticide
organic data using the manual innovative data validation approach at Level M2.
approach focuses on the use of information contained on the CLP forms and a revie\jv of
chromatograms as summarized in Table M2-PEST-1.
' "''.:' '.-.. " "'-'"^'"'i-. ">ฃ'. .'' ^' *-'..'' - ' ' .- V ' .'
The procedure is applicable to me Pesticide/PCB obtained using the Contract
Program Statement of Work (CLP SOW). Hard copy data conforming to the applicable
CLP, SOW specifications are essential in orderto carry out the procedure.
Data validated using this procedure are considered usable for the following typ
purposes; however, the data users: must decide on a case-by-case basis whether! the
procedure is suitable for their intended data uses. The suggested data uses are: .= \
" . " . ' " .' i'
Oversight of activities led by other parties
Comparison to action levels
Initial site investigation
Contamination sources
Nature and extent of contamination
*
Preliminary risk assessment
Risk assessment with known high levels of toxics
Feasibility study
Preliminary design
Treatability study
Initial cleanup verification
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Procedure No.: M2-PpST
Revision: 1
Date: 06/30/95
Page 2 of 31"
Table M2-PEST-1
QC CHECKLIST FOR LEVEL M2
CLP RAS PESTICIDES-POLYCHLORINATED BIPHENYLS
QC MEASURES .
. Action Level Notification
GC/ECD Performance Check -!
Initial Calibration (CF)
Initial Calibration (96RSD)
Continuing Calibration (RPD)
.Laboratory Blank
MS/MSD (%R, RPD)
Field Quality Control (dup., blnk., PE samp.)
Sample Paperwork . .
Holding Time
Retention Time
Surrogate Recovery
Dilution Factor
Moisture Content
Pesticide Cleanup Checks
Chromatograms
Raw Data
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Procedure No.; M2-PEST
Revision: 1
Date: 06/30/1995
Page 3 of 31
2. Quality Control Measures Checked
Table M2-PEST-1 highlights the quality control (QC) indicators evaluated under this data
validation procedure.
3. Frocedure
; '"'- -, ' :- '-.' i ;" -
The following subsections describe for each of the QC indicators the acceptance criteria,
location and retrieval of QC data, evaluation of the QC date, actions taken in the event the
QC acceptance criteria are exceeded, and documentation of the QC violations in a
standardized report form.
The pesticides data requirements to be checked are listed below:
3.1 Action Level Notification
3.2 Technical Holding Times (CCSContractual holding times only)
I . -,''.
3.3 GC/ECD Instrument Performance Check
3.4 Initial Calibration (CCS)
3.5 Continuing Calibration (CCS)
3.6 Blanks
3.7 Surrogate Spikes (CCS)
3.8 Matrix Spikes/Matrix Spike Duplicates
3.9 Pesticide Cleanup Checks -
3.10 Reported Contract Required Quantitation Limits (CRQLs)
Two forms have been developed to assist in the performance and documentation of
implementing Level M2. The first form, M2-PEST-QUAL, summarizes holding time,
calibrations, blanks, surrogates, and internal standards. The second form, M2-PEST-SPK,
summarizes surrogate and matrix spike quality control checks. These forms are presented
on the following pages as Tables M2-PEST-2 and M2-PEST-3.
Reporting requirements for Level M2 are as follows:
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 4 of 31
Hand annotate the Form I's, including:
.Data validation qualifiers
- Sample identification number
- Sampling location
Provide a narrative that includes:
- - A statement that defines the level of the data review, i.e., M2
Major and minor problems associated with the analysis
- Highlight issues that may have affected detection limits
Include the following attachments: :
- Ust of data validation qualifiers
- Support documentation including forms that support assigning data
.' qualifiers^;,-.-; .'-.' '-. ; : : .. . / '. ..
- Chain of custody form -
- > Samples affected by calibration should be listed on the appropriate
calibration^forms .v . . . -
Data qualifiers assigned in this review are as follows: ,
*'' . '
Codes Relating to Identification (Confidence Concerning Presence or Absence of
Compounds):
U = Not detected. The associated number indicates approximate sample
concentration necessary to be detected.
(NO CODE) = Confirmed identification.
B . = Not detected substantially above the level reported in laboratory or field
blanks.
R = Unreliable result. Analyte may or may not be present in the sample.
Supporting data necessary to confirm result.
N = Tentative identification. Consider present. Special methods may be
needed to confirm its presence or absence in future sampling efforts.
Codes Related to Quantitation (can be used for both positive results and sample
quantitation limits):
J = Analyte present. Reported value may not be accurate or precise.
-------
Method 608/8080
Cซซe No:
SDG No:
Procedure No.:j M2-PEST
Revision: 1
Date:
06/30/1995
Rage 5 of 31
TABLE M2-PEST-2
PESTICIDE/PCBS QUALIFIER SUMMARY (CALIBRATIONS, BLANKS, HOLDING TIME, SURROGATES, INTERNAL
STANDARDS) . f
Date Analyzed:
Matrix
Instrument' ID:
Method Blank ID:
Extraction Date:
dilnmM; Primary
Secondary
Compound.
. Sample Identifier:
. .- '
' ;.:;;;:' ' '.- '
.. '.- :-: ';':..'. ;
'. ''"' -'-'-:v . -''.*" ' '
'y-. / ;. ..- -
..'..;'.''
Hold Time
Out. davs
Ext.
Anal.
Last IND Standard before Analysis
1
' ,':. " -.'. -,. .' : '
2
..
.' *.V.
- . .'.
''*.'
3
-. .' .'iซ.
:'/';??
VN?$
=^^8
'^sM
. 4 ..
AV.;;:,>'
'$$&#ฃ
:5ft#M
^^>!
l>ป_ซi*'lr,^'ป
ซ^?l-''V- .;-
;v.-..---v-
*? ::
5: ซ
t
| .
1
.<.....
?:- '
i* '.
,
,_.:.:.s.:;lvj,.!.i..;:;, '
..''''. ' . ' CaKbmrinnซt ' . ' ' .;. '.*ป!
InhVGaL -
ปRSD>10
'/' . '.', i ConLCal..d
aloha-BHC
beta-BHC
delta-BHC ' '
nmma-BHC fTJndanet '
Hentachlor
Aldrin
Hentachlor enoxide '
Endosulfan T
Dieldrin
4.4'-DDE
Endrin
Endosulfan II
4.4'-DDD
Endosulfan sulfate
4.4--DDT
Methoxvchlor
' Endrin ketone
alnha-chlordane
eamma-chlordane
Toxanhene
Aroclor-1016 fPCB-1016)
Aroclor-1221 fPCB-122H
Aroclor-1232 (PCB-12321
Aroclor-1242 fPCB-12421
Aroclor-1 248 fPCB- 1248)
Aroclor-1254(PCB-l254)
'Aroclor-1260 (PCB-1260)
Dinntvlchlorendnte (DBO SUIT.
ate/month
Tinie
.: '
,'
,^ฃ:.'. -, C*u&
';*>?$''"
-.; .,....
"'T "
~. ;.: .
'" ' "
iimklf^l
J. '
'
D> 15% or 20% .'.'"..4:.-V:rt
" 4 '
'.'"* .'
; '.."
*
''^t$
::?*??$
:r^;.^4
'.- ' '" /
. .ป.'
* . -u
.
~->,
. ;.
S;
'Tr^v -'""' v-
ri?*w^*-ป^**''*1
?,:.-,;-' -
^.!- ;=.-:-.
..';'> :' '
-- . .
XI
uklifien
x f
**
\
!
|
i
Validation Criteria:
Delected compounds
Undetected compounds
Primary Column
%D < 15
56D < 20
and
or
Secondary Column
56D < 20
ซD < 20
-------
Method 608/8080
Case No:
SDGNo:
Procedure No.: M2-PEST
Revision: I
Date: 06/30/1995
Page 6 of 31
Table M2-PEST-3
PESTICIDE/PCBS SURROGATE AND MATRIX SPIKE QUALITY CONTROL
SUMMARY
Surrogate Data Summary
Sample Identifier:
(Acceptance Range, %K):
'.' .-'-. '.'.' '
i
i ... "' ' '
!-"'' % ' - ;"
.'.'.' ' '' .' "
, '.'..'''
' . ' ' .
'
'' ' ' '' "'."
Surrogate Recoveries, 5CR
Aqueous
(24-154)
' -. '- .' .
, ' ' :
' * ";'.-':
..' ': .."'ii.!;-
.--.-;;
' . ''. ' '
;. '..;.
Soil
(20450)
' ' -
,. .-^ ->ป.- '
'-;':;.";. ''
' \'
,' - ' :-..
' '':C'-'
'. ::''i^v^r'
' :&:
-: :--:-;\ v". ':
'- ''""'-
''.'':' '
. -V
Qualifier! (+/-)
. .'
, - ;. - . .
-
. V "'. ~~ '
. . ' '
. . " ' '
Surrogate Dibutylchlorendate (DBC)
. MS/MSP Data Summary
Spike Compound:
Matrix Spike, .Recovery,
%R
Range
Actual
Matrix Spike Duplicate,
, Recovery. %R
Range
Actual
MS/MSD
Precision. RPD
Range
Actual
Qualifiers
(+/-)
AQUEOUS SAMPLES ,
(jamma-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4.4'-DDT
56-123
40-131
40-120
52-126
56-121
, 38-127
v
56-123
40-131
40-120
52-126
56-121
38-127
,
14
20
22
18
21
27
SOIL SAMPLES
panima-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4.4'-DDT
46-127
35-130
34-132
31-134
42-139
23-134
46-127
35-130
34-132
31-134
42-139
23-134
50
31
43
38
45
50
I
-
-------
Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 7 of 31
K = Analyte present. Reported value may be biased high. Actual value is
expected lower.
L = Analyte present. Reported value may be biased low. Actual value is
expected to be higher.
UJ = Not detected, quantitation limit may be inaccurate or imprecise.
TJL = Not detected, quantitation limit is probably higher.
Other Codes :
Q . = No analytical result . * - .
* = Results reported from diluted analysis.
' " >''".*.
3.1 Action Level Notification
The purpose behind action level notification is to make the EPA Remedial Project Officer
(RPM) or the Site Project Officer (SPO) aware of the potential human health risk at the
site. In accordance with the Region ffl Hazardous Waste Division policy, the EPA RPM
or SPO must be promptly notified of any contaminant exceeding the established action level
or the 10-day health advisory limit. The data for contaminants exceeding die action levels
must be validated as a top priority and reported to the RPM or SPQ. Validation of the rest
of the data may then be completed normally.
3.1.1 Acceptance Criteria for Action Level Notification
EPA's Office of Solid Waste and Emergency Response has established 10-day advisory
limits or the action levels for several organic compounds and elements of special health risk
concerns based on the Safe Drinking Water Act. The pesticide organic compounds and
their 10-day health advisory limits apply only to aqueous samples and are listed in Table
M2-PEST-4. The criteria for action level notification are. as follows:
The contaminant concentration must be equal to or above the established 10-
day health advisory limits.
Data for contaminants exceeding the action levels must be validated as a top
priority.
The following EPA personnel must be notified of the action level
exceedances:
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 8 of 31
EPA RPM or SPO
EPA Section Chiefs:
Site Investigation (SI)
Remedial
Enforcement
RCRA
EPA Section lexicologists:
- Enforcement
Superfund
RCRA
.-.(
' ' * ' '- . ' -*" " -
The remaining data validation.should be completed per normal procedures.
Any special instructions from the Hazardous Waste Division should be
followed.
Records should be'kept of the data review, action level notification and any
follow up instructions and actions.
Table M2-PEST-4
PESTICIDES AND POLYCHLORINATED BIPHENYLS AND ACTION
LEVELS
Compound
ii
Chlordane
Heptachlor
Methoxychlor
Action
Level*
63
10
2,000
Compound
Endrin
Lindane
Toxaphene
Action
Level*
5
1,200
80
*A11 units are ug/1.
3.1.2 Data Requirements and Retrieval of Data
All data required to perform Level M2 validation, as detailed in the following sections, are
necessary for carrying out action level notification. The.location of the data and their
retrieval procedures are also discussed below.
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Procedure No.; M2-PEST
Revision: 1
Date: 06/30/1995
Page 9 of 31
3.1.3 Evaluation Procedure
The evaluation process preceding action level notification will primarily consist of
comparing the results on Form I's with the action levels presented in Table M2-PEST-4.
Following the identification of the contaminants exceeding the action levels, focused data
validation should be .performed using the criteria, and procedures described in the
appropriate sections below.
3.1.4 Action
The action resulting from focused data validation will be the notification of action level
exceedance to the personnel identified above in Section 3.1.1.
' '' ' * * . '. '
3.1.5 Reporting '''.
Copies of Form I's can be used to highlight the contaminants above the action levels. The
findings of the focused validation can be summarized in a memorandum/.land the data"
qualifiers resulting from focused validation may be written on the Form I*s. < The marked
up forms should be clarified, that they represent validation of only the contaminants
exceeding the action levels, and not all data.
3.2 Technical Holding Times
The objective is to ascertain the validity of results based on the holding time of the sample
from time of collection to-time of sample extraction and analysis.
3.2.1 Acceptance Criteria
Technical requirements for sample holding times have only been established for water
matrices. The holding times for soils are currently under investigation. When the results
are available they will be incorporated into the data evaluation process. In addition, results
of holding time studies will be incorporated into the data review criteria as the studies are
conducted and approved. The maximum holding time, as stated in the current 40 CFR Part
136, for pesticides and Aroclbrs in cooled (@ 4ฐC) water samples is 7 days from sample
collection to extraction and 40 days from sample extraction to analysis. It is recommended
that pesticides and Aroclors in soil samples be extracted within 7 days of sample collection.
The contractual holding times, which differ from the technical holding times, state that
extraction of water samples by separatory funnel must be completed within 5 days of
validated time of sample receipt (VTSR), extraction of water samples by continuous liquid-
liquid extraction procedures must be started within 5 days of VTSR, and soil/sediment
samples are to be extracted within 10 days of VTSR. Also, contractually both water and
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 10 of 31
soil sample extracts must be analyzed within 40 days of extraction. However, the
contractual delivery due date is either 14 days or 35 days after receipt in the laboratory of
the last sample in the SDG, depending on the contract.
3.2.2 Review Items
Form I PEST, EPA Sample Traffic Report, and/or chain-of-custody.
3.2.3 Evaluation Procedure
Technical holding times for sample extraction are established by comparing the sample
collection date on the EPA Sample Traffic Report with the dates of extraction on Form I
PEST. To determine if the samples were analyzed-within the holding time after extraction,
compare the dates of extraction on Form I PEST. : . :
Verify that the traffic report indicates that the samples were received intact and iced.. If the
samples were not iced or there were any problems with the samples upon receipt, then.
discrepancies in the sample condition jcould affect the data. v .
3.2.4 Action -\( /
1. If technical holding times are exceeded, qualify all detected compound results as
estimated "J" and sample quantitation limits as estimated "UJ," except for PCBs
which are not expected to degrade significantly during storage.
2. If technical Holding times are grossly exceeded, either on the first analysis or upon
reanalysis, the reviewer must use professional judgment to determine the reliability
of the data and the effect of additional storage on the sample results. The reviewer
may determine that detected compound results or the associated quantitation limits
are approximates and should be qualified with "J" or "UJ," respectively. The
reviewer may determine that nondetected target compound data are unusable (R).
3. Due to limited information concerning holding times for soil samples, water holding
time criteria should be applied.
4. The reviewer should also be aware of the scenario in which the laboratory has
exceeded the technical holding times, but met contractual holding times. In this
case, the data reviewer should notify the Regional TPO (where samples were
collected) and/or RSCC that shipment delays have occurred so that the field
problem can be corrected. The reviewer may pass this information on to the
laboratory's TPO, but should explain that contractually the laboratory met the
requirements.
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 11 of 31
3.3 GC/ECD Instrument Performance Check
Performance checks on the gas chromatpgraph with electron capture detector, (GC/ECD)
system are performed to ensure adequate resolution and instrument sensitivity. These
criteria are not sample specific. Conformance is determined using standard materials;
therefore, these criteria should be met in all circumstances.
3.3.1 Acceptance Criteria
1. Resolution Check Mixture
a. The Resolution Check Mixture must be analyzed at the beginning of every
initial calibration sequence, on eath'GC column, and instrument used for
analysis. The Resolution Check Mixture contains the following pesticides
and surrogates: ^: ' ..'-'
gamma-Chlordane
EndosulfanI
4,4'-DDE
Dieldriri
Endosulfan sulfate
Endrinketone
Methoxychlor
Tetrachlorb-m-xylene
DecachlorobiphenyL.,
b. The depth of the valley between two adjacent peaks in the Resolution Check
Mixture must be greater than or equal to 60.0 percent of the height of the
shorter peak. ~
2. Performance Evaluation Mixtures
a. The Performance Evaluation Mixture (PEM) must be analyzed at the
beginning (following the resolution check mixture) and at the end of the
initial calibration sequence. The PEM must also be analyzed at the
beginning of every other 12-hour analytical period. The PEM contains the
following pesticides and surrogates.
gamma-BHC
alpha-BHC
4,4'-DDT
beta-BHC
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 12 of 31
Endrin
Methoxychlor
Tetrachloro-m-xylene
Decachlorobiphenyl
b. The resolution of adjacent peaks for the PEM injections in each calibration
(initial and continuing) must be 100 percent for both GC columns.
. - -
c. The absolute retention times of each of the single component pesticides and
surrogates in all PEM analyses must be within the specific^retention time
windows centered around the mean retention times determined from the
three-point initial calibration using the individual Standard Mixtures. , A list
of the retention time windows is found in Attachment 1, Table &ฃ '^
". ":/' -.'...- ,- . '" '-,- <:&ฃ$$ฃ$* '"'.;.
For example, for a given pesticide the mean, retention time is first
determined from the initial calibration and found to be 12.69 minutes. The
retention time window for this pesticide is ฑ0.05 minutes, ; Therefore, the
calculated retention time window would range from 12.64 to 12.74 minutes.
d. The relative percent difference (RPD) between the calculated amount and the
true amount for each of the single component pesticides and surrogates in
the PEM analyses must be less than or equal to 25.0 percent. _
ij .
e. The percent breakdown is the amount of decomposition that 4,4'-DDT and
Endrin undergo when analyzed on the GC column. For Endrin, the percent
breakdown is determined by the presence of Endrin aldehyde and/or Endrin
ketone in the GC chromatogram. For 4,4'-DDT, the percent breakdown is
determined from the presence of 4,4'-DDD and/or 4,4'-DDE in the GC
chromatogram. The equations used to verify these calculations are provided
in Attachment 1, Equations A and B.
i. The percent breakdown for both 4,4'-DDT and Endrin in each PEM
must be less than or equal to 20.0 percent for both GC columns.
ii. The combined percent breakdown for 4,4'-DDT and Endrin in each
PEM must be less than or equal to 30.0 percent for both GC
columns.
3.3.2 Review Items
Form VI PEST-4, Form VH PEST-1 Form VIII PEST, and chromatograms.
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 13 of 31
3.3.3 Evaluation Procedure
1. Resolution Check Mixture
'
Verify from the Form VIE PEST that the resolution check mixture was
analyzed ai the beginning of the initial calibration sequence on -each GC
cx)lunm and instrument used for analysis.
" '
b. , Check the resolution check mixture data and Form VI PEST-4 to verify that
the resolution criterion between two adjacent peaks for the required
compounds is less'than or equal to 60 percent.
' '' " ' '
2. Performance Evaluation Mixture
Verify from ^brii^EST that the Performance Evaluation Mixture (PEM)
was analyzed at^^po^erl^rrequency and position sequence.
:' '-y;-fi^^^^^':'-" - ''.'
a. Check the PEM data from the initial and continuing calibrations to verify
that the'resolution between adjacent peaks is 100 percent on both GC
columns. '': ;"v: " v
b. Check the PEM data from the initial and continuing calibrations and Form
VH PEST-1 to verify that the absolute retention times for the pesticides in
each analysis are within the calculated retention time windows based on the
mean RT from the three-point initial calibration using equations and
examples found in Attachment 1, Table 1. "
d. Verify that the relative percent difference (RPD) between the calculated
amount and the true amount for each of the pesticides and surrogates is less
than or equal to 25.0 percent. '
e. Verify that the individual breakdowns for 4,4'-DDT and Endrin are less than
or equal to 20.0 percent, and that the combined breakdown is less than or
equal to 30.0 percent.
3.3.4 Action
Resolution Check Mixture: If resolution criteria are not met the quantitative results
may not be accurate due to inadequate resolution. Detected target compounds that
were not adequately resolved should be qualified with "J." Qualitative
identifications may also be questionable if coelution exists. Nondetects with
retention times in the region of coelution may not be valid, depending on the extent
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 14 of 31
of the problem. Professional judgment should be used to determine the need to
qualify data as unusable (R).
2. Performance Evaluation Mixture Retention Times: Retention time windows are
used in qualitative identification. If the retention times of the pesticides in the PEM
do not fall within the retention time windows, the associated sample results should
be carefully evaluated. All samples injected after the last in-control standard are
potentially affected. It should be noted for TPO action if the PEM retention time
criteria are grossly exceeded. ~
- - ; -.. .' ' ' -is .-.;
a. For the affected samples, check to see if the sample chromatograms contain
any peaks that are close to the expected retention time window of the.
pesticide of interest. If no peaks are* present either within,or .close .to. the
retention time window of the deviant target pesticide compound, then there
is usually no effect on the data (i.e., nondetected values can be considered
valid). Sample data that are potentially affected by standards not meeting
. the retention time windows should be noted in the data review'narrative.
b. If the affected sample chromatograms contain peaks /which -may be of
concern (i.e., above the CRQL and either close to or within the expected
retention time window of the analyte of interest), then the reviewer should
determine the extent of the effect on the data and may choose to qualify
detected target compounds "N" and nondetected target compounds "UJ."
In some cases, additional effort by the reviewer may be necessary to
determine if sample peaks represent the compounds of interest, for example:
i. The reviewer can examine the data package for the presence
of three or more standards containing the pesticide of interest
that were run within a- 72-hour period during which the
sample was analyzed.
ii. If three or more such standards are present, the mean and
standard deviation of the retention time window can be
reevaluated.
Hi. If all standards and matrix spikes fall within the revised
window, the valid positive or negative sample results can be
determined using this window.
iv. The narrative should identify the additional efforts taken by
the reviewer and the resultant impact on data usability. In
addition, the support documentation should contain all
calculations and comparisons generated by the reviewer.
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 15 of 31
c. If the reviewer cannot do anything with the data to resolve the problem of
concern, all positive results and quantitation limits should be qualified "R."
3. Performance Evaluation Mixture Resolution: If PEM resolution criteria are not met
then the quantitative results may not be accurate due to inadequate resolution.
Positive sample results for compounds that were not adequately resolved should be
qualified with "J." Qualitative identifications may be questionable if coelution
.exists. Nohdetected target compounds that elute in the region of the coelution may
not be valid depending on the extent of the coelution problem, Professional
judgment should be tosed td qualify data as unusable (R).
4 If RPD criteria are not met/ qualify all associated positive results generated during
the analytical sequence with-v'J" and thejample quantitation limits for nondetected
target compounds wito "OT." ;-V '
. ;';: :4K-;- ''':.'.. ; ".'.'.'':'.'.
5. 4,4'-DDT/Endrin Breakdowii:
a. If 4,4'-DDT breakdown is greater than 20.0 percent:
i. Qualify all positive results for DDT as "L" biased low. If DDT
was not detected, but DDD and DDE are detected, then qualify the
quantitation limit for DDT as unusable (R).
ii. Qualify positive results for DDD and/or DDE as presumptively
present at an estimated quantity (N).
b. If Endrin breakdown is greater than 20.0 percent:
i. Qualify all positive results for Endrin with "J." If Endrin was not
detected, but Endrin aldehyde and Endrin ketone are detected, then
qualify the quantitation limit for Endrin as unusable (R).
ii. Qualify positive results for Endrin ketone as presumptively present at
an approximated quantity (N).
c. If the combined 4,4'-DDT and Endrin breakdown is greater than 30.0
percent:
i. Qualify all positive results for DDT and Endrin with "J." If Endrin
was not detected, but Endrin aldehyde and Endrin ketone are
detected, then qualify the quantitation limit for Endrin as unusable
(R). If DDT was not detected, but DDD and DDE are detected, then
qualify the quantitation limit for DDT as unusable (R).
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 16 of 31
ii. Qualify positive results for Endrin ketone as presumptively present at
an estimated quantity (N). Qualify positive results for DDD and/or
DDE as presumptively present at an approximated quantity (N).
'.''. ' i '
6. Potential effects on the sample data resulting from the initial calibration problems
/ should be noted in the data review narrative.
3.4 Initial Calibrkiim H >
Compliance requirements for satisfactory initial calibration are established to ensure that
the instrument is capable of producing acceptable qualitative and quantitative data for
pesticide and Aroclor target compounds. Initial calibration demonstrates that the
instrument is capable of acceptable performance at the beginning of the analytical sequence
and of producing a linear calibration curve. .
3.4.1 Acceptance Criteria .
\. Individual Standard Mixtures
a. Individual Standard Mixtures A and B (containing all of the single
component pesticides and surrogates) must be analyzed at low, midpoint,
and high levels during the initial calibration, on each GC column and
instrument used for analysis.
b. The resolution between any two adjacent peaks in the midpoint concentration
of Individual Standard Mixtures A and B in the initial calibration must be
greater than or equal to .90.0 percent on both columns.
c. The absolute retention times of each of the single component pesticides and
surrogates are determined from three-point initial calibration using the
Individual Standard Mixtures. A list of .the retention time windows are
included in Attachment 1, Table 1. ,
d. At least one chromatogram from each of the Individual Standard Mixtures A
and B must yield peaks that give recorder deflections between 50 to
100 percent of full scale.
e. The concentrations of the low, medium, and high level standards containing
all of the single component pesticides and surrogates (Individual Standard
Mixtures A and B) must meet the following criteria on both GC columns.
The low point corresponds to the CRQL for each analyte. The midpoint
concentration must be four times the low point. The high point must be at
least 16 times the low point, but a higher concentration may be chosen.
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f. The Percent Relative Standard Deviation (%RSD) of the calibration factors
for eaqh of the single component pesticides and surrogates in the initial
calibration on both columns for-Individual Standard Mixtures A and B must
be less than or equal to 20.0 percent, except as noted below. For the two
surrogates, the %RSD must be less than or equal to 30.0 percent. Up to
two, single component target pesticides (other than the. surrogates) per
column may exceed the 20.0 percent limit but the %RSD must be less than
or equal to 30.0 percent. Calculation is included in Attachment 1,
Equation D. . '' ' ./.- ' -\ ;^v-r;'\.-;
Note: Either peak area or peak height may be used to calculate the calibration
factors that are, in turn, used to calculate %RSD. However, the type of
peak measurement used to calculate/each calibration factor for a given
compound must be consistent. For example, if peak area is used to calculate
the low point calibration factor for endrin, then the^mid-^anci high-point
calibration factors for endrin must also be calculated using peak area.
2. Multi-Component Target Compounds
a. The multi-component target compounds (the 7 Aroclor and Toxaphene) must
each be analyzed separately at a single concentration level during the initial
calibration sequence. The analysis of the multi-component target compounds
must also contain the pesticide surrogates.
b. For each multi-component analyte, the retention times are determined for
three to five peaks. A retention time window of ฑ0.07 minutes is used to
determine retention time windows for all multi-component analyte peaks.
c. Calibration factor data must be determined for each peak selected from the
multi-component analysis.
3.4.2 Review Items
Form VI PEST-1, 2, 3, and 4, Form VII PEST-1, "Form VHI PEST, and chromatograms.
3.4.3 Evaluation Procedures
1. Individual Standard Mixtures
a. Verify from the Form VIII PEST that the Individual Standard
Mixtures A and B were analyzed at the proper frequency-on each
GC column and instrument used for analysis.
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2. Multi-Component Target Compounds
a. Verify from the Form VIE PEST that each of the multi-
component target compounds were analyzed at the required
frequency.
b. Check the data for the multi-component target compounds and
Form PEST VI-3 to verify that a least three peaks were used for
calibration and that retention time and calibration factor data are
available for each peak. --
3.4.4 Action
1. If the initial calibration sequence was not followed as required, then professional
judgment must be used to evaluate the effect of the non-compliance on the sample
data. If the requirements for the initial calibration sequence were not met, then this
should be noted for TPO action. If the non-compliance has a potential effect on the
data, then the data should be qualified according to the professional judgment of the
reviewer and this should be noted in the data review narrative.
2. If resolution criteria are not met, then the quantitative results may not be accurate
due to peak overlap and lack of adequate resolution. Positive sample results for
compounds that were not adequately resolved, should be qualified with "J."
Qualitative identifications may be questionable if coelution exists. Nondetected
target compounds that elute in the region of coelution may not be valid depending
on the extent of the coelution problem. Professional judgment should be used to
qualify data as unusable (R).
3. If the %RSD linearity criteria are not met for the compound(s) being quantified,
qualify all associated positive quantitative results with "J" and the sample
quantitation limits for nondetected target compounds with "UJ."
4. Potential effects on the sample data due to problems with calibration should be
noted in the data review narrative. If the data reviewer has knowledge that the
laboratory has repeatedly failed to comply with the requirements for frequency,
linearity, retention time, or resolution, the data reviewer should notify the TPO.
3.5. Continuing Calibration
Compliance requirements for satisfactory instrument calibration are established to ensure
that the instrument is capable of producing acceptable qualitative and quantitative data.
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Continuing calibration checks and documents satisfactory performance of the instrument
over specific time periods during sample analysis. To verify the calibration and evaluate
instrument performance, continuing calibration is performed, consisting of the analyses of
instrument blanks, the PEM, and the midpoint concentration of Individual Standard
Mixtures A and B.
3.5.1 Acceptance Criteria
1. An instrument blank and the PEM must bracket one end of a 12-hour period during
which samples are analyzed, and a second instrument blank and the midpoint
concentration of Individual Standard Mixtures A and 8 must bracket the other end
of the 12-hbur period. -'r^S^;
'' - i -, '.': : '. ' -jf- "' .''. '"<:' ';?'Ashts-V-r '__
2. The resolution between any two adjacent peaks in the midpoint'Concentration of
.Individual Standard Mixtures A and B must be greater rthan^ror equal to
90.0 percent ';_,- . ;-.' '^"-ป4/.';'- ' -.
3. The absolute retention time for each single component pesticide and surrogate in the
midpoint concentration of Individual Standard Mixtures A and B must be within the
retention time windows determined from the initial calibration. ""'
4. The RPD between the calculated amount and the true amounrfor each of the
pesticides and surrogates in the midpoint concentration of the Individual Standard
Mixtures A and B must not exceed 25.0 percent. :
3.5.2 Review Items
Form Vn PEST-1 and 2, Form VHI PEST, and chromatograms.
3.5.3 Evaluation Procedure
1. Check the Form Vm PEST to verify that the instrument blanks, PEMs, and
Individual Standard Mixtures were analyzed at the proper frequency and that no
more than 12 hours was elapsed between continuing calibration brackets in an
ongoing analytical sequence.
2. Check the data for the midpoint concentration of Individual Standard Mixtures A
and B to verify that the resolution between any two adjacent peaks is greater than or
equal to 90.0 percent.
3. Check the data for each of the single component pesticides and surrogates in the
midpoint concentration of Individual Standard Mixtures A and B and Form VII
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PEST-2 to verify that the absolute retention times are within the appropriate
retention time windows.
4. Check the data from the midpoint concentration of Individual Standard Mixtures A
and B and Form VH PEST-2 to verify that the RPD between the calculated amount
and the true amount for each of the pesticides and surrogates is less than or equal to
25.0 percent.
3.5.4 Action
1. If the continuing calibration sequence was not followed as required, then
professional judgment must be used to evaluate the effect of the noncompliance on
the sample data. If the requirements for the'continuing calibration sequence were
not met, then this should :1>e noted for TPO action. If the noncompliance has a
. potential effect on the data, then the data should be qualified according to the
professional judgment of me reviewer and this should be noted in the data review
narrative. V : ,
2. If resolution criteria are not met than the quantitative results may not be accurate
due to inadequate resolution. Positive sample results for compounds that were not
adequately resolved should be qualified with " J." Qualitative identification may be
questionable if coelution exists. Nondetected target compounds that elute in the
region of coelution may not be valid depending on the extent of the coelution
problem. Professional judgment should be used to qualify data as unusable (R).
3. Retention time windows are used in qualitative identification. If the standards do
not fall within the retention time windows, the associated sample results should be
carefully evaluated. All samples injected after the last in-control standard are
potentially effected. ,
a. For the affected samples, check to see if the sample chromatograms contain
any peaks that are close to the expected retention time window of the
pesticide of interest. If no peaks are present either within or close to the
retention time window of the deviant target pesticide compound, then
nondetected values can be considered valid. Sample data that is potentially
affected by the standards not meeting the retention time windows should be
noted in the data review narrative. If the retention time window criteria are
grossly exceeded, then this should be noted for TPO action.
b. If the affected sample chromatograms contain peaks which may be of
concern (i.e., above the CRQL and either close to or within the expected
retention time window of the pesticide of interest), then the reviewer should
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follow the guidelines provided in Section 3.3 to determine the extent of the
effect on the data.
4. If the RPD is greater than 25 percent for the compound(s) being quantified, qualify
all associated positive quantitative results with "J" and the sample quantitation
iimits for nondetects with "UJ." .
;. ' ' . " "">'' '''..-. ' " ' ' '.'' '
5. Potential effects on the sample data due to problems with calibration should be
noted in the data review narrative. If the data reviewer has knowledge that the
' laboratory has repeatedly failed to comply with the requirements for frequency,
linearity, retention time, resolution, or DDT/Endrin breakdown, the data reviewer
should notify the TPO.
3.6 Blanks
The purpose of laboratory (or field) blank analyses is to determine the existence and
magnitude of contamination problems resulting from laboratory (or field) activities. The-
criteria for evaluation of laboratory blanks apply to any blank associated with the samples
(e.g., method blanks, instrument blanks, and sulfur cleanup blanks). If problems with any
blank exist, all associated data must be carefully evaluated to determine whether or not
there is an inherent variability in the data, or if the problem is an isolated occurrence not
affecting other data.
3.6.1 Acceptance Criteria
1. No contaminants should be present in the blanks.
2. Frequency:
a. Method BlanksA method blank analysis must be performed for each
20 samples of similar matrix in each sample delivery group (SDG) or
whenever a sample extraction procedure is performed.
b. instrument BlanksAn acceptable instrument blank must be run at least once-
every 12 hours and immediately prior to the analysis of either the
performance evaluation mixture or Individual Standard Mixtures A and B,
depending on the place in the analysis sequence.
c. Sulfur Cleanup BlanksA sulfur cleanup blank must be analyzed whenever
part of a set of samples extracted together requires sulfur cleanup. If the
entire set of samples associated with a method blank requires sulfur cleanup,
then the method blank also serves the purpose of a sulfur blank and no
separate sulfur blank is required.
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3,6.2 Review Items
Form I PEST, Form IV PEST, and chromatograms.
3.6.3 Evaluation Procedure
1. Review the results of all associated blanks, Form I PEST, Form IV PEST, and
chromatograms to evaluate the presence of TCL pesticides.
2. Verify that method blank analysis has been reported per SDG, per matrix, per
concentration level, for each GC system used to analyze samples,-- and for each
extraction batch. v v
3. Verify that the method blank analyses do not contain any target pesticide or
Aroclor/Toxaphene at greater than its Contract Required Quantitation Limits
(CRQL). : ,. ;
4. For the surrogates in each method blank, verify that .the observed retention times'
are within the appropriate retention time windows calculated 'from the initial
calibration. ,. .
5. Verify that the instrument blank analysis has been performed every; 12. hours as part
of the continuing calibration and following a sample analysis which contains an
analyte(s) at high concentration(s), and that the instrument blanks do not contain any
target analytes above one-half the CRQL, assuming that the material in the
instrument resulted from the extraction of a 1-L water sample.
6. Verify that the sulfur cleanup blanks were analyzed at the required frequency and
that they do not contain any target compound above the CRQL, assuming that the
material in the instrument resulted from the extraction of a 1-L water sample. If a
separate sulfur cleanup blank was prepared, one version of Form IV PEST should
be completed associating all the 'samples with the method blank, and a second
version of Form IV PEST should be completed listing only those samples associated
with the separate sulfur cleanup blank.
3.6.4 Action
If the appropriate blanks were not analyzed with the frequency described in Criteria 3, 4,
and 5, then the data reviewer should use professional judgment to determine if the
associated sample data should be qualified. The reviewer may need to obtain additional
information from the laboratory. The situation should be brought to the attention of the
TPO.
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Action in the case of unsuitable blank results depends on the circumstances and the origin
of the blank. Detected compound results should be reported and qualified "B" if the
concentration of the compound in the sample is less than or equal to 5 times (5x) the
amount in the blank. In instances where more than one blank is associated with a given
sample, qualification should be based on a comparison with the associated blank having the
highest concentration of a contaminant. The results must not be corrected by subtracting
the blank value. r--'--v"^-;''/:;- :" . " -v'-'';;:-.--;'.'.
Specific actions are as follows:
1. If a target pesticide or Aroclor/Toxaphene is found in the blank but hot found in the
sample(s), no qualification is required. If the contaminant(s) is found at level(s)
significantly greater than the CRQL, then-this should be noted in the data review
narrative. - " !
'- i ป **-/"" ' - -, .-'--:."."._.
. - ป ' ' . ' . '
2. Any pesticide or Aroclor/Toxaphene detected in the sample, that was also detected
in any associated blank, is qualified if the sample concentration is less than five.
times (5x) the blank concentration. The quantitation limit may also be elevated:
Typically, the sample CRQL is elevated to the concentration found in the sample.
The reviewer should use professional judgment to determine if further elevation of
the CRQL is required.
The reviewer should note that analyte concentrations calculated for method blank
may not involve the same weights, volumes, or dilution factors as the associated
samples. These factors must be taken into consideration when applying the "Sx"
criteria, such that a comparison of the total amount of contamination is actually
made.
In addition, there may be instances when little or no contamination was present in
the associated blanks, but qualification of the sample, was deemed necessary.
Contamination introduced through dilution is one example. Although it is not
always possible to. determine, instances of this occurring can be detected when
contaminants are found in the diluted sample result, but absent in the undiluted
sample result. Since both results are not routinely reported, it may be possible to
verify this source of contamination. However, if the reviewer determines that the
contamination is from a source other than the sample, he/she should qualify the
data. In this case, the "5x" rule does not apply; the sample value should be
reported and qualified "B" and a note should be added to the narrative.
3. If gross contamination exists (i.e., saturated peaks), all affected compounds in the
associated samples should be qualified as unusable (R), due to interference. This
should be noted in the data review narrative if the contamination is suspected of
having an effect on the sample results.
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4. If inordinate amounts of other target pesticides or Aroclors/Toxaphene are found at
low levels in the blank(s), it may be indicative of a problem at the laboratory and
should be noted in the data review narrative.
5. If an instrument blank was not analyzed following a sample analysis which
contained an analyte(s) athighconcปntration(s), sample analysis results after the
high .concentration sample must be evaluated for carryover. Professional judgment
should be used to determine if instrument cross-contamination has effected any
. s\- '-'.* - ,. . ., X '.'' *
: positive compound identificationฎ, and if so, detected compound results .should be
qualified. If instrument cross-contamination is suggested, then this should be noted
in the data review narrative if the cross-contamination is suspected of having an
effect on the sample results. ^:U->,
' ' '
The following are examples of applying the blank qualification guidelines. Certain
circumstances may warrant deviations from these guidelines: /v. ;^j>
'-.^i*:ซ''.'?"'-; :'.". ' '
ซ' "" . .ซ " -
Example 1:' Sample result is greater than the CRQL, but is less than the 5x
multiole of the blank result
multiple of the blank result.
Blank Result : 1.0
CRQL 0.5
Sample Result 4.0
Qualified Sample Result 4.0B
In this case, sample results less than 5.0 (or 5 x 1.0) would be
qualified as nondetected target compounds.
Example 2: Sample result is less than the CRQL, and is also less than the 5x
multiple of the blank result.
5jc
Blank Result 1.0
CRQL 0.5
Sample Result 0.4J
Qualified Sample Result 0.4B
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Example 3: Sample result is greater than the 5x multiple of the blank result.
Blank Result 1.0
CRQL 0.5
Sample Result 10.0
-Qualified Sample Result 10.0 v
In this case, the sample result exceeded the adjusted blank result (5x
1.0) and the sample result is not qualified.
. '.- ; -iv-Jfti^^^sSv; v v
' 3.7 'Surrogate
. ". ' ; ".
Laboratory performance oniindi>idual samples is established by means of spiking samples
prior to extraction and analysis 'to determine surrogate spike recoveries. All samples are
spiked with surrogate compounds prior to sample extraction. Hie evaluation of the
recovery results of these surrogate .spikes is not: necessarily straightforward. The sample
itself may produce effects due to such factors as interferences and high concentrations of
target and/or nontarget ahalytes. Since the effects of the sample matrix are frequently
outside the control of the laboratory and may present relatively unique problems, the
evaluation and review of data based on specific sample results is frequently, subjective and
demands analytical experience and professional judgment. Accordingly, this section
consists primarily of guidelines, in some cases with several optional approaches suggested.
3.7.1 Acceptance Criteria
1. Two surrogate spikes, tetrachloro-m-xylene and decachlorobiphenyl, are added to
all samples, Individual, Standard Mixtures, PEMs, blanks, and matrix spikes to
measure their recovery in sample and blank matrices.
2. The advisory limits for recovery of the surrogates tetrachloro-m-xylene (TCX) and
decachlorobiphenyl (DCB) are 60 to 150 percent for both water and soil samples.
3. The retention times of both of the surrogates in the PEM, Individual Standard
Mixtures, and samples must be within the calculated retention time windows. TCX
must be within ฑ0.05 minutes, and DCB must be within ฑ0.10 minutes of the
mean retention time determined from the initial calibration.
3.7.2 Review Items
Form II PEST, Form Vffl PEST, and chromatograms.
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3.7.3 Evaluation Procedures
1. Verify that the recoveries on the Surrogate Recovery Form n PEST are accurate
and within the advisory limits and that the retention times on the Pesticide
, Analytical Sequence Form Vm PEST are accurate and within,the retention time
" limits.-' . .; ''/ "...''." . . ' .' , -.'-.-..
2. If low surrogate recoveries are observed, the reviewer should investigate whether
me low recoveries were a result of sample dilution.
3. In the special case of a'blank analysis with surrogates out of specification, the
reviewer must give special consideration to the validity of associated sample data.
The basic concern is whether the blank problems represent an isolated problem with
the blank alone, or whether there is a fundamental problem with the analytical
. process. For example, if one or more samples in the batch show acceptable
surrogate recoveries, the reviewer may choose to consider the blank problem to be
an isolated occurrence. .
3.7.4 Action
1. If surrogate spike recoveries are.outside of advisory limits, the following guidance
is suggested. Professional judgment must be used in applying these-criteria.
a. If low recoveries (i.e., between 10 and 60 percent) are obtained,f this may
be an indication of a low bias in sample results and associated detected
compound data should be qualified ' 'L'' and quantitation limits 4 'UL.''
b. If high recoveries (i.e, greater than 150 percent) are obtained, this may be
an indication of a high bias due to co-eluting interferences. Qualify
associated detected compound data with "K", nondetected analytes do not
require qualification.
c. If either pesticide surrogate recovery is reported as between zero percent and
10 percent, the reviewer should examine the sample chromatogram to assess
the qualitative validity of the analysis. If low surrogate recoveries are found
to be due to sample dilution, then professional judgment should be used to
determine if the resulting data should be qualified. If sample dilution is not
a factor, then detected target compounds may be qualified "L" and
nondetected target compound results should be qualified unusable (L).
d. If zero pesticide surrogate recovery is reported, the reviewer should examine
the sample chromatogram to determine if the surrogate may be present, but
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slightly outside its retention time window. If this is the case, in addition to
assessing surrogate recovery for quantitative bias, the overriding
consideration is to investigate the qualitative validity of the analysis. If the
surrogate is not present, qualify all nondetected target compounds as
unusable (R). . ';
*ป''.''
2. If surrogate retention times in PEMs, individual standards, and samples are outside
of the retention time limits,.qualification of the data is left up to the professional
judgment of the reviewer. Refer to Section 3.3.4.2 for more guidance.
3. Extreme or repeated analytical problems with surrogate recoveries should be noted
for TPO action. ; -..=.&##.':' ;;-, ' . : -.\V./ ': '- .-:
4. Potential effects of the data resulting from surrogate recoveries not meeting the
advisory limits should be noted in the data review narrative.
3.8 Matrix Spikes/Matrix Spike Duplicates
'"."' ' '"; :':'^^: ?':'' ' . ; :
Data for matrix spikes (MS) and matrix spike duplicates (MSD) are generated to determine
long-term precision and accuracy of the analytical method on various matrices. These data
alone cannot be used to evaluate the precision and accuracy of individual samples.
However, when exercising professional judgment, MS/MSD data should be used in
conjunction with information on other deficiencies.
3.8.1 Acceptance Criteria
1. Matrix spikes (MS) and matrix spike duplicate (MSD) samples are analyzed at a
frequency of at lest one MS and MSD per 20 samples of each matrix.
2. Matrix spike recoveries should be within the advisory limits provided on Form m
PEST-1 and PESTV2 and in Attachment 1, Table 2.
3. Relative percent difference (RPD) between MS and MSD recoveries must be within
the advisory limits provided on Form in PEST-1 and PEST-2 and in Attachment 1,
Table 2.
3.8.2 Review Items
Form HI PEST-1 and PEST-2, and chromatograms
3.8.3 Evaluation Procedures
1. Verify that MS and MSD samples were analyzed at the required frequency and that
results are provided for each sample matrix.
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2. Inspect results for the MS/MSD Recovery on Form ffl PEST-1 and PEST-2 and
verify that the results for recovery and RPD are within the advisory limits.
4. Check that the matrix spike recoveries and RPD were calculated correctly.
5. Compare %RSD results of npnspiked compounds between the original result, MS,
and MSD.
3.8.4 Action
1. No action is taken on MS/MSD data alone. However, using informed professional
judgment the data reviewer may use the MS- and MSD results in conjunction with
other QC criteria and determine the need for some qualification of the data.
2. The data reviewer should first try to determine to what extent the results of the
MS/MSD affect the associated sample data. This determination should be made.
with regard to the MS/MSD sample itself, as well as specific analytes for all sample *
associated with the MS/MSD.
3. In those instances where it can be determined that the results of the MS/MSD affect
only the sample spiked, then qualification should be limited to this- sample alone.
However, it may be determined through the MS/MSD results that la laboratory is
having a systematic problem in the analysis of one or more analytes, which affects
all associated samples. For example, if the recoveries for MS and MSD are
consistently low for both water and soil samples, this could be indicative of a
systematic problem in the laboratory and recoveries should be examined in all
associated samples.
4. The reviewer must use professional judgment to determine the need for qualification
of positive results of nonspiked compounds.
NOTE: If a field blank was used for the MS/MSD, a statement to that effect
must be included for the TPO.
3.9 Pesticide Cleanup Checks
Pesticide cleanup procedures are utilized to remove matrix interferences from sample
extracts prior to analysis. The use of the Florisil cartridge cleanup procedure significantly
reduces matrix interferences caused by polar compounds. Gel permeation chromatography
(GPC) is used to remove high molecular weight contaminants that can interfere with the
analysis of target analytes. Pesticide cleanup procedures are checked by spiking the
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cleanup columns and cartridges, and verifying tne recovery of pesticides through the
cleanup procedure.
3.9.1 Acceptance Criteria
1. Florisil Cartridge Cleanup
a. Florisil cartridges must be used for the cleanup of all sample extracts.
b. Every lot number of Florisil cartridges used for sample cleanup must be
checked by spiking with 2,4,5-trichlorqphenol and the midpoint
concentration of Individual Standard Mixture A. '
c. The lot of Florisil cartridges is acceptable if the recoveries for all of the
pesticides and surrogates in Individual Standard Mixture A are within 80 to
120 percent, if the recovery of 2,4,5-trichlorophenol is less than 5 percent,
and if no peaks interfering with the target analytes are detected.
2. Gel Permeation Chromatography (GPC)
a. GPC is used for the cleanup of all soil sample extracts and for water sample
extracts that contain high molecular weight components that interfere with
the analysis of the target analytes.
b. At least once every 7 days, the calibration of the GPC units must be checked
by spiking with two check mixtures: the matrix spiking solution and a
mixture of 0.2 ug/ml Aroclors 1016 and 1260.
c. The GPC calibration is acceptable if the recovery of the pesticides in the
matrix spiking solution are within 80 to 110 percent, and the Aroclor
patterns should match those generated for previously run standards.
d. A GPC blank must be analyzed after each GPC calibration and is acceptable
if the blank does not exceed one-half the CRQL for any target analytes.
3.9.2 Review Items
Form IX PEST-1 and 2 and chromatograms
3.9.3 Evaluation Procedure
1. Florisil Cartridge Check
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Check the data from the Florisil cartridge solution analyses and the Form DC PEST-
1 and recalculate some of the percent recoveries to verify that the percent recoveries
, of the pesticides and surrogates in Individual Standard Mixture A are within 80 to
120 percent, the recovery of 2,4,5-trichlorophenol is less than 5 percent, and no
interfering peaks are present. Compare the raw data to the reported results and
verify that no calculation or transcription errors have occurred.
2. Gel Permeation Chromatography (GPC)
Check the data from the GPC calibration check analyses and the Form DC PEST-2
and recalculate some of the percent recoveries to verify that the percent recoveries
of the pesticides in the matrix spike solution are within 80 to 110 percent and that
the Aroclor patterns are similar to those ofj>revious standards. Check to make sure
that no transcription errors have occurred.
3.9.4 Action
1. If Florisil Cartridge Check criteria are not met, the raw data should be examined'
for the presence of polar interferences and professional judgment should be used to
qualifying the data. If a laboratory chooses to analyze samples under an
unacceptable Florisil Cartridge Check, then the TPO should be notified.
2. If Gel Permeation Criteria are not met, the raw data should be examined for the
presence of high molecular weight contaminants and professional judgment should
be used in qualifying the data. If a laboratory chooses to analyze samples under
unacceptable Gel Permeation Criteria, then the TPO should be notified.
3. If zero recovery was obtained for the pesticide compounds and surrogates during
either check, then the nondetected target compounds may be suspect and the data
may be qualified unusable (R).
4. If high recoveries (i.e, greater than 120, percent) were obtained for the pesticides
and surrogates during either check, use professional judgment to qualify detected
target compounds as biased high (K). Nondetected target compounds do not require
qualification.
5. Potential effects on the sample data result from the pesticide cleanup analyses not
yielding acceptable results should be noted in the data review narrative.
3.10 Reported CRQLS
The objective is to ensure that contract required quantitation limits (CRQLs) are accurate.
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Procedure No. t M2-PEST
Revision: 1
Date: 06/30/1995
Page 31 of 31
3.10.1 Acceptance Criteria
The adjustment of the CRQL, must be calculated according to the equations provided in
Attachment 1, Equations N and O.
3.10.2 Review Items
Form 1 PEST, Form X PEST-1 and PEST-2, and chromatograms.
k
3.10.3 Evaluation Procedure
1. Verify that the CRQLs have been adjusted to reflect all sample dilution,
concentrations, splits, cleanup activities and dry weight factors that are not
accounted for by the method. .
' - *" ' . ' " .
3.10.4 Action
1. If there are any discrepancies found, the laboratory may be contacted by the
designated representative to obtain additional information that could resolve any
differences. If a discrepancy remains unresolved, the reviewer must decide which
value is the best value. Under these circumstances, the reviewer may determine if
qualification of the data is warranted. A description of the reasons for data
qualification and the qualification that is applied to the data should be documented
in the data review narrative.
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page: 1 of 6
Attachment 1 to Appendix C-2
Multi-Media, Multi-Concentration
Contractual Requirements and Equations
for Pesticide Data Review
GG/ECD Instrument Performance Check
Check the Performance Evaluation Mixture calculations using equations IL2, n.3, and n.4 to
ensure correct calculation of DT and Endrin breakdown. The breakdown of DDT and Endrin
in both of the PEM injections must be less than 20.0 percent, and the combined breakdown of
DDT and Endrin must be'.'less than 30.0 percent. . .
^m found in ngfpDD^DDEtx 100 (A)
'Amount in ng of DD7 injected
% Breakdown Endrin =
. - '
Amount found in ng (Endrin aldehyde + Endrin ketone) x 100 ^\
Amount of Endrin injected in ng ' . __
Combined % Breakdown - % Breakdown DDT + % Breakdown Endrin (Q
All peaks in both the injections of the Performance Evaluation Mixture must be 100 percent
resolved on both columns. The relative percent difference of the calculated amount and the
true amount for each of the single component pesticides and surrogates in the PEMs must be
less than or equal to 25.0 percent using equation D.
= F~"ป " Cซ*l x 100 (D)
nom
Where:
True concentration of each analyte
Calculated concentration of each analyte from the analysis of the
standard
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page: 2 of .6
Initial Calibration
Retention time windows for each analyte and surrogate are calculated using Table 1. Windows
are centered around the mean absolute retention time for the analyte established during the
initial calibration. For example, for a given pesticide the mean retention time is first
determined from the initial calibration and found to be 12.69 minutes. The retention time
window for this pesticide is ฑ0.05 minutes. Therefore, the calculated retention time window
would range from 12.64 to 12.74 minutes. ..-',-.
Table 1
RETENTION TIME WINDOWS FOR PESTICIDE TARGET COMPOUNDS
Pesticide Compounds
alpha-BHC .;
beta-BHC
gamma-BHC
delta-BHC
Heptachlor .
Aldrin
aipha-Chlordane > ... '
gamma-Chlordane
Heptachlor epoxide
Dieldrin
Endrin
Endrin aldehyde
Endrin ketone
DDD
DDE
DDT
Endosulfan I
Endosulfan n
Endosulfan sulfate
Methoxychlor
Aroclors
Toxaphene
Tetrachloro-m-xylene
Decachlorobiphenyl
Retention Time Windows in Minutes
ฑ005
ฑ0.05
ฑ0.05
ฑ0.05
ฑ0:05
ฑ0.05
ฑ0.07
ฑ0.07
ฑ0.07 -
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.05
ฑ0.10
The %RSD of the calibration factors for each single component target compound must be less
than or equal to 20.0 percent. The %RSD for the two surrogates must be less than or equal to
30.0 percent. Up to two single component target compounds per column may exceed the 20.0
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
'Page: 4 of.6
RPD
x 100
(I)
nom
Where:
= True concentration of each analyte
= Calculated concentration of each analyte from the analysis of the
standard . . ~
Surrogate Spikes
The advisory limits for recovery of tetrachloro-m-xylene (TCX) and decachlorobiphenyl (DCB)
are 60 to 150 percent for both water and soil samples. The surrogate percent recovery is
calculated using equation J. The retention times of both surrogates must be within the
calculated retention time windows, i.e., TCX must be within ฑ0.05 minutes of the mean
retention time determined from the initial calibration and DCB must be within ฑ0.10 minutes
of the mean retention time determined from the initial calibration. . .
O,
Surrogate Percent Recovery = --= x 100 (J)
Where:
Qd = Quantity determined by analysis
Q, = Quantity added to sample/blank
Matrix Spikes/Matrix Spike Duplicate
The matrix spike/matrix spike duplicate recovery and RPD requirements are listed in Table 2.
The matrix spike recoveries and RPD are calculated using equations K and L.
Table 2
MS/MSD CONTRACTUAL REQUIREMENTS
Compound
gamma-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4'-DDT
% Recovery
Water
56-123
40-131
40-120
52-126
56-121
38-127
RPD
Water
. 15
20 .
22
18
21
27
% Recovery
SoU
46-127
35-130
34-132
31-134
42-139
23-134
RPD
Soil
50
31
43.
38
45
50
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page: 3 of 6
percent limit for %RSD, but those compounds must have a %RSD of less than or equal to
30.0 percent. Calibration factors are calculated using equations G and H and the %RSD is
calculated using equations E and F.
%KSD = StandardDeviation f ^ (E)
Mean
where:
ฃ*-ป!.;.
StandardDeviation - | f/2
Where:.:. '" .-..."/''-. . ' .." f
& - each individual value used to calculate the mean
x = the mean of n values
n = the total number of values
_ Peak Area (V Height} of the Standard
', Mass injected (ng)
" CF
CF = ^ (H)
i i n
Where:
CF = Mean calibration factor of n values
CFj = i* calibration factor
n = Total number of values
Continuing Calibration
The retention time (RT) for each target compound and surrogate must be within RT window as
calculated above using the mean absolute RT established during the three-point initial
calibration. The relative percent difference of the calculated amount and the true amount for
each of the compounds in the mid-point concentration of the Individual Standard Mixtures must
be less than or equal to 25.0 percent using equation I.
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page: 5 of. 6
Spike Recovery = -- x 100 (K)
Where:
SSR = Spike sample result
SR = Sample result
SA = Spike added .
' > ' . ' .
\MSR-MSDR\
1/2 (MSR + MSDR)
Where:'.-' ''-'';;;,: '.'.. ' ' : '. ...-. :
- RPD = Relative percent difference
MSR = Matrix spike recovery
MSDR Matrix spike duplicate recovery . ..
The Vertical bars in the formula above indicate the absolute value of the
difference, hence RPD is always expressed as a positive value.
Pesticide Cleanup Check
Every lot number of Florisil cartridges used for sample cleanup must be checked by spiking
with 2,4,5-trichlorophenol and the midpoint concentration of Individual Standard Mixture A.
The recoveries for all of the pesticides and surrogates in Individual Standard Mixture A must
be within 80 to 120 percent, the recovery off 2,4,5-trichlorophenol must be less than 5
percent, and no peaks must interfere with the target analytes. Percent recovery is determined
using equation M.
Q.
Percent Recovery = - x 100 (M)
^ซ
Where:
Qd = Quantity determined by analysis
Q. = Quantity added to sample/blank
The gel permeation chromatography (GPC) apparatus must be calibrated every 7 days. The
calibration is acceptable if the recovery of each single component analyte is within 80 to 110
percent and the Aroclor patterns match patterns previously generated by standards.
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page: 6 of .6
..Reported CRQLs
The CRQL of the single component pesticides is calculated using equations N and O, as
appropriate. .
CRQL for waters:
Sample CRQJL = Reference CRQLx Df (N)
' I '-.:
Df = Dilution factor
CRQL for soils/sediments (dry weight basis):
Sample CRQL = Reference CRQL x (O)
100 - % moisture
100
-------
Appendix D
Validation of Inorganic Analyte Data
Level IM-1
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 1 of 26
VALIDATION OF TARGET ANALYTE LIST METALS
AND CYANIDE DATA
MANUAL APPROACH BM-1
1. PURPOSE AND APPLICABIIJTY
this procedure provides instructions to manually validate the target analyte list (TAL)
metals and cyanide data using a manual innovative data validation approach that is based on
the EPA's National Functional Guidelines for Data Review and EPA Region Hi's
Modifications to the National Functional Guidelines for Data Review. Specifically, the
approach is based on the use of quality control (QQ information contained on. the
laboratory QC summary forms, and does not utilize' the raw data. The information that is
obtained from the QC summary.; forms is indicated ton Table D^WNORG-^.j^iThis
procedure is applicable to the TAL metal and cyanide data obtained using the (Hontract
Laboratory Program Statement of Work (CLP SOW). -
Data validated using this procedure are considered usable for the following types of
purposes; however, the data users must decide on a case-by-case basis whether the
procedure is suitable for their intended data uses. The suggested data uses are:
Oversight of activities led by other parties
Comparison to action levels
Initial site investigation
Contamination sources
Nature and extent of contamination
Preliminary risk assessment
Risk assessment with known high levels of toxics
Feasibility study
Preliminary design
ซ Treatability study
Initial cleanup verification
1M-1-INORO
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 2 of 26
2. QUALITY CONTROL MEASURES CHECKED
Table IM-1-INORG-QC highlights the quality control (QC) indicators evaluated under this
data validation procedure. These measures fall under one or more data validation steps
highlighted below.
2.1 PROCEDURES
Data validation is performed primarily with respect to the technical data quality criteria;
however, there are certain contractual criteria that may reflect on a participating
laboratory's compliance with the terms and conditions of the program and future audits of
the laboratory. The term "CCS" next to a validation step indicates that there is a
contractual criteria in addition to the technical criteria. It is incumbent upon a data
validator to point put the^cMtractUal deficiencies to-the laboratory's CLP Technical Project
Officer (TPO) for clarificMons and corrective action. The data validation steps, are as
follows: ' ','-'->'fyฃ:V^X':.-i;:
Action Level Notification
Technical Holding Times (CCS - Contractual holding times only)
Calibration
Initial (CCS)
Initial and Continuing Calibration Verification (CCS)
CRDL Standards
Blanks
Initial Calibration Blank (CCS)
Continuing Calibration Blank (CCS)
Preparation Blank (CCS)
ICP Interference Check Sample (CCS)
Laboratory Control Sample (CCS)
Duplicate Sample (CCS)
1M-MNORO
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 3 of 26
Table IM-1-INORG-QC
QC CHECKLIST FOR LEVEL IM-1
CLP RAS TARGET ANALYTE LIST INORGANICS
1 ' ' . . ' 1 .. ' '
'..< QC MEASURES
' . ' . . '' 1
Action Level Notification .
Holding Times
v
Initial Calibration
Initial Calibration Verification / . ^
Continuing Calibration Verification '
..**.. ' v . ' . . ' . ' _
Laboratory Blank '.
Kjf interterence mecK . .
Laboratory Control Sample
Duplicate Precision
Matrix Spike Recovery
Furnace QC (MSA)
ICP Serial Dilution
Field Duplicates
Reporting Limit Verification
Sample Paperwork ,
Raw Data
| IM-1 |
|: . x \
x
X
.x/ '"' .
' x' : " ". '
-.-.-'xrj
. ';.X; ::.; '
x
X
X
X
X
X
X
X
X
^M
M2
1 x
x
1
X
X
' "' -.-x .. .
,-: ." x :
X
x
^^ X
X
X
X
X
X
X
X
X
1M-1-D40RG
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 4 of 26
Matrix Spike Sample^CCS)
Graphite Furnace Atomic Absorption QC (CCS)
v
Method of Standard Addition (MSA) .
ICP Serial Dilution (CCS)
. . '! . . ''..'. '"..' ' ;
Field Duplicates (if included)
" . \ ' ''''''. ' ' ' ' ป.",.'
Reporting Limit Verification (IDLs, linear range, dilution factors and
moisture content)
I : .-,'- . . ' -
Sample Paperwork ^-?:
REPORTING REQUIREMENTS
Several forms have been developed to assist in the performance evaluation and in keeping;
track of the data quality qualifiers: The first form, IM-1-INORG-HT, summarizes the'
holding times. The second form, IM-1-INORG-CAL allows documentation of the
calibration and blank QC violations. The third form, IM-1-INORG-SPK is used for the
spike recoveries, duplicate precision, and control sample analyses data. The fourth form,
IM-1-INORG-QL is used for summarizing all qualifiers for the samples. The EPA Region
HI Inorganic Regional Data Assessment form is used by the data validator to summarize
contractual deficiencies for the laboratory's CLP Technical Project Officer (TPO). All
forms are appended at the back of this SOP.
A memorandum describing those elements that were outside of established QC criteria, the
actions which were taken and the impact on data usability must be prepared with
substantiating documentation. The report-and the supporting documentation should include
the following:
1. Hand annotated Form Is with
a. data validation qualifiers
b. sample identification number
c. sampling location
2. A narrative description with
a. a statement that defines the level of the data review, i.e., IM-1
b. major and minor problems associated with the analysis
c. issues that may have affected detection limits
1M-1-INORO
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 5 of 26
3. The following attachments
a. list of data validation qualifiers
b. documentation which includes forms that support the assigned data
qualifiers. Samples affected; by noncompliant quality control
. measures should be listed on these forms.
c. chain of custody form(s)
GLOSSARY OF DAT A QUALIFIER CODES (INORGANIC)
The codes described below are (hose recommended in the EPA's national Functional
Guidelines and the Region ffl's modifications.
Codes Relating to
(confidence concerning presence or absence of analytes):
U =' ':'.'' ': r >^ :iileปciid. ^The associated number indicates approximate
sample'ooncentration necessary to be detected.'
. . . ' .'" _ >:" v-fe^v-^fcv'-v-Vv.-, "':: -' :..'.' :.:'
(NO CODE) = Confirmed identification.
B = Not detected substantially above the level reported in laboratory
or field blanks. - -Z^
R = Unreliable result. Analyte may or may not be present in the
sample. Supporting data necessary to confirm result.
Codes Relating to Quantitation
(can be used for both positive results and sample quantitation limits):
J = Analyte present. Reported value may not be accurate or precise.
K = Analyte present. Reported value may be biased high. Actual
value is expected lower.
L = Analyte present. Reported value may be biased low. Actual
value is expected to be higher.
UJ = Not detected, quantitation limit may be inaccurate or imprecise.
UL = Not detected, quantitation limit is probably higher.
IM-l-INORO
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 6 of 26
Other Codes
Q = ; No analytical result.
* = Results reported from diluted analysis.
The following subsections describe for each of the QC indicators die acceptance criteria,
location and retrieval of QC data, evaluation of the QC data, actions taken in the event the
QC acceptance criteria are exceeded, and documentation of the QC violations in a
' ' '
2 3 ACTION LEVEL NOTIFICATION
'-..'."'' ' ' .ii,",- .' '.' '.'!.' '.'-.. ".''' '". ,. ' . ... '.< . .' *.ซ=ป--.. :: ..-'.. .'.-. '.:.- ..'
The purpose behind action level notification is to make the EPA Remedial Project Officer
(RPM) or the Site Project Officer (SPO) aware ef the potential human health risk at the
site. In accordance with me Region "ID Hazardous Waste Division policy, the EPA RPM
or SPO must be promptly notified of any contaminant exceeding the established action level
^or the 10-day health advisory limit The data for contaminants exceeding the action levels
must be validated as a top priority and reported to the RPM or SPO, as soon as possible.
Validation of the rest of the data may then be completed within the normal time frame.
2.3.1 Acceptance Criteria
* i ..''.'-."-' ' * .
EPA's Office of Solid Waste and Emergency Response has established -10-day advisory
limits and action levels for several organic compounds and elements of special health risk
concerns based on the Safe Drinking Water Act The target analytes and their 10-day
health advisory limits are listed in Table IM-1-INORG-AL. The criteria for action level
notification are as follows:
The contaminant concentration must be equal to or above the established 10-
day health advisory limits.
Data for contaminants exceeding the action levels must be validated as a top
priority.
The following EPA personnel must be notified of the action level
exceedances:
EPA RPM or SPO
EPA Section Chiefs
The remaining data validation should be completed per normal procedures.
1M-1-INORO
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Procedure No.: 1M-1-INORG
Revision: 2
Date: 06/30/95
Page: 7 of 24
Any special instructions from the Hazardous Waste Division should be
followed.
Records should be kept of the data review, action level notification and any
follow up instructions and actions.
Table IM-1-INORG-AL
TARGET ANALYTE LIST METALS AND ACTION LEVELS
Compound "
Arsenic, - ' -; W- ... .:
.. .1 .':.'.'
Chromium - :
Nickel
'Action
Level'
-.x;'--,5d-v- .'
1000
- .^1000 '-:<;
Compound .
Cadmium -'
Lead'" '" '' '' '': ,''' -
Cyanide ,,.. :'- ''''-.
' ' Action
Level'
yr>/r'.40.
v -.-? if'-
200
' All units are ug/1. ' ' . . . :
- ... - .- ^. r .'"'-' -J - ' ' ". '.'.'' ' ' ' - * '
b Lead also has an action level of 500 mg/kg (ppmw) for soil samples.
2.3.2 Data requirements and Retrieval of Data ,_
' ' * * *^-*.
All forms required to perform Level IM-1 validation, as detailed in the following sections
are necessary for carrying out action level notification.
2.3.3 Evaluation Procedure
The evaluation process preceding action level notification will primarily consist of
comparing the results on Form Is with the action levels presented in Table IM-1-INORG-
AL. Following the identification of the contaminants exceeding the action levels, focused
data validation should be performed using the criteria, and procedures described in the
appropriate sections below.
2.3.4 Action
The action resulting from focused data validation will be the notification of action level
exceedance to the personnel identified above in Section 2.3.1. Copies of Form Is can be
used to highlight the contaminants above the action levels. The findings of the focused
validation can be summarized in a memorandum, and the data qualifiers resulting from
focused validation may be written on the Form Is. The marked up forms should state that
they represent validation of only the contaminants exceeding the action levels, and not all
data.
1M-MNORO
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Procedure No.: 1M-1-INORG
Revision: 2
Date: 06/30/95
Page: 8 of 24
2.4 HOLDING TIMES
The primary objective is to ascertain the validity of results based on the holding time of the
sample from time of collection to time of sample extraction and analysis. The secondary
objective is also to verify compliance with the contractual extraction and analysis holding
times from the verified time of sample receipt (VTSR> at the laboratory.
2.4.1 Acceptance Criteria;
Technical requirements for sample holding times have only been established for water
matrices. The following holding times (from the time of sample collection) and
preservation requirements were established under 40 CFR 136 (dean Water Act), and are
found:in Volume49, Number209 of the Federal Register, page43260, issued on
October 26V 1984i \ ;''" ~
>.-^. -,^.:I<*L<; ,.
'."/ : Metals: 6 months; preserved to pH < 2
Mercury: 28rdays; preserved to pH < 2
Cyanide: 14 days; preserved to pH > 12
Contractual holding times have been established by the CLP for the water and soil/sediment
samples. The times are counted from the time of sample receipt at the laboratory, and are
as follows:
Metals: 180 days
Mercury: 26 days
Cyanide: 12 days
Generally, the holding times are calculated using the dates only and not the times.
2.4.2 Data Requirements and Retrieval of Data
Forms 1, 13, 14, and EPA Traffic Reports and Sample Shipping Logs.
2.4.3 Evaluation Procedure
Technical holding times are established by comparing the sampling date on the EPA
Sample Traffic Report with the dates of sample preparation/extraction and analysis found
on the extraction and instrument run logs (Forms 13 and 14, respectively).
Technical Holding Time (days) = Analysis Date - Sampling Date
Contractual holding times are established by comparing the sample receipt date on Form Is
with the sample preparation/extraction and analysis dates on the extraction and.run logs
(Forms 13 and 14, respectively).
1M-1-INORO
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Procedure No.: 1M-1-INORG
Revision: 2
Date: 06/30/95
Page: 9 of 24
Contractual Holding Time (days) = Analysis Date - Receipt Date
2.4.4 Action
The following actions are required only for the violations of the technical holding times. If
contractual holding times are exceeded, then the TPO must be notified of the violation.
1. If 40 CFR 136 criteria for technical holding times and preservation are not met,
qualify all results > Instrument Detection Limit (DDL) as biased low (L) and the
results < IDL as estimated detection limits biased low (UL).
2. If holding times are exceeded by two times (2X) the criteria for mercury and
cyanide, qualify the non-detected results (results < IDL) as unusable (R).
3. If there are gross violations of the holding times for the metals, use professional
judgment to determine the reliability of the data. A low bias would be expected for
significantly longer holding times, and the reviewer may reject the non-detected
data (results < IDL) as unusable (R).
.. v ''' ' "'..'
4. Although the technical holding times for soil samples have not been established,
apply the water holding, time criteria to the soil samples. If the soil sample data are
qualified using the water holding time criteria, this must be clearly "documented in
the narrative report.
2.5 CALIBRATION
Requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable quantitative data. Initial calibration
demonstrates that the instrument is capable of acceptable performance at the beginning of
the analysis run, and continuing calibration verification documents that the initial
calibration is still valid.
Standards at concentrations near the lower limit of detection are also required to be run to
determine the linearity of the instrument.
2.5.1 Acceptance Criteria
1. Initial Calibration. Instruments must be calibrated daily and each time the
instrument is set up. Specific requirements for each type of analysis are as follows:
ICP Analysis
A blank and at least one standard must be used in establishing the
analytical curve.
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Procedure No.: 1M-1-INORG
Revision: 2
Date: 06/30/95
Page: 10 of 24
Atomic Absorption Analysis (AA)
A blank and at least three standards, one of which must 'be at the
Contract Required Detection limit (CRDL), must be used in
establishing the analytical oirve.
Mercury Analysis ';".: ',*.-'.' '
A blank and at least four standards must be used in establishing the
analytical curve. -.', -'
The correlation coefficient must be ^ 0.995. (This is a technical
.'critmon and not a contractual one;)
Cyanide Analysis
_, , . A blank and at least three standards must be used in establishing the
analytical curve. ; ซ
The correlation coefficient must be ^ 0.995. (This is a technical
criterion and not a contractual one.)
2. Initial and Continuing Calibration Verification flCV and CC\0.
Analysis results must fall within the control limits of 90 to 110 percent
Recovery (%R) of the true value for all analytes except mercury and
cyanide.
Analysis results for mercury must fall within the control limits of 80 to
120%R.
Analysis results for cyanide must fall within the control limits of 85 to
3. CRDL Standards for ICP (CRT) and AA (CRAV
A CRI must be run at a concentration of 2X CRDL, or 2X the IDL,
whichever is greater, for each ICP analyte (except Al,.Ba, Ca, Fe, Mg, Na
and K) at the beginning and end of each sample run or a minimum of twice
per 8 hours.
A CRA must be run at a concentration equal to the CRDL, or the IDL,
whichever is greater, at the beginning of each sample run.
1M-1-INORO
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 11 of 26
The CRDL standard recoveries should be between 90-110% of the "true
values.,
2.5.2 Data Requirements and Retrieval of Data
Forms 1, 2A, 2B arid 14. .
2.5.3 Evaluation Procedure
1. Verify that the instrument was calibrated daily and each time the instrument was set
up using the correct number of standards and blank. ^?>"i- ;
2. Recalculate one or more of the ICV and CCV %R per type of analysis (ICP,
GFAA, etc.) using the following equation and verify that the recalculated value
agrees with the laboratory reported values on Form 2A. Due to possible rounding
discrepancies, allow results to fell within 1 percent of the contract Windows (e.g.,
80 to 111 percent),
%R = Found x 1QO
True
where:
Found = Concentration (in ug/L) of each analyte measured in the analysis of
the ICV or CCV solution v
True = Concentration (in ug/L) of each analyte in the ICV or CCV source
3. Verify from the run log (Form 14) that the CRAs and CRIs were run at the
required frequency.
4. Verify from Form 2B that the CRIs were at 2X CRDL, or 2X IDL, whichever, was
greater, and the CRAs were at the CRDL, or the IDL, whichever was greater.
2.5.4 Action
1. If the minimum number of standards as defined above were not used for initial
calibration, use professional judgment in qualifying the data. However, if the
instrument was not calibrated daily and each time it was set up, qualify the data as
unusable (R). Document the noncompliance with the calibration requirements in the
narrative and document on the EPA Region III Inorganic Regional Data Assessment
Form.
1M-1-INORQ
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2.
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 12 of 26
If the ICV or CCV %R falls; outside the acceptance windowns, using the following
guidelines for qualifying the data.
Percent Recovery (%R)
Metals
90-110
75-8?
>110
<75
Cyanide
85-115
,70-84 '
>115
<70 ::
Mercury
J; 80420
:'^;'65V79';' .
'<ฃ >120 ; ;
3-;<ฅ-:. :
Qualifier
>IDL
None
Vv--L-V:'ซ:>
.-:.-". K ......
'.-' L. /./
IDL as biased low (L), and results < IDL as biased low (UL).
> If the ICVor GGV %R is >110 (metals) or 5;20
: results < IDL are acceptable. Results > IDL should be qualified as biased
high(K). >
If the IGV or CCV %R is <75 percent (medals) or <70j)ercent (CN) or
< 65 percent (Hg), qualify all positive results as unusable (R).
Please be advised, there are no National Functional Guidelines to qualify the data
based on the CRDL analyses; however, EPA Region HI has developed specific
guidance to qualify the data.
If the recovery for the CRI or CRA is >110% and the reported sample
results are >EDL, but < 2X CRDL, qualify the data as biased high (K).
If the recovery for the CRI or CRA is between 50-89%, qualify results >
IDL, but < 2X CRDL as biased low. Qualify results < IDL as biased low
(UL).
If the recovery for an element is <50%, qualify the results > IDL, but <
2X CRDL as biased extremely low (L). Qualify results < IDL as unusable
(R).
1M-1-INORO
-------
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 13 of 26
2.6 BLANKS
Blank results are assessed to determine the existence and magnitude of contamination
problems. The criteria for evaluation of blanks applies to any blank associated with the
samples. If problems with any, blank exist, all data associated with the Case must be
carefully evaluated to determine whether or not there is an inherent
variability in the data for the Case, or if the problem is an isolated occurrence not affecting
. fl * V . - -..-...-' . , ;.'.;&&, .'-,".. ( , .- ' - '
other data. .
2.6.1 Acceptance Criteria
No contaminants should be in the blank(s) at concentrations, > IDL.
2.6'. 2 Data Requirements and Retrieval of Data
.,'"- :- ' - .- . -' "'-. - '.', ,'-;'* '< \*-*?ri* "1*:"^*'' V't; ' - * -
: ' :>-\--ซ--.^>-V1:-:y-':v:'.->^i:-^-v.- - v' : .
Forms land 3. ; .; ;
2.6.3 Evaluation Procedure
' - . \ ' ' - .
,, . - _ , . . .
Review the results reported on the Blank Summary (Form 3) for all blanks. Note that the
instrument blanks serve two purposes: One, to determine any sample -carryover, and
second, to determine the shift in the instrument baseline. It is common that the instrument
baseline may shift upward or downward from the calibration reference point (zero
concentration standard) during a sample run. This shift is not necessarily indicative of any
carryover from the previous sample. Negative blank results are common indicating a shift
in the baseline. Professional judgment should be used when qualifying data based on the
instrument blanks.
2.6.4 Action v
Action in the case of unsuitable blank results depends on the circumstances and origin of
the blank.
Sample results > IDL but < five times the amount in any blank should be
qualified as (B).
' Any blank with a negative result whose absolute value is > CRDL must be
carefully evaluated to determine its effect on the sample data.
Qualify the field blanks in a manner similar to that for samples. A field
blank may not be used to qualify another field blank.
1M-MNORO
-------
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 14 of 26
< i
When multiple field blanks are present in a SDG, use the highest detected
concentration for each analyte in the field and laboratory blanks when
qualifying the sample data.
Note: The blank analyses may not involve the same weights, volumes, or dilution factors
as the associated samples. In particular, soil sample results reported oh Form 1 will not be
on the same basis (units, dilution) as the calibration blank data reported on Form 3.
2.7 ICP INTERFERENCE CHECK SAMPLE ' ; ;t t J
The ICP Interference Check Sample (ICS) verifies the contract laboratory's interelement
and background correction factors. ^
2.7.1 Acceptance Criteria *-'. ^; ' ^y
1. An ICS must be run at the beginning and end of each sample analysis run (or a
minimum of twice per 8-hour working shift, whichever is more frequent).
"' ' ; ". '. ' .../,' '.' . . .' '. '. . '" .=' .V*1*- .;'; : '- .
2. Results for the ICS solution AB analysis must fall within the control limits of ฑ "
20 percent of the true value. ,
2.7.2 Data Requirements and Retrieval of Data
Forms 1 and 4 '-.'"
2.7.3 Evaluation Procedure~ ....
1. Verify at random the reported %Rs for the Solution AB using the true and found
values. Use the following equation:
, ,GS %R m Found-Solution AB x m
True. Solution AB
where:
Found Solution AB = Concentration (in ngfl) of each analyte measured in the
analysis of solution AB v
True'Solution AB = Concentration (in /ug/1) of each analyte in solution AB
i1 . '
2. Check the results with an absolute value > DDL for those analytes which are not
present in the ICS solution.
1M-1-INORO.
-------
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 15 of 26
2.7.4 Action
1. For samples with concentrations of aluminum, calcium, iron, and magnesium which
are comparable to or > their respective levels in the Interference Check Sample:
If the ICS recovery for an element is > 120 percent and the sample results
are < IDL, this data is acceptable for use. .
If the ICS recovery for an element is > 120 percent and the sample results
are > IDL, qualify the affected data as biased high (K).
If the ICS recovery for an element falls between 50 and 79 percent and the
- sample results are > IDL, qualify the affected data as biased low (L).
'. .'"'... ''''-. -v5iN^''' "'"' ''" ''-':' ""*..' .'' .'"' . '' ' '
If sample; results are < IDL, and the ICS recovery for mat analyte falls
within the range of 50 to 79 percent, the possibility of false negatives may
exist. Qualify the data for these samples as detection limits biased low
If ICS recovery results for an element is < 50 percent, qualify results >
IDL as biased low (L)r and results < DDL as unusable (R).
2. ซIf results > IDL are observed for elements which. are not present in the ICS
solution, the possibility of false positives exists. An evaluation of the associated
sample data for the affected elements should be made. For samples with
comparable or higher, levels of interferents.. and., with. analyte concentrations that
approximate those levels found in the ICS (false positives), qualify sample results
> IDL as biased high (K).
3. If negative results are observed for elements that are not present in the EPA ICS
solutions, and their absolute value is > 'IDL, the possibility of false negatives in the
samples may exist. If the absolute value of the negative results is > IDL, an
evaluation of the associated sample data should be made. For samples with
comparable or higher levels of interferents, qualify results for the affected analytes
< IDL as biased low (UL), qualify results for the affected analytes > DDL as
biased low (L).
4. In general, the sample data can be accepted if the concentrations of aluminum,
calcium, iron, and magnesium in the sample are found to be < or equal to their
respective concentrations in the ICS. If these elements are present at concentrations
> the' level in the ICS, or other elements are present at concentrations > the level
in the ICS, or other elements are present in the sample at > 10 mg/L, the reviewer
should investigate the possibility of other interference effects by using the Table
found in the most recent version of the SOW. These analyte concentration
1M-MNORO
-------
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 16 of 26
equivalents presented in the: table should be considered only as estimated values,
since the exact value of any analytical system is instrument specific. Therefore,
estimate the concentration produced by an interfering element. If the estimate is
>2X CRDL and also > 10 percent of the reported concentration of the affected
element, qualify the affected results as biased high (K).
2.8 LABORATORY CONTROL SAMPLE
The laboratory control sample (LCS) serves as a monitor of the overall performance of all
steps in the analysis, including the sample preparation.
2.8.1 Acceptance Criteria
1. All aqueous LCS results, must fall within the control limits of 80 to 120%R, except
Sb and Ag which have no control limits.
2. All solid LCS results must fall within the control limits established by the EPA.
This information is available from EMSL/LV.
2.8.2 Data Requirements and Retrieval of Data
Forms 1 and 7.
2.8.3 Evaluation Procedure
1. Review Form- VII and verify that results fall within the control limits.
2. Randomly verify the reported recoveries on Form VQ using the following equation:
LCS %R - Found x 100
LCS True
where:
LCS Found .= Concentration (in /zg/1 for aqueous; mg/kg for solid) of each
analyte measured in the analysis of LCS solution
LCS True . = Concentration (in /tg/1 for aqueous; mg/kg for solid) of each
analyte in the LCS source
2.8.4 Action
1. Aqueous LCS:
1M-1-INORO
-------
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 17 of 26
If the LCS recovery for any analyte falls within the range of SO to
79 percent, qualify results > IDL as biased low (L). If the LCS recovery is
> 120 percent, qualify results > IDL as biased high (K).
If results are < IDL and the LCS recovery is > 120 percent, the data are
acceptable.
If results are < IDL and LCS recovery Ms within the range of SO to
79 percent, qualify the data for the affected analytes as biased low (UL).
If LCS recovery results are < . 50 percent, qualify results > DDL as biased
low (L), and results < IDL as unusable (R).
2. Solid LCS: .
If the solid LCSlre^oyery^ibr any analyte is below the lower acceptable
control limit, qualify all sample results > IDL as biased low (L). If the
LCS recovery is above the upper control limit, qualify the results > IDL as -
'. biased ' "'' '' "
If the LCS results are lower than the control limits, qualify all sample
results < IDL as detection limits biased low (UL). '
If the LCS results are higher than the control limits and the^ sample results
are < IDL, the data are acceptable.
2.9 DUPLICATE SAMPLE ANALYSIS
Duplicate analyses are used to determine the laboratory precision for each sample matrix.
2.9.1 Acceptance Criteria
1. Samples identified as field blanks cannot be used for duplicate sample analysis.
2. A control limit of ฑ20 percent (35 percent for soil) for the Relative Percent
Difference (RPD) shall be used for sample values >5X CRDL.
3. A control limit of ฑ CRDL (ฑ2X CRDL for soil) shall be used for sample values
< five times CRDL, including the case when only one of the duplicate sample
values is < five times CRDL.
1M-1-INORG
-------
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 18 of 26
2.9.2 Data Requirements and Retrieval of Data
Forms 1 and 6.
2.9.3 Evaluation Procedure
1. ... Review Form 6 and verily that results fall within the control limits.
' ' '
2. Recalculate one or more RPD using the following equation to verify that results
have been correctly reported on Form 6.
where: " ,.--. - - .
S '' First sample value (original) >
D = Second sample value (duplicate)
3. Verify that the field blank was not used for duplicate analysis.
2.9.4 Action
1. If duplicate analysis results for a particular analyte fall outside the appropriate
control windows, qualify results > IDL, for that analyte in all associated samples
of the same matrix as estimated (J), and results < IDL as estimated (UJ).
i
2. If the field blank was used for duplicate analysis, all other QC data must be
carefully checked and professional judgement exercised when evaluating the data.
Document this information on the EPA Region m Inorganic Regional Data
Assessment Form. -
2.10 MATRIX SPIKE SAMPLE ANALYSIS
The matrix spike sample analysis provides information about the effect of each sample
matrix on the digestion and measurement methodology.
2.10.1 Acceptance Criteria
1. Samples identified as field blanks cannot be used for spiked sample analysis.
1M-1-INORO
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 19 of 26
2. Spike recovery (%R) must be within the limits of 75 to 125 percent However,
spike recovery limits do not apply when sample concentration exceeds the spike
concentration by a factor of four or more.
3. If the matrix spike recovery limits are not met and the. sample concentration does
not exceed 4X the spike added, a post-digestion spike must be performed for the
ICP, CN and flame AA analyses. This criteria does not apply 'to silver. The post
digestion spike must be performed at 2X the sample concentration or 2X CRDL,
whichever is greater. :ฃ <%:
2.10.2 Data Requirements and Retrieval of Data
2 J0.3 Evaluation Procedure
1. ' Review .Form 5A and verify that results fall within the specified limitsV _;;.-.
2. Recalculate one or more %R using the following equation to verify that results were
correctly reported on Form 5A.
%R = 125 percent and the reported sample results are < IDL,
the data is acceptable for use.
2. If the spike recovery is > 125 percent and the sample results are > IDL, qualify
the data for these samples as biased high (K).
1M-1-INORO
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Procedure No.: IM-WNORG
Revision: 2
Date: 06/30/95
Page: 20 of 26
3. If the spike recovery is < 75; percent and the sample results are > IDL, qualify the
data for these samples as biased low (L).
4. If the spike recovery .falls within the range of 30 to 74 percent and the sample
results are < IDL, qualify the data for these samples as detection limits biased low
''' ' '
5, If spike recovery results fall < 30 percent and the sample result .are < IDL,
qualify the data for these samples .as unusable (R). If the results are > IDL,
qualify the data as biased extremely low (L).
6. If the field blank was used for matrix spike analysis, all other QC data must be
carefully checked and professional judgement exercised when evaluating the data.
Report this information on the EPA Region HI Inorganic Regional Data Assessment
form. . , '.'. ' . ... -'..:.-; i; . .' .. .
7. If a post-digestion spike ^was not performed when required, or the recoveries fall
outside me matrix spike recover
digestion recovery data are not used for data qualification as acceptable recovery
limits have not been established by the EPA yet.)
.-. \ " -, " ' ( - '*
2.11 FURNACE ATOMIC ABSORPTION QC
Duplicate injections and post-digestion/analytical spikes are required for each element and
sample analyzed by the furnace atomic absorption technique. Additionally, a reanalysis by
the method of standard addition (MSA) is required for samples meeting certain conditions
specified in the most recent version of the SOW. The post-digestion/analytical spike
recoveries for the GFAA metals are reported on Form 14 under the %R column. The
correlation coefficient (r) can be found on Form 8 for samples requiring MSA. The flag
"+" is placed on Form Is for samples and analytes with r <0.995.
2.11.1 Acceptance Criteria
1. The post-digestion/analytical spike recovery for the GFAA metals must be within
85-115%..
3. The correlation coefficient (r) for the samples requiring reanalysis by the MSA must
be 0.995 or better using the ordinary least squares linear regression. (A formula for
linear regression can be found in the SOW, or some computer software applications
have the linear regression function built-in.)
1M-MNORO
-------
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 21 of 26
2.11.2 Data Requirements and Retrieval of Data
Forms 1, 8 and 14.
2.11.3 Evaluation Procedure
1. Evaluate the %Rs from Form 14 for a comparison with the analytical spike
. recovery requirement of 85-115%.
..'.''.'' ~ .
2. Verify by random recalculation that the r values reported on Form 8 are accurate
and equal to or greater than 0.995.
2.11.4 Action
1. If the analytical spike recovery is less than 85%, but greater than 40%, qualify
results > IDL as biased low, (L), and results < IDL as biased low (UL). "
2. If the analytical spike recovery is greater than 115%, qualify results > IDL as
biased high (K), sample results < IDL are acceptable.
3. If the analytical spike recovery is less than 10% and the results are < IDL, the data
should be qualified usable (R). Sample results > IDL should be qualified biased
extrememly low (L). . . --x" -"....
4. If the MSA correlation coefficient is < 0.995, qualify the data as estimated (J).
2.12 ICP SERIAL DILUTION
The serial dilution determines whether significant physical or chemical interferences exist
due to sample matrix.
2.12.1 Evaluation Criteria
If the analyte concentration is sufficiently high (concentration in the original sample is
minimally a factor of 50 above the IDL), an analysis of a 5-fold dilution must agree within
10 percent Difference (%D) of the original results.
2.72.2 Data Requirements and Retrieval of Data
Forms 1 and 9.
1M-1-D4ORG
-------
Procedure No.: M-1-INORG
Revision: 2
Date: 06/30/95
Page: 22 of 26
2.12.3 Evaluation Procedure
1. Recalculate at random the %Ds using die following equation to verify the dilution
analysis results reported on Form 9.
where:
I = Initial sample, result
S = Serial dUutionresult,instrument reading X 5)
2. Determine whether thereof negative interference. Generally ;x a diluted sample
should offer lesser interference; hence, more accurate and higher reported values.
However, it is also possible to obtain lower values for the diluted sample, indicating
a potential for negative interference. The apparent negative mterference may be
related to sample concentrations in the less accurate .regions, of the "IGP
instrumentation i.e., near the IDL or the upper limit of the linear range. Carefully
evaluate if the negative interference is real.
2.12.4 Action
1. Whan the diluted sample results are outside the range of 90-110% of the original
sample result, qualify the associated data as estimated (J).
2. If evidence of negative interference is found, use professional judgement to qualify
the data.
2.13 FIELD DUPLICATES
i
Field duplicate samples may be taken and analyzed as a indication of overall precision.
These analyses measure both field and lab precision; therefore, the results may have more
variability than laboratory duplicates which measure only laboratory performance. It is
also expected that soil duplicate results will have greater variance than water matrices due
to difficulties associated with collection identical field samples.
2.13.1 Acceptance Criteria
ji
There are no review criteria for field duplicate analyses comparability.
-------
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 23 of 26
2.13.2 Data Requirements and Retrieval of Data
Form 1.
2.13.3 Evaluation Procedure
. ;; '^.v.-^i^-.j/.i.-i'i:-,--/.
Samples which are field duplicates should be identified using EPA Sample Traffic Reports
or sample field sheets. The reviewer should compare the results reported for each sample
and calculate the Relative Percent Difference (RPD), if appropriate. V ;::
2.13.4 Action
Any evaluation of the field duplicates should be provided with the narrative report. At the
reviewer's discretion, a table listing the RPDs between the original and.the duplicate
samples may be prepared.
2.14 REPORTING LIMIT VERIFICATION r
Reporting limit verification is performed to verify that the CRDLs were met; to ensure that
the reported quantitation results were accurate, and to ensure that the ICP data were not
reported beyond the upper linear range of the instrument.
The positive results themselves are not verified for accuracy, as this would require the use
of raw data. However, the undetected values are checked for proper application of dilution
factors and moisture content normalization. Indirectly, a check on the reporting limits
would suggest that the sample results have been properly adjusted for the dilution factors
and moisture content.
2.14.1 Acceptance Criteria
Minimally, the laboratory should meet the basic CRDLs specified in the most recent
version of SOW. This implies that the laboratory's IDLs must be equal to or less than the
CRDLs. The laboratory has a choice of using the ICP or AA instrumentation for analyses
of metals; however, the sample results for As, Pb, Se and Tl must be greater than 5X HDL.
Otherwise, AA instrumentation must be used.
ICP data must not be reported beyond the established linear range without sample dilution.
The linear range for each ICP metal is established on a quarterly basis.
-------
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 24 of 26
I!
Furthermore, the dilution factor and moisture content correction, must be made to the
sample results, as applicable. This may apparently raise the reporting limit above the
CRDLs for some analytes.
. V i .
2.14.2 Data Requirements and Retrieval of Data
Forms 1, 10 and 12. .
2.14.3 Evaluation Procedure
1. Verify from Form 10 that the IDLs reported for each analyte and instrument meet
the CRDLs at a minimum. There may be several Form 10s for the ICP, AA, Hg
and CN analytes. ,.'../. :
ป , ' r~ '-..."'';-" - - ' - . "*'"_
2.. Verify mat the linear ranges for the ICP metals are reported on Form 12, and no
undiluted sample data are reported above the linear ranges. ~ '
3. Verify on the Form Is that the CRDLs have been adjusted for any dilution factors.
and moisture content, as applicable. . '.-,.'.-.
4. Verify that the sample results are >SX ICP IDL, if ICP analysis results are used
for As, H, Se] or Pb.
2.14.4 Action
!' '
If there are any discrepancies found, the laboratory may be contacted by the designated
representative to obtain additional information that could resolve any differences. If a
discrepancy remains unresolved, the reviewer may determine qualification of the data is
warranted.
2.15 SAMPLE IปAPERWORK
The purpose for evaluating the sample paperwork is to determine that the samples being
validated are indeed the ones taken from the site, and have not been tampered with.
Accurate sample identity is of paramount importance in substantiating the sample data.
Without unequivocal sample identity and chain-of-custody procedures, the sample data may
not be defensible or enforceable.
i
Under the current CLP contracts, the original paperwork (i.e., the purge package or the
administrative recdrd) is included in the data package from the laboratory. It is assumed
that the data validator is not privy to the original paperwork; therefore, the evaluation
criteria and procedures described below apply only to the documents that are generally
1M-1-INORO
-------
Procedure No.: IM-MNORG
Revision: 2
Date: 06/30/95
Page: 25 of 26
included in the data validation package. These documents are the chain-of-custody forms
and Region m Shipping Record.
2.25.1 Acceptance Criteria
Criteria for acceptability or authenticity of the sampling paperwork, document control and
chain-of-custody have been established, by the National Enforcement Investigations Crater
(NEIC), to support the CLP. Overall criteria are too numerous and subjective to be
discussed here, but the criteria that apply to data validation are:
The chain-of-custody form should be properly and completely filled out
including the sampler signatures, date and time of sampling, sampling station
identification, analyses requested, traffic numbers,tag numbers, etc. These
data are minimally required to confirm the authenticity of the sample and its
.data,- . ;-'::CV/^.:; '''..' "' ' .' ". :-:(y . : ' .
The chain-of-custody must be maintained at all times., The custody, transfers
between different parties must be signed and dated.
2.15.2 Data Requirements and Retrieval of Data
A copy of the chain-of-custody form is essential to confirm the identity of the samples.
The Region m Shipping Record is required to identify the field QC samples. The chain-
of-custody form and Shipping Record are generally located in front of the data package.
2.75.3 Evaluation Procedure
Ensure that the chain-of-custody form was signed and dated by the samplers, and a time
and date were entered for sample collection. The laboratory copy of the chain-of-custody
must have the signature of the laboratory sample custodian. Any errors on the form should
have been crossed out with a single line through the entry. Verify that all collected
samples have unique station identification, traffic numbers and sample tag numbers.
Ensure that the Region HI Shipping Record correctly reflects the information on the chain-
of-custody.
2.15.4 Action
The action to be taken in qualifying the data is highly dependent on the nature of the
problem. Some errors in paperwork are practically unavoidable in real situations. An
effort should be made to reconcile the differences by cross checking the field notebooks
against the sampling paperwork. Occasionally, the samplers may forget to sign the chain-
of-custody; however, the field notebooks may amply describe the sampling event.
Problems are also inevitable in noting or cross-referencing sample tag numbers and traffic
1M-1-INORO
-------
Procedure No.: IM-1-INORG
Revision: 2
Date: 06730/95
Page: 26 of 26
numbers. Generally, there are several alternate sources of information to substantiate or
refute the problem.
Any discrepancies found in the paperwork must be immediately brought to the attention of
the EPA RPM or SPO. Clearly define the problems in a memorandum to the responsible
parties. Attach marked copies of the chain-of-custody forms to substantiate the findings.
1M-1-INORO
-------
Case No.; .
SDG No.:Z
Data Reviewer/Date:,
Site:- --1 :.' :--' >'S'.
Procedure No.: 1M-1-INORG
Revision: 2
Date: 06/30/1995
"'"-':-' r - ' '
Sample
Hg (28 Days)
CN (14 Days)
Number
Date
Coll.
Date
Reed.
Lab.-
ปS
: Days
Qual.
Date
Prep.
Anal.
Hold.
Time,
Days
Qual.
Date
Prep.
Anal.
Hold.
Time,
Days
Qual.
II
//*
1 1
77-
II
11 -
/ A
7 /
1 /
/ 7 :-
:/'
//
/ /
/ /
* -.
-------
Case No.:.
SDG No.:
Data Reviewer/Date:.
Site:
Procedure No.: IM-1-INORG
Revision: 2
__ Date: 06/30/1995
Table Dt-1-INORG-CAL. TAL Metals and Cyanide Calibration and Blank Qualifier Summary
ICP Instrument ID:
Instrument Calibrated? __Yes _Nb
ICP Date Started:
ICP Date Ended.'
AA Instrument IDs: As P
Instruments Calibrated?
AA Date Started: ' . v
AA Date Ended: ';.
Analyte (Criteria)
Aluftiiinifii Al *
-Antimony , Sb
Arsenic . ' >'.As
Barium Ba
Beryllium Be
Cadmium Cd
Calcium Ca
Chromium Cr
Cobalt Co
Copper Cu
Iron Fe
Lead Pb
Magnesium Mg
Manganese Mn
Mercury . Hg
Nickel Ni
Potassium K
Selenium Se
Silver Ag
Sodium Na
Thallium Tl
Vanadium V
Zinc Zn
Cyanide CN
,V ".'.' "' '' ." '^f'-"'.
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1. ,
2. .' A ' ' . '
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,:4i%^fe;:'. '.. ; ' : . '.; -. -.
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AgJWf>r-.V.-. ;
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:% :-'.,
Qual.
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18. ;:' '- ..- ' .
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Qual.
^
The ICV and CCV criteria: He = 80-120% R, CN = 85-1 15% R.
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Uase No.:.
SDG No.: ~
Data Reviewer/Date:.
Site:
/
Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/1995
Table IM-1-INORG-SPK. TAL Metals and Cyanide Matrix Spike, Duplicate and ICP Serial Dilution Qualily Control Summary
Analyte
(Criteria):
Alnabnm AI
*afiซr.Wป~
jiaa&&$&
jtarhim-^Ba-'
BerfOhan - : fie
Cadmium ' '.Cd
ciiM^t*."
'titaoUn^Ck'-
:0*il$fฃcoV
Copper >--< 'Ob
'tiriB^v'W*;
Lead."-:.''- :"''."Po
Majmeffam ME
MangBncff Mn
Mercury. HE
N34yป/ ' N! '
Potassium ' 1C
Selenium Se
Silver Ag
Sodium Na
Thallium Tl
Vanadium V
Zinc Zn
Cyanide ' CN
Matrix Spike/Duplicate
Rec,%R
75-125
...
' >
i ": ; '
-. : -''.
. ' :
'; ; .:. .'''"
'. , '" .".-.
"o. :':"'.''
; .i ' " . ' '
' ;-'- ,'...'
-
RPD
25(35)ป
'''" .'-. ''
'.""'uh-:
.: ;..'
~. *' . :
/:::,;,
;;..-.;..,..::;.
''./.:'.,:.;'.
' " " ";. - '.'
- ; :: '';-.'''
.' ";'' ' '
_ '- . ._
Qualc,
".', v ' . -
H^|^::
;;sf^'^.
;W*&
:?^g^i
'.'^'S??*?'"'-"
;g^^:
".ป-*: ->",^ "- -..' ;'
/r-.^pf"
v.';^*;;v.
.:-".:ป
. " - .
' .
'
ICPSer. Dil. .
+/-1096
' .'-'' ''
-ฃ^-." '
"l^"^-"-
r^^v ..;
~-:^/'<:-'
fe;^:r- '
^^tB::',:;
i^v-y -;
--. ~. '**--. .
"!' '. 7'* -?Hi' .- -; .
: ._ .-'. -.. .""
Quals.
'_ ..
f.jฃ
Post Digest/Anal. Spike*,
ICP
75-125%
'r *'
- . -
AA
85-115%
' ;. :.
:' ' ' '^
'..-.- .."'ii
' :' -:v'-
.'.' ' '":"
;.
- . . V.
.., . .:.^-iซ.
" ' ' '.
Quals.
. jtii ' :iX:.',*>-t':
$$%$!$:
^SS
"Si^v
'^f^
-' *-* '.- - -'
' :'.'.-"'''J-.-:-:
- """ "^-Z..
''-^^'
LCSRecoverv
80-120%-
: ?:,-; .
$$&&ฃ
H^':V:"'
r?is^--.-
:^r-;v
iR'-'v-
^fe:v,
^t^:^ ::;
S^P.V :t\
''i&?--'" '.:
**-iV'!'i. '".
.:...: '
' ' ' . . *
.
t
'
Quals.
1
l'>'V;:-
'': ^.''
.: *
- '-. r . ' .
:'-': . - ' :
.'. "."." SJr>"
' "v
. Note: See the SOP for the exact criteria under special situations.
TThere are no criteria at the present time to qualify the ICP metals or Cyanide based on the post-digestion spike recoveries.
* The precision RPD for soil samples is 35. . '
'ffhe-range of 80-120% R is used only for the aqueous LCSs. Solid LCS samples have specific recovery ranges for each analyte.
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Case No.:.
SDG No.:
Data Reviewer/Date:.
Site:
Procedure No.: Hf-1-IHORG
Revision: 2
Date: 06/30/1995
Table IM-1-INORG-<|L. Summary of Data Qualifiers ,
Sample
Number
- --. - _-. ,_
Analyte i .
Al
-
Sb
As
Ba
-
Be
Cd
-
Ca
'. .
Cr
"l
(
\
Co
-
/
. *
Cu
, .-
. ' ; '''/
' -ill-
Fe
, w .
<' ,*'
*Jf
;.r; :.-.'. \-:-
*
-.. ..
':'.' ;v.
. .
i ' '
. .
.Pb
-
'&
:iOj-
.^-..C?*ii>i
VW0^
; ';,:..''!;
i .
._'
. . t >:' '
' :-:d-':-
' ซ )
t
\
;Mg.
' *.
*=- ,-'
:,V-'4t
.j!,v,.'V^:O
^
Wf&
tftx-
"
'f?&
""* .-. ., '
'.
Mn
,'-.--''.
ป f.'*
it-vSV-f.
iH
IP
1ฎ
:>'";
v.'V'^'-''
!f^;
''. tv.-'
Hg
'"":" .
^;v
^-.A'!*-
iK
K>XHW.
^
IK
h."
'ป.
N.
-
vV?.";!:'.
utr. .'.'-'::
s*T.ซcs ;
^^:
:*irt*-
^y'4''
-
Ni
; . . t
V,'."'.V.-"
i/vte
^^K
ซ
t?.^f-
t^;
:'.-'.. K
.-.
'A-"":{'
.if.;-:;''
K
,-.'.. -i.
^
ijjj^
^
i;=j-'*ii
';1;SJ;y
. " .-.
' ;'-U
...t1-*
.' '.<<'"&
-. 4' - *>
-'. .-Iv'-V.
T ' '
,Se
>
'v *...' ;
;.v-'-.'--
^
SI
^
v?>3;ฃ'-
*
.".. '.
:i- 1:5>'
-.- .. -. 5-
k**'.'*;
;*ฃ*)-
f^-s-1'
;..-."}
' '
Ag
- ' -
'<-*'.' " .
.".' : .
-it : '/
*%* :
\' -'
_;!:X. ''.
-.
',? ..
*.
Na
ซ
Tl
V
t .
Zn
-
it
CN
-------
Case No.:_
SDG No.:"
Data Reviewer/Date:,
Site:
rocedure No: IM-1-INORG
Revision: 2
Date: 06/30/1995
Table IM-1-INORG-IRDA
EPA Region m
Inorganic Regional Data Assessment
Case No.
Site
Laboratory
SDG No. _
SOW No.
IPO: Action
FYI.
Number of Samples/Matrix.
Reviewer (if not CRL)
Reviewer's Name .
. Completion Date .
Holding Times
Calibrations .. '
ds
Data Assessment Summary
ICP . AA
Cyanide
Duplicate Analysis
Matrix Spike .
Post Digestion/Analytical Spike
MSA
Serial Dilution
Held Duplicates .
. Reporting Limit Verification
Sample Paperwork
o =
M =
Z =
X =
Action Items:
Data had no problems/or qualified due to minor problems.
Data qualified due to major problems.
Data unacceptable.
Problems, but do not affect data.
Areas of Concern:
Notable Performance:
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