INNOVATIVE APPROACHES TO DATA
VALIDATION
UNITED STATES ENVIRONMENTAL
PROTECTION AGENCY
REGION III
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
0) organic review procedures (M-i, 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 leyeipresented in this document. The "levels " ^ 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 levds are described in detail in this document. The
SOPs describing how to apply these levds to a data-package are in Appendices A through D.
All procedures require full CLP or CLP equivalent data package, deliverables:.
In general, organic Levd 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 fidd or laboratory-induced contamination. If the
answer is negative, thai 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, thai the emphasis is shifted accordingly to an evaluation
of data qiuriity parameters, false negatives, and detection limits (Level M-2 or IM-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 levd 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 (SOFs)
A. Validation of Volatile Organic Analyte Data (Levels Ml and MQ)
A-l. Manual Levd Ml (for VOAs)
1. Purpose and Applicability .... . . 1
2. Quality Control Measures Checked — ............. 1
3. Procedure. •. •. ,..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 RetentionTimes . . . ................... 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 VOA 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
Tablfes
M2-VOA-1 QC Checklist for Level M2 CLP RAS Volatile Organics .......... .2
M2-VOA-2 VOA Qualifier Summary .. . . . . . . . . . ......... .« .' >> . •. . 5
M2-VOA-3 VOA Surrogate and Matrix Spike Quality Control Summary. /. . * . . . . 6
M2-VOA-4 Volatile Organic Analytes and Action Levels . . .. . ... . .9
M2-VOA-5 Qualification of Volatile Analytes Based on Technical Holding Times /.ll
M2-VOA-6 Qualification of Volatile Analytes Based on System Monitoring
Compound Recoveries ....................... 27
B. Validation of Semivolatile Data (Levels MTand AO)
B-l. Manual Level Ml (for SVOAs)
1. Purpose and Applicability .... . -1
2. Quality Control Measures Checked . . ... .. . . ^ . . 1
3. Procedure V... .. ; . . v . . . .. . . .1
3.1 . Action Level Notification .. . ... . . 3
3.2 Evaluation of Mass Spectra for Detected
Compounds .5
3.3 Evaluation of Chromatograros .............. • . 9
3.4 Evaluation of Reteition Times . . . ... ................ 15
3.5 Evaluation of Blanks 16
3.6 Sample Paperwork . . ...... 17
Tables
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 SVOAs)
1. Purpose and Applicability 1
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 . . j 20
3.6 Blanks . . . . , 22
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CONTENTS (Continued)
Page
M2-SVOA-1
M2-SVOA-2
M2-SVOA-3
M2-SVOA-4
M2-SVOA-5
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 37
Tables
QC Checklist ^irlevel M2
SVOA Qualifier Summary ............. .... . 5
SVOA Surrogate and Matrix Spike QC Summary . . . V.\ 7
Semivolatile Action Levels .... 10
Qualification of Semivolatiles Based on Surrogate Recoveries . , . . . . . 31
C. Validation of Pesticide/PCB Data (Levels Ml and M2)
C-l. Manual Levd Ml (for Pesticides/PCBs)
1. Purpose and Applicability .... . . .
2. Quality Control Measures Checked . .
3. Ploccdure . .. . ... . •.• . . •
3.1 Action Levd Notification
3.2 Evaluation of Retention Times
3.3 Evaluation of Chromatograms ,
3.4 Evaluation of Blanks
3.5 Sample Paperwork .......
Tables
Checklist for Level Ml PEST/PCB
PEST/PCB Action Levels. ......
M1-PEST4
Ml-PEST-2
Ml-PEST-3
Ml-PEST-4
.2
........ ... 4
PEST/PCB Retention Time for Windows 8
PEST/PCB Retention Time for Evaluation Summary. 9
• • • ¦
.1
.1
.1
.3
.5
.7
14
19
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)
Page
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/PCBQualifierSummary.. . . ...... . . . .5
M2-PEST-3 PEST^^^^hmiinaty .. v.. .....••.. ... .6
M2-PEST-4 PEST/PCBActionLevel. . ........ . 8
Attachment to Appendix C-2
D. Validation of Analyte Data (Level Ml)
1. Purpose andAppUrability . .. . 1
2. Quattty Control Measures Checked ..... ;..................... . 2
2.1- Proceduies • * * *¦* • •. • • • .*. .. ... . .2
2.2 RegmrtingRequirements ... .4
2.3 Action -Level Notification . ......,......... .... . 6
2.4 Holding Times .................................8
2.5 Calibration ....... . ..... . ............... .9
2.6 Blanks .. . .... ........... 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 Spite 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 . . . . •. . 1 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 (back)
IM-1-INORG-SPK. Summary of Spike Recovery/Duplicate Precision ................ (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 percent difference
%R percent recovery of spiked amounts of analytes
AA atomic absorption .
AOB analytical operationsbranch ¦>
APO administr^Veprqjectbfficer,
BPB BromofluorobenzeneYvolatileinstrumentperfarmancex^^
BNA basefaeutral/ac^f^^^ 5.:^s,.:.•; -•'••" *wv~~
CADRE computer ud^ dai^revi^'and evaluation
CARD CLP analytical ri^ts database -
CCB continuing calibration blank r^;v.
CCS contract compliance screwing ! }V:
CCV continuingcali^^
CF caHbradonfec^:^^^^^ ^
CLP contract labonto^ .^gia^a 5
CLP RAS contract l^orate^i^gram^routme a^ytical'sera^S'
CRDL contract required d6^ ' " ' ? >: ^ ^
CRQL computer required quantitation limit
CSF complete SDG file
CV Coefficient of Variation
DAS delivery of analytical services .
DFTPP Decafluorotriphenylphosphine (semivolatile instrumentperformance
check)
DPO deputy project officer
DQOs data quality objectives
DV data validation
ECD electron-capture detector
EICP extracted ion current profile
EMSL-LV Environmental Monitoring Support Laboratory-Las Vegas
EPA United States Environmental Protection Agency
GC gas chromatography
GC/EC gas chromatography/electron capture
GC/MS gas chromatography/mass spectra
GPC gel Permeation Chromatography
HAZRAP Hazardous Waste Remedial Actions Program
ICB initial calibration blank
ICP inductively coupled plasma
ICS interface check sample
ICV initial calibration verification
IDL instrument detection limits,
IRDA Inorganic Regional Data Assessment
IS internal standards
LCS library control sample
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MCL
ml
MS/MSD
MSA
m/z
NEESA
NEST
OADS
ORDA
PB
PC
PCB
PEST/PGB
PEP
QA/QC
QAQP
QG
QL
QN
RAS
RIC
RI/FS
RPD
RPM
RRF
RRT
RSD
RT
SAS
SDG
SMC
SMO
SOP
SOW
SVOA
TAL
TCL
TIC
TPH
TPO
VOA
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 jand Environmental Support Activity
National Institute of Standards and Technology
organic analysisdatasheet (Form I)
suiMce/qiMLlity control
tyassunmcef
routine ao^^^^moes
• v -Jiv.v-jrLi. •.
remedialmvestiganon/feasibility
relative response factor
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 absoibance versus concentration of standards.
Case
A finite,
collected over a given time period for a particular site.
A Case consists of oneor more Sample Delivery
Group(s).
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Appendix A
Validation of Volatile Organic Analyte Data
• Subappendix A-l covers 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. JPwpOsepd 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 Levd Ml;
|£he procedure is applicable using|i^|C^^
Stat^rat of Work (Ct^Sp^^iHs^copy data confo^^g^ the CLP SOW
^specifications are essential in ord^|b csui}^but the procedure. '
.Data validated using this procedure are . considered usable fen: the following types of
purposes; however* the data us^ >must;>:dedde oh a case-by-case bads whether the
procedure is suitable ;for their intended dak 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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1 • Table Ml-VOA-1
'
QC CHECKLIST FOR LEVEL Ml
| CLP RAS VOLATILE ORGANICS
Manual
QCMEASDSES
BO
M3
Actum LevelNotification^
¦¦¦ r i
t x
Instrument Tune
X
Initial Calibration(RRF)'' ..
^ ; x
Initial Calibration (%RSD)^
X
&.• :;X •
Continuing Calibr&an(R]$!)t
' x,
Continuing Calibration(96D)
7 x
Laboratory Blank
1 * J
x
MS/MSD (%R, RPD)V
. V .
x
x
Internal Standard Area '
. X
X
Field Blank
HH
x 7
: x
Sample Paperwork
x
X
Holding Time
1 x
X
Retention Time
1 x 1
X
X
Surrogate Recovery
X
X
Dilution Factor
X
X
Moisture Content
X
Mass Spectra
1 X 1
/
X
Chromatograms
I x 1
¦ x
I i
X
Raw Data
X
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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. 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-VOA-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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EPA RPM or SPO
EPA Section Chiefs:
— Site Investigation (SI)
— Remedial
— Enforcement
— RCRA
EPA Section Toxicologists: -^
¦ Enforcement
— Superfund
RCRA
The renaming 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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" Table Ml-VOA-2
VOLATILE ORGANIC ANALYTES AND ACTION LEVELS
Compound
Action
Level*
Compound
Action
Level*
Benzene
233 '
Carbon tetrachloride
160
Chlorobenzene
; 1,800
l,24)icM(nx>ethane
¦ 740
1,1-Dichloroethylene
1,000
cis-1,2-Dichloroethylene
1,000
trans-1,2-
Dichloroethylene
2-720
Dichloromethane v
(methylene chloride) .
1,500
1,2-Dichloropropane ;
90
Effiylbenzene
-2,100
Methylethyl ketone
(MEK, 2-butanone)
7,500
Styrene
20,000
Tetrachloroethylene
34,000
Toluene
6,000
1,1,1-Trichloroethane .
35,000
Vinyl chloride
2,600
Xylenes
7,800
—
~All units are ug/1.
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. Hie 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-VOA-2.
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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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 Detected Compoundst
The primary QC indicate Checked in Level Ml is the mass spectra for the detected
compounds. This indic^ pertains to evaluating a compound's presence by matching its
•mass spectrum with a st^d^ (kndwn) mass spectrum for the omipound.>;N6'assessm«it
is made of the reported quantity; of the compound or any quantitative quality control
indicators that could laid some uncertainty to the reported value.
3.2.1 Acceptance Criteria;
The acceptance criteria ifor mass spectral matching axe 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.
• 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 in 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 (knowfi) 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 helpftd 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. Hie raw data
should then be tagged for every sample for evaluating the mass spectra and the
chromatograms (reconstructed ioik 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-, -CI, -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 b^lj^roupdrsubtraciedi sample
spectrum for the presence of the base, parent and other characteristic ions. Although
background-subtracted and unaltered mass spectra are generally provided, |he 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 betweenrthestandardand the
sample spectra can be considered satisfactory. The comparison is ratfier 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 taigetcompound and the interfering compounds can be quite
different. Inseparable isomers reflect a limitation of the gas chromatography 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 Guidelineswhichrecommend 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
i^ected. 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 fdr%rany%uiposes such as risk assessment therefore, rejection of
data is notbeneficial to a project The conflict of improper characterization should be
brought up and rectifiedv^^ tiie^aborato^.)
If there is some evidence of thecompound's presence (as determined by visual matching of
the base ion, parent ion and fingerprint pattern despite a poor fit score), the compound
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 upon a data validator to make appropriate recommendations to the project
manager or the remedial officer.
3 2.5 Reporting
The most convenient form of reporting the mass spectral evaluation is through a brief
memorandum to appropriate authorities. The highlighted Form Ts and the mass spectra in
question should be appended to the memorandum in support of the conclusions. Also fill
out and attach the Mass Spectral Evaluation Form, as depicted in Table Ml-VOA-3, to the
report as a record of what was done. Record the date(s) of analyses. Field sample
numbers should be transcribed 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:
X—Acceptable mass spectrum.
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Procedure no.: Ml-VOA
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Date: 06/30/1995
Page 10 of 18
• N—Tentative identification. Partial proof of a compound's presence, but all
identification criteria not met,
• U—No mass spectral match. Using professional judgment, the compound is
considered undetected.
• R—No mass spectral match. Using professional judgment, the . compound
data are rgected 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 analyticalerrors. Checking for positive data as described under mass
spectraTeyaluation does not :o£fer any insight into-dafca that, are not reported (Lp.* reported •
as nondetects). laboratory error gross interference from other compounds could be the
reasons for erroneous repotting. . The gas chromatograms or the reconstructed ion current
(RIC) profiles are the primary tods used for the false negative evaluation under Levd Ml.
3.5.1 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 HCs. 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.
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Case No.:__ Procedure No,: Ml-VOA
SDG No.: Revision: 1
Data Reviewer - ¦ Date: 06/30/1995
Site:_ ' Page 11 of 18
Table Ml-VOA-3
VOA MASS SPECTRAL EVALUATION SUMMARY
Dates Analyzed:
Sample THwirifipr;
; Comments on rhramntovnim
1
1
T
7 " _ .....
* ¦ -
* ¦ ¦ ¦ ' '
Indnmifri ID?
«
a
•t. "¦ •'
7
.
•?- V "
* '¦ : ' " '' r
O ' "
9.
• : \ ¦
!
¦ ¦
• ••••
v' -
*
10
. V
.. ;>
-.*• • "7'
' Sample Identifier
;
¦v-
I
:/ • 2"" '
MS
s
-4"
1- ~
6
7 •;
9
10
MS
RT
MS
ST
MS
RT
MS
RT
RT
MS
RT
MS
RT
MS
RT
MS
RT
MS
RT
CUofometfaane
<*)
•y *'..
- '
••V- .
Bromome&ane '" • •
•
...v"
'••••-'vv.
» •
Vmvl Chloride
:
Chloroe&aoe
• s
*• .
'• -
Methylene Chloride
.....
Acetone
.
Carbon Disulfide ; '
i .
'1
1,1-Dichloroethene
o
1,1-Dichloroethanc
• *
1,2-Dichloroethene (total)
Chloroform
<*>
-
1,2-Dichloroethane
2-Butanone
1,1,1-TrichIoroe thane
Carbon Tetrachloride
Bromodichloromethane
1,2-Dichloropropane
(*>
cis-1,3-Dichloropropene
Trichloroethene
Dibromochloromethane
1,1,2-TrichIoroethane
Benzene
AR
trans-1,3-Dichloropropene
Bromoform
(fl
4-Methyl-2-Pentanone
1
2-Hexanone
Tetrachloroethene
\
.
1,1,2,2-Tetrachloroethane (#)
Toluene (*)(AR)
Chlorobenzene (<0(AR)
Hthylbenzene (»)(AR)
Styrene
(AR)
Xylenes (total)
(AR)
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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 Chrpmitiograms
Visually inspect the chromai^rams for. all peaks that appear to be at least' 10 percent in
height of the nearest intraiial standard. Compare that the scan number 6r the retention time
that appears on the *-axi$~of tJieRIC profile with that listed on the quantitation report for
the TCLs or &e Ubr^ search record for the TTCs. 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 ispmeric or homologous compounds are difficult to separate. But generally, there *
should be at 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 standardsand 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.
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
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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 n(M-TC^4^^^Q peak with an
area equal to or ^greater than 10 percent area of tfaeMi^^1|nternal standard
must also be i^olyed ^with thelaboratory. TICs ^tluleM than lO percent
area are not required to be reported according to th^^f-RAS protocols.
In the event, the "discrepancy cannot be resolved Wiethe laboratory, the
problems should be documented and brought to ihe attention of, the CLP-
TPO, thie RI^ and theSM. Hie data for unrepOTb^;^CL TICs may be
considra^ uniis^le until the problems are resolved^
• If a peak resolution problem is evident for the sampl^ and iappears to be
systematic (i/e., /present in all calibration samples, QC-samples, and field
samples and increasing as the run progresses), additionalQC measures such
as tile continuing
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Procedure no.: Ml-VOA
Revision: 1
Date: 06/30/1995
Page 14 of 18
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 bd;ltfp^gh^to the attention of the laboratory for a corrective action.
J^fessicM^udgmsat should be used when and if qualifying any data due to
iin!^mmetrieaks.First the problem should be defined in terms of
persistim^Jb^py^hout the chromatogram and also from sample to sample.
Additio^^jffie^^pes and area counts for the internal and surrogate
.standgr^^ to see if the problem could have affected
<»mp6^^|^ectipn and/or quantification. Data qualification may be
unraUei^^i^standard^area counts are acceptable.
33.5 Reporting
The Mass Spectral By^v^d(^i;$Fpnn (Table Ml-VOA-3) presented earlier may be used to *
note any brief comments'on thechromatographic evaluations. The comments may be noted
against each sample idoitifier.v For more descriptive commits, 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.
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.
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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 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.
• 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.
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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.
3.5.1 Acceptance Criteria
Criteria for blank evaluation iare specified in the EPA's functional guidelines. In addition,
Region in 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-of bottle blanks, and laboratory method
blanks. While there are several criteria for evaluating the blanks, the only criterion
applicable to Levd Ml i$ the comparison of the blank and sample concentrations. This
criterion is:
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.
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Procedure no.: Ml-VOA
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Date: 06/30/1995
Page 17 of 18
3.54 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 in data validation guidelines.
3.5.5 Reporting
Form I's may be used to write die "B" data qualifier for the data not meseting 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 ftfaie 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 m 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 chairi-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.
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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
Ensure that the chain-ofrcustody form was signed and dated by the samplers, and a time
and date wefe altered forsamplecollection. The laboratory copy of the chain-of-custody
must have the signature of (he laboratory sample custodian. Any errors on the form should
have befen 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 SKippmgRecord correefly reflects the information on the chain-
of-custody.
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
oarties. Attach marked copies of the chain-of-custody forms to substantiate the findings.
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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
l.Purpose and Applicability
This procedure provides step-by^stcp instructions to manually vaUda&1heVolatUe organic
analyte (VOA) data using the manwd innovative data validation approach.at Ixvel M2.
This approach focuses on the use of information contained on the CLP formsand a. review
of chromatograms as summarized in Table M2-VOA-1. The procures are based on
modifications to Regions.iniYNational Functional Guidelines for QrganicDataReView.
Tiie procedure is appncaDie to tne vuA aata optamea using tne contract uatxnatory
Program Statement of Work (GLPSOW). Hard copy data conforming to Ihe CLP SOW
specifications are essential in ordertp carry out the procedure. 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 investigatior
• 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-VOA
Revision No.: 1
Date: 06/30/1995
Page 2 of 34
Table M2-YOA-1
QC CHECKLIST FOR LEVEL M2
CLP RAS VOLATILE ORGANICS
QCMEASDRES
Action Level Notification
Instrument Tune
Initial Calibration (RRF)
Initial Calibration (%RSD)
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
ill
M3
X
X
Combined
CI
X
X
C2
x
C3
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Procedure No.: M2-VOA
Revision: 1
Date: 06/30/1995
Page 3 of 34 -
2. Qualify Control Measures Checked
Table M2-VOA-1 highlights the quality control (QC) indicators evaluated under this data
validation procedure.
3. Procedure
The following subsec^ons deso^Tor each of the QC indicators the acceptance criteria, -
data requirements and ietri^yailofQC data, evaluation of the QC data, actions taken in the
event the QC acceptance Mt«^ lure exceeded, and documentation of the QC violations in
a standardized report form..
The volatile data requiremoits\to be xhebked are listed below:
3.1 Action Level Notification
3.2 Technical Holding Tiines (CCS - Contractual holding times only)
- 1 •
3.3 GC/MS Instrument Performance Check (CCS)
3.4 Initial Calibration.(CCS)
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)
i
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.
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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
Data validation qualifiers
Sample identification number
Saioqilii^lpba^
• Provide a narrativethat includes
A statementthat defines the levelof the data reyieWj ie.. M2
Jtojorandrrimor problems associated with the analysis
Highlight issues that may have affected detection limits!
• Include thefoUom^attachments
list *>£3ai£vatidation qualifiers
Supiraf documentation including forms that support assigning data
qualifiers .X'
Chain of custody form
Samples affected by calibration should be listed oh the appropriate
calibration &
The data qualifiers assigned in this review are as follows:
Codes Relation io Identification (Confidence concerning presence or absence of
compounds)
U =
(NO CODE) =
B
R
N
Not detected. Th& associated number indicates approximate sample
concentration necessary to be detected.
Confirmed identification.
Not detected substantially above the level reported in laboratory or
field blanks.
Unreliable result. Analyte may or may not be present in the sample.
Supporting data necessary to confirm result.
Tentative identification. Consider present. Special methods may be
needed to confirm its presence or absence in fiiture sampling efforts.
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case No.:
SDGNo.:.
Data Reviewer:
Site: .
Procedure No.: M2-VOA
Revision: 1
Date: 06/30/1995
Page 5 of 34
.Table MZ-VOA-2. VOA Qualifier Smnmaiy (CaSbratioos, Blanks,.Holing Time, Surrogates, Internal Standards)
Date(s) Analyzed:
Samples Analyzed Within 12 Hours of
Tune? Yes No
Instalment ID:
Tune OK? Yes No
Method Blank ID: .
Sample Identifier:
Hold Time
Out. da vs
s
[S
ISTDs
AR
All
SI
S2
S3
IS1
IS2
IS3
1. •
2.
¦
3.
4.
V
6.
1.
%.
9-
19.
.
Date:
Time:
Compound:
SPCC(f)
CCC(»)
Initial CaL
Continuing CaL
OuaEfiers
Aromatic (AR)
RRF<.05
«RSD>30
RRF<.05
«D>25
Meth.
Trin
{+/.)
Ifh
1
Brvmoarcttmnc
,
Acetone
I
S
1.1 -Dichloroethene
#
1
1.2-DiehIoroetheneYtotan
Chloroform
m
1,2-Dichloroethane
1.1.1-Trichtoroethane
Caifcon Tetrachloride
"
Bromodichloromethane
I
cis-1.3-Dichlon»rooene
S
TriRhlomethene
#
Dibromochloromethane
2
Benzene
AR
Bromoform
art-
2-Hexanone
I
1.1.2.2-Tetrachloroethane
S
(*VAK)
#
Chlorobenzene
3
(*VAR-)
Stvrene
fAR^
Xylenes ftotal>
fAR^
leported as:
RT
(uelke. uefL)
TlCs Repotted In Blank(s):
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Case No.: ; Procedure No.: M2-VOA
SDG No.: . ^ Revision: 1
Data Reviewer: Date: 06/30/1995
Site: ' Page 6 of 34
Table M2-V0A£. VOA Surrogate and Matrix Spike Quality Control Summary
Surrogate Datfl ftr""rY
Sample Identifier:
Aaueous Sample Recoveries. %R
Soil Sample Recover
jr. %R
Oualifien (+/-)
SI
SI
S3 '
SI
S2
S3
(Acceptance Range. SR):
>8-110
86-115
76-114
84-138
59-113
70-121
•
1.
2.
3.
4.
. " ' V'
5.
6.
7.
8.
9.
>
" ¦ !
10.
11.
12.
13.
SI ¦ Toluene-d8, S2 «= Bromofhioroberaene,S3 « 1,2-dichloroethane-d4
MR/Mfn IWa ^mnmarv
SPCCtf)
CCC (~)
Matrix Spike, Reeweqr, %R
Matrix Spike Duplicate,
Recovery. %R
MS/MSD Precision, RPD
Qualifiers
<+/-)
Spike CompoundiAromatic (AR)
Range
Actual
Range
Actual
Range
Actual
AQUEO
US SAMPLES
1.1-Dichloroethene
(*)
61-145
61-145
14
Tricbloroetbene
71-120
7M20
14
Benzene
AR
76-127
76-127
11
,
Toluene
<*)CAR)
. 76-125
76-125
13
Chlorobenzene
MAR)
75-130
75-130
13
SOIL
SAMPLES
¦¦
1.1 -Dichloroethene
(*)
59-172
59-172
22
Trichloroethene
62-137
62-137
24
• Benzene
AR
66-142
66-142
21
<
Toluene -
r»HAR)
59-139
59-139 ,
21
Chlorobenzene
m(AR)
60-133
60-133
ii
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Procedure No. : M2-VOA
Revision: 1
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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 oe accurate or precise.
K = Analyte present. Reported value may be biased high. Actual value
is expected lower.
L = Analyte preiseiht. Reported value may be blaii^ l^^Actual value is
expected to be higher.
UJ
UL
Other Codes
Q = No analytical result.
* = Results reported from diluted analysis.
3.1 Action Level Notification
The purpose behind action level notification is to mate 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 III 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.
Not detected; ; quantitation limit may be inaccurate or imprecise.
Not detected,^quantitation limit is probably Kgher.:
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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:
Sitelnvestigation (SI)
• : •
EPA SeclogcToxicologis^:
- 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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Table M2-VOA-4
VOLATILE ORGANIC ANALYTES AND ACTION LEVELS
Compound J;
Action
Compound >
Action
®Ee*eI»
Benzene
#i%233
Ca^ntetrachloridei?#^
IS®!#),
Chlorobenzene
^-1^800 ¦¦ '¦
1,2-Dichloroethane > •,
1,1-Dichloroethylene
i 1*000
cis-l,2-Dichloroethylene '
1,000
trans-1,2-
Dichloroethylene
2,720
Dichloromethane <
(methylene chloride):'%ff V-
^P^OOr: •
1,2-Dichloropropane ¦
:7:-; 90
¦¦ Ethylbenzene
§Si2,100. '
Methylethyl ketone '
(MEK, 2-butanone)
; ^,500
Styrene . ,
.^^20,0°°
Tetrachloroethylene
34,000
Toluene ~
^6;doo ;
1,1,1-Trichlordethane
35,000
Vinyl chloride
2,600
Xylenes
7,800
—
w —.
~All 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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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-yalidation may be written on the Form I'S. The marked
up forms should rq>resoit validation of only the contaminants
exceeding the
3.2 Technical
The objective is to asmt^lffielviUdity of results based on the holding time of thesample
from time of coUection to^^^f lnalysis.
3.2.1 Acceptance'Crlte,
Technical requirements fOT-^jptesto)ldin^ times have only been established for water
matrices, llie holding;tim«^^^ps (and other non-aqueous matrices such as sediments,
oily wastes, and sludge)im
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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 Ftam I VOA
Examine the sample recofds to determine if samples were prcsovefl.' If it is
indicated that th^wei^^problems with the samples, Uien lhe^t^.|^;Of the
and professional judjm|^^^dbe
3.2.4 Action
i. If technical holding times are exceeded, qualify the sample resul^asjToIlows. (Also
see Table M2-VOA-5). "
If there is no evidence that the samples were prc^ppi^sayed and the
techmcd holdtag times exceeded 7 days, qualify pos^i^^^ibs with "L"
and sample rqusmidtition limits with "UL" for smi^^p^npDunds.. Use
profesamial- judg^nit to determine if and how^fo^a^^ii^itic volatile
compounds should also be qualified.
If the samples were properly preserved but the technical holding times
exceeded 14 days, qualify all positive resulte with 'T'-T^and all sample
quantitation limits with "UL."
Table M2-VOA-5
QUALIFICATION OF VOLATILE ANALYTES BASED ON TECHNICAL
HOLDING TIMES
Matrix
Preseryed
> 7 Days
14 Days
No
All Aromatics*
All Compounds
Water
Yes
None
All Compounds
Non-aqueous
No/Yes
None
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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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 suapected laboratory contamination), the reviewer should follow the
hierarchy of qualifiera^In particular, if for any reason the reviewer doubts the
presenceofa compound^the data summary should di^lay; ohly ^ii^'B'' or "R"
quaMer and ^Me|^^|il^ifier. This is because no net'direc^\tf can be
inferred under : tii^^i^ttitions. When results are reported by me: laboratory as
bdow the qualifier is used ovesr tiie ^" qualifier.
4. Customized;JQu|tifie^ Forms should be filled to show holding time
performance(oneTpCT;12-hour periodper instrument).
3.3 GC/MS InstramentlPerformance Check
Gas chromatograpMna^.^ (GC/MS) instrument performance xhecks (formerly,
referred to as tuning) ra^pe^^ ensure mass resolution, identification, and to some~
degree, sensitivity. not 'sample specific, Conformance is determined
using standard, materials, therefore, these criteria should be met in ail circumstances.
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
m/z Ion Abundance Criteria
50
75
95
96
173
174
175
176
177
8.0 - 40.0% of m/z 95
30.0 - 66.0% of m/z 95
Base peak, 100% relative abundance
5.0- 9.0% of m/z 95
Less than 2.0% of m/z 174
50.0 - 120.0% of m/z 95
4.0 - 9.0% of mass 174
93.0-101.0% of m/z 174
5.0 - 9.0% of m/z 176
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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 VOA.
3.3.3 Evaluation rroceaure ,
1. Compare the data presented for each Instrument Performance Check (Form V
VOA) with each mass listing submitted to ensure the following:
• Form V ^OA* k/presoit and completed for each 12-hour period during
which ^ples'were^analyzed.
• The appropriate number of significant figures has been reported (number of
significant figures given for each ion in the ion abundance crit^ column)
and that rounding is correct. (See SOW for requirements).
2. Verify that the mass assignment is correct and that the mass listing is normalized to
m/z 95.
3. Verify that the ion abundance criteria was met. The criteria for m/z 173, 176, and
177 are calculated by normalizing to. the specified m/z.
NOTE: All instrument conditions must be identical to those used in the sample
analysis.
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. This should be
noted on the ORDAS form.
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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 ate not met, professional judgment may be applied to
determine to what extent the data may be utilized. Ouide^m^,\tQ^aid in the
application of professional judgment to this topic are discussed as follows:
The most nimporfcuit factors to consider are the empir^jreswts uiat are
relativelyinsensitive to location on the (^matogn^AlcjEn^^pd the type
of instrumentation. Therefore, the critical ion abunidanceT^ma for BFB
are the jn/z 95/96, 174/175, 174/176, and 176/177 fltiapA, .The relative
abundances of jh/z 50 and 75 are of lower inqkntance,''
5. If the xeviewe^:jtias rea^to believe that instrument perfon^recheck criteria
were achieved using techniques other than those described inlD.|>.4; then additional
information on the/instrument performance checks ^ould b^^tauied. If the
techniques employed are found to be at variance with the contj^ requirements, the
performance and procedures of the laboratory may merit evid^Qn. . ^Concerns or -
questions regarding laboratory performance should be noted Sot TPO action in the
ORDAS form. For example, if the reviewer has reason to teSieve 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 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.
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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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 uiiheated purge and the calibration
for low levd soil samples is performed with a heated purge;
3. Initial ralihratinn^nriaiti: Relative Response Factors (RRFs) forvolatile target
compounds and;^||m^rautoring compounds (surrogates) muit be greater than or
equal to 0.05. (C^tra^tual initial calibration RRF criteria are listed in Appendix
A).
4. The Percent Rdative^tattdard Deviation (%RSD) from the initialcalibration must
be less than or <^1^^30.0% for all cojjipqunds. (Contractual dilibration %RSD
criteria are listed^.mvAi^ndix A).
3.4.2 Review Items
Form VIVOA andchrdMtopams.
3.4.3 Evaluation Procedures
1. Verify that the correct concentration of standards were used^ for the initial
calibration (i.e., 10, 20, 50, 100, and 200 ug/L for water).
2. Verify that the correct init&l 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 woe 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 analvzed 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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Volatile Target (impounds Exhibiting Poor Response
• Acetone
• 2-Butanone
• Carbon disulfide
• Chloroethane
^Chloromethane
p^Pl^oroethene (total)
*5 l,2-I)ichloropropane
• 2-Hexanone
« Methylene chloride
^4-Methyl-2-pentanone
?Toluene-d8 ¦ ^
l^Dichloroethane-d4
NOTE: Compounds in bold are system monitoring compounds..
5. Evaluate the %RSI). for all volatile target compounds and system monitoring -
compounds:
a. Verify 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 of 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 perrormers" iisiea 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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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:
a. if any of ^ required volatile compounds have a %RSD greater than 30.0%,
and if diffiSiii^g ;'dtiier the high or the low point of the curve does not
restore the %RSD to less than or equal to 30.0%:
i. Qualify positive results for that compound(s) with "J".
' ii. No Qualifiers are needed for volatile target compounds inai were not
detected. If the %RSD is grossly exceeded (i.e., >50%),
profe^biial judgment is used to qualify non-detectswith "IXJ".
b. If the/high pdiritofthe curve is outside of the linearity criteria (e.g., due to
saturation):
i. No qualifiers are required for positive results in the linear portion ot
thecurve.
ii. Qualify positive results outside of the linear portion of the curve with
a "J".
iii. No qualifiers are needed for volatile target compounds mat 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
thecurve.
ii. Qualify low level positive results in the area of non-linearity with
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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NOTE: If a, b, or c options are used, a description of the process must be clearly
stated in the date 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.
4. The potmtial efife^ts^on die data due to unacceptable calibration criteria should be
noted in the data review narrative.
5.. If calibration criteria are exceeded, this should be noted on the ORDAS.
3.5 Continuing Calibration
Compliance requir^ratsrfor satis&ctory instrument calibration are established to ensure
that the instrument is cajole acceptable qualitative and quantitative data.
Continuing calibnitifm^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.
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 ± 25.0%.
o
3.5.2 Review Items
Review Items: Form VII VOA and chromatograms.
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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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 historical performance data indicate pocir jes^onse and/or erratic
behavior,Athie -compounds listed in Section 3.4.3^ above,have no contractual
mayiiTiiii^^nfcriteria Contractually they miist'Vimeet 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.
3. Evaluate the caHbratioix»KRF and continuingcalibration RRF for
one or mbre cbmpoSwi&^)|
Verify 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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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 Jiotavailable, the reviewer must use professional judgment to assess
the data.
3. Thepotential effectSuon^the data due to unacceptable calibration criteria should be
noted in the diata reyi^, narrative.
4. If calibration criteria are exceeded, this should be noted in the ORDAS.
3.6. Blanks
The purpose of lalyna^ blank analysis is to determine the existence and
magnitude of cohtaininad^j^ulting from laboratory (or field) activities. The criteria for.
evaluation of blanks. i^ply^O'any blank associated with the samples (e.g., methods blanks,'
instrument blanks, trip bUmks, and equipment blanks). If problems with asx blank exist,
all associated data must te 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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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 Kwieriw-^'iue the Method Blank Summary (Form IV VOA) to
identify the samples assodated with each method blank.
3. Verify that the instalment blank analysis has been performed following any sample
analysis where a target analyte(s) is reported at high concentration®.^
3.6.4 Action
If the appropriate blanks were not analyzed wun the frequency described in Criteria 2, 3,
and 4, thai the data reviewer should use professional judgment to determine if th&
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 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 (5x) 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, then this should be
noted for TPO action in the ORDAS.,
2. Any volatile oompowd detected in the sample (other than the common volatile
laboratory contaminants),4hat was also detected in any associated blank, is qualified
"B", what 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.
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 amount of contamination is actually made.
Additionally, there may be instances wftere little or no contamination was present in
the 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 sampleresulL 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 (TlCs), which are found in both the sample and
associated blank(s). (See VOA Section XM 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 IPO action if the cross-contamination is suspected of having an
effect on the sample results. Sample results which are pbsdble attifacts of cany-over
should be flagged as unusable (R).
8. When there is convincing evidence that contamination is restricted to a particular
instrument, matrix, or concentration levd, the Sx/lQx rule will only be applied to
compare contaminated blanks to certain associated samples ~(^ Opposed to all samples
in the case). Some Examples are as follows^
Column bleed (siloxanes) may be localized to a particular instrument.
Methanol extractions in the medium soil volatile analysis -protocol can give rise to.
contaminants that are not seen in the low-level aqueous analyses;
Common laboratory comaminanis, such as methylene chloride, are generally too
unpredictable to safely assume contamination is restricted to a particular instrument,
matrix, or concentration leveL
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
lOx Sl
Blank Result 7- 7
CRQL 5 5
S ample Result 60 !30
Final .Sample Result 60B 30B
In theexamplefarthe "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 35n(or3 x 7)' would 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
lOx
Blank Result 6 6
CRQL 5 5
Sample Result 4J 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 orlOx multiple of the blank result.
Rule
lOx 5x
Blank Result 10 10
CRQL 5 5
Sample Results 120 60
Final Sample Result 120 60
For both the "lOx" 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 performaiice 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. Hie sample itself may produce
effects due to such factors as interferences and high concentrati<^/pfSince the
effects of the sample matrix are frequently outside the control 6f|S^|ib^iibry and may
present relatively unique problems, the evaluation and review oif^M^ueSl'bii 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. Three system monitoring compounds (l,2^chloroethane^4, bromdfluoroboizraie, and
toluene-d8) are added to all samples and blanks to measure thdr recovery in
environmental samples and blank matrices.
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 Form—Form II 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 Med 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
criteria.
3. Any time there ar^two or more analyses for a particular sample, the reviewer must
determine which are the best data to report. Considerations should include but are not
limited to:
a. System monitoring compound recovery (marginal versus gross deviation);
b. Technicalholding times.
c. Comparison of the values of the target compounds reported in each sample
analysis.
d. Other QC information, such as performance of internal standards.
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-VOA-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".
b. Non-detected volatile target compounds are qualified as unusable, "R".
4. it two or tniee system monitoring compounds in the volatile, sample^have recoveries
outside acceptance limits, refer to Table M2-VOA-6.
5. In the special case of a blank analysis with system monitoring compounds out of
specification, the reviewer must give special consideration to the validity of associated
sample data. Hie basic concern is whether the blank problems tepresoit an isolated
problem with the blank alone, or whether ihere is a fimdameritailproblemwith the
analytical process. For example, if one or more samples in the batch show acceptable
system monitoring compound recoveries, the reviewer may^choose to consider the
blank problem to be an isolated occurrence. However, even if ihis judgment allows
some Use of the affected data, analytical problems should be noted for TPO action oa
the ORDAS. Also note if there are potential contractual problems associated with the
lack of reanalysis of samples that were out of specification.
6. Whenever possible, potential effects of the data resulting from system monitoring
recoveries not meeting the advisory limits should be noted in the datareview narrative.
7. Positive results for compounds already flagged for blank contamination, "B", will not
need a separate flag for system monitoring compound recoveries. However, these
situations should be addressed in the data review narrative and the support
documentation.
Table M2rVOA-6
QUALIFICATION OF VOLATILE ANALYTES BASED ON SYSTEM
MONITORING COMPOUND RECOVERIES
1 or more
< 10%
1
High/Low
2 or 3
High/Low
2 or 3
All Low
2 or 3
All High
Detected
Analytes
L
J
J
L
K
Non-Detected
Analytes
R
UJ
UJ
UL
None
8. When dilutions are performed which prevent detection of system monitoring
compounds, the data review narrative and support documentation should indicate that
extraction efficiency/method accuracy cannot be verified.
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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, ifa demonstrated laboratory contaminant is detected in one analysis
but not in the other/the negative result may be more appropriate to report.
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 *re 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(J), 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 on 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 ID 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 HI 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 ot tne
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 m 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 ±30 seconds from
the retention time of the associated calibration standard.
. • ' i
3.9.2 Data Requirements and Data Retrieval
Form Vn 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 "J".
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, "fe".
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 datsufor 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.
3.10A 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.
2. The reviewer must assure that any results in errorbymore^th^:l,Opercent are
identified and corrected on the sample data summary. If labofa^iy rewbmission is
not performed, the reviewer should document his/her changes ito ^e data in the
narrative and support documentation. Calculation errors should 'also be noted on the
ORDAS.
3. Numerous or significant failures to properlj^eyaluate and adjustiCRQLs should be
noted for TPO action on the ORDAS.
3.11 Tentatively Identified Compounds
Chromatographic peaks in volatile fraction analyses that are not target analytes, system -
monitoring compounds or internal standards are potential tentatively identified compounds
CTICs).
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 TTCs.
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 reportedas sample TICs.
Examples:
a. Common laboratory contaminants: COj (m/z 44), siloxanes (m/z 73),
diethyl ether, hexane, certain freon& (1,1,2-trichloro-l ,2,2-trifluoroethane or
fluorotrichloromethane), 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 condensation reaction products of acetone include: 4-hydroxy-4-
methyl-2-pentanone, 4-methyl-2-penten-2-one, and 5,5-dimethyl-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-HC 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 I-HC that is included in the validation report^;
To be considered quesaonaoie, 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. For VOA data, an instrument level comparison is: used unless the
contamination is - proven to originate during samjfc 4'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.
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-HC 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 Semivolatilet)rganic Analyte Data
• Subappendix B-l covers Level Ml
• Subappendix A-2 covers Level M2
WDCR565/03Z 52
f
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Appendix B
$alMoiiiiSW^^ "Organic AnalyteData
• 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
purpose and Applicability
this procedure prp^ides ste^by-st^ instructions to manually validate the semivolatile
organic analytethemanual innovative data validation abroach at Level
Ml.
The procedure' is ^U^lii!3Q^he^SVOA data-obtained using the Contract Laboratory
Program Statmi»t^^^^^C^^SOV0. Harifcopy data conforming to the CLP SOW
spedfications to carry out the procedure.
Datavalidated tising;3I&|f^^ are considered usable for the following types of
purposes; however^ users must decide on a case-by-case basis whether the
procedure is suitable fortheir intended data uses. The suggested data uses are:
• Oversight of activities led by other paraes
• Comparison to action levels
® . Initial site investigation
0 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.
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Table Ml-SVOA-1 1
QC CHECKLIST FOR LEVEL MI
CLP RAS SEMIVOLAHLE ORGANICS
Mannal
JC MEASURES
1 m 1
m
M3
ActionLevel Notification
rn
¦ *
3C
Iostnimeottune
X
X
Initial Calibration(RRF)
X
X
Initial Calibration (%RSD)
X
X
Continuing Calibration (RRF)
«
X
ContinuingCalibration (%D)
X
x
LaboratoiyBlank
i- *J
X
MS/MSD (KR, RPD)
X
X
Internal Standard Area
X
X
Field Blank
i * i
*
x
Sample Paperwork
rn
*
x
Holding Time
1 X
x
Retention Time
* J
¦ X
x
Surrogate Recovery
X
x
Dilution Factor
X
x
Moisture Content
X
Mass Spectra
Uj
X
Chromatograms
rn
x
X
Raw Data
X
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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 (hat 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 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 Toxicologists:
— Enforcement
— Superfund
RCRA
The remaining data validation should be completed per normal procedures.
Any special instructions front 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
Action
Action
Compound
Level*
Compound
Level*
1,3-Dichlorobenzene
8,930
1,4-Dichlorobenzene
10,700
Pentachlorophenol
300
— '
—
~All 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 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 personnd 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.
3.2.1 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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• 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 in the sample spectrum)
• Ions, present in the sample above 10 percent relativeabundancemust be
accounted for.
3.2.2 Review Items
Form I's for each field sample, field blanks, and laboratory blante mdwted .in a Sample
Ddivery Group (SDG) sue necessary to compile* list of the detected compounds . Mass
spectra are thai necessary for each of the detected compounds in $ sample, ^llie required
mass spectra include both the sample spectra as wdl as the standard speqtnu: v
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 evaluatidn may be significantly-, reduced by
performing the blank evaluation first. Hie 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
Revision: 1
Date: 06/30/1995
Page 7 of 19
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 thai be
performed that all target compounds for which mass spectra are pitivided 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 o£»tfie' fit of all criteria is produced. The
score is based on a basis o>f 1(X) wlOOO 'far a perfect match ofthepresence of major ions
and their relative abundances^ ^nlhe 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) isgenerally
considered acceptable for positive identification for a compound.
Visual comparison of a mass spectrum involves looking for thebase ion (the mass fragment
with the highest intensity), the parent ion (mass fragment equalto the molecular weight of
the compound) and other characteristic ions representing removal of one or more functional
groups (such as -CH3, -CH2-, -CI, -OH, or a combination thereof) from theparent 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 separatedby 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 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
Revision: 1
Date: 06/30/1995
Page 8 of 19
different. Inseparable isomers reflect a limitation of the gas chromatography 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 totemthemapart. Homologous compounds generally have different
ret&tioa times;4hea«^ not be of much concern. Thus, coeduting compounds do
not pose significant problems whai evaluating the mass spectra.
Seldomdoes aCLP^l^ incorrectly interpret a mass spectrum, but there is a
subjective dement to mass spectral interpretation. While working within the CLP
guidelines, the; have their own reporting practices at the limit of the
instrum^'s «ensitiY^ mass spectral identification problems occur near the
limit of dete
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Procedure No.: Ml-SVOA
Revision: l
Date: 06/30/1995
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 ate history is also
an important equation; ^ essential to perform such an evaluation On
contrast to 'validation') -imy iiotbe easily available to a data validator. Nonetheless, it is
incumbent uppn a data v^dato 'to make- appropriate recommendations to the project
manager or toe remedial office?.
3.2.5 Reporting
The most convenient Spectral evaluation is through a brief
memorandum to q>prppf^^a^doities. The highlighted Forms Is and th^ mass spectra in
question should be append^ to'the memorandum in support of the conduaons. Also fill
out and attadi ihe iti^;Spe^^ as depicted in Table Ml-SVOA-3, to
Ihe report as a: ieconl of ^i^ was done. Record the date(s) of analyses. Fidd sample
numbers should be transcribed 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:
• X—Acceptable mass spectrum.
• N—Tentative identification. Partial proof of a compound's presence, but all
identification criteria not met.
• U—No 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 tool used for the false negative evaluation under Level Ml.
-------
Case No.:.
. SDGNo.:.
Data Reviewer:
Site:.
Procedure No.: Ml-SVOA
Revision: 1
Date: 06/30/1995
SVOA Mass Spectral Evaluation Summary
-Dates Analyzed:
Sample Identifier
Comments on Chromatoenms
1..'
i.
2.
2.
3.
3.
4.
4.
IuLlD:
S.' '¦
5. * . ' ' ' ' '
••6.. "
6/ • " ' ' ¦' \ • " •
7.
7. " • ' ¦
8.
8.
¦
>
'9.- ' . ^
9. '
10. •
10. . •'
SPCC (0 CCC(*j
^ 'Samnle Identifier
Addk(A)
- ' 2
•V 3 " '
j
¦- 4 ••
- • .
5
6
¦ : 7
; 8
; : 9
10
Coaqmnd: . Base/Neofcral (BN]
MS
RT
MS
RT
MS
RT
Mis
RT
MS
RT
MS
RT
MS
RT
MS
RT
MS
RT
;MS
SCT
Phenol /*VA1
< -
fBNl
-
rAi
•
¦' >
YBNI
/
wraw
raw
¦
1
(A-\
2.2'-oxvbi»n-CMoroorooane'>
fBNl
fAI
1 .
• .-
nsNV/n
raw
Nitrobenzene
raw
laonhorone
raw
' '
2-NitroohenoI
fA>W
¦
CA1
1
bisf2-Chloroethoxv1methane
raw
2.4-DichloronhenoI
CA1
-
-
1.2.4-Trichlorobenzene
raw
Naohthalene
raw
\
4-Chloroaniline
raw
-
Hexachlnmhutadiene
mwr»v
.
4'
4-Chloro-3-methvlohenol
(M(*)
2-MethvI naohthalene
raw
¦ '
HexachlorocvcloDentadiene
(BNlffl
2.4.6-TrichloroDhenol
fAW»>
•
- 2.4.5-Trichloroohenol
fAI
2-Chloronaohthalene
raw
2-Nitroaniline
raw
Dimethvlnhthalate
raw
Acenaohthvlene .
raw
2.6-Dinitrotoluene
raw
3-Nitroaniline
raw
- Acenaohthene
f*traw
2.4-DinitroohenoI
(Mm
1
4-Nitroohenol
fA)W
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Procedure No.: Ml-SVOA
Revision: 1
Date: 06/30/1995
SPCC d) CCC(*
Sample Identifier
Acidic (A)
1
2
3
4
5
6
7
8
9
10
Compound; Base/Nentral (BN)
MS
RT
MS
RT
"MS
RT
MS
RT
MS
RT
MS
RT
MS
RT
MS
RT
MS
RT
MS
RT
Dibenzofuran
fBNI
_2.4-DinitrotoIuene
raro
•
(8N1
•
'
fBNl
• - .
V
fHNI
CA1
flBNl
- - v'
-
mv
-
'...'jy.-
¦
fAV*)
fBNY
mm
fBNl
¦ >;•••
. .
"mwi
¦ •
(raw
' -
• -
fBNl
--
nrm
IBM
- ¦
1 mm
,•
biiA-edivIhexvTkDhdiala^e
mwi
'
.
mm
®nm
Vbni
- •
Benzofklfluonnthene
(BNl
-
BenTiWaVivyene
fBNW
Indenofl .2.3-c
-------
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 chromatogramsfor 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 die diron^grams that are not
accounted for as TCLs or TTCs. Significant ^eaks aiel those with a
minimum peak height of 10 percent of idle closest; internal standard.
• The chromatograms should ideally have base-line resolution between
adjacent peaks. Also, there should nebbe 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.
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 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 TTCs. 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
Revision: 1
Date: 06/30/1995
Page 13 of 19 -
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.
Rapid peak rising or peak tailing indicate problems-'with the gas chromatographic column,
such as depleted stationary phase on the column, decomposition of the stationaiy.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 probleijr 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. TTCs 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
Revision: 1
Date: 06/30/1995
Page 14 of 19
evaluated to determine if the peak resolution problem could affect detection
or quantification. Ifdetermined 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 jeopardised
by poor resolution of adjacent peaks.:
• Broad envelops of, homologous compounds could- interfere with
quantificationoreven detection. If the interferenceis evident from the
recoveries of vthe internal and surrogate standards in the yicinijy of the
envelop, associated. compounds may also bis interfered , wdth. Using
professional discretion, the positive and negative data may texonsidered as
estimated, "J" and "UJ", respectively. If the project-objectives cannot be
met withtheestimated data, alternative sample preparationand cleanup
procedures mky need to be developed and specified.
• Discrete shifts in *the baseline in the middle of: a im 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 cc^dored estimated*
(M7V and '*UJy 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 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 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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Date: 06/30/1995
Page 15 of 19
3.4 Evaluation of Retention Times
While not unequivocalin 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 tiie 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
The criteria for ret^ldto 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.
3.4.2 Review Items
Quantitation reports for the sample and continuing calibration are required tor 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
luggested.
WDCR656/027.51
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Procedure No.:- Ml-SVOA
Revision: 1
Date: 06/30/1995
Page 16 of 19
* 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
Hie 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 may
be recorded under tije-'VRT" column. A data qualifier code* may be added to the values ,
exceeding 0.06 BRT 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.
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
Revision: 1
Date: 06/30/1995
Page 17 of 19
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
naphrtialftne, 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, chromatograms, quantitation reports, etc., are essential for performing a
validation of the blanks first.
3.5.3 Blank 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. Mate 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.
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 m 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 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 IH 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:
• The chain-of-custody form should be properly and completely fillefd 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. Hie 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 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
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 III 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
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 approachat 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
oh modifications to Regions m's National Functional Guidelines for Organic Data Review.
The procedure is applicable to the SVOA data obtaihed 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 carry out the procedure.
Data validated using this . procedure are considered usable for the lollowing types of
purposes; however, the data users must decide on a case-by-case basis whether the
procedure is suitable for thrir 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: 1
Date: 06/30/1995
Page 2 of 39
Table M2-SVOA-1
QC CHECKLIST FOR LEVEL M2
CLP RAS SEMIVOLATILE ORGANICS
QC MEASURES
Manual
Ml
M2
M3
Action Level Notification
x
X
X
Instrument TVrne
X
X
Initial Calibration (RRF)
X
X
Initial Calibration (%RSD)
X
X
Continuing Calibration (RRF)
X
X
Continuing Calibration (%D)
X
X
Laboratory Blank
X
X
X
MS/MSD (%R, RPD)
X
X
Internal Standard Area
X
X
Field Blank
X
X
X
Sample Paperwork
X
X
X
Holding Time
X
X
Retention Time
X
X
X
Surrogate Recovery
X
X
Dilution Factor
X
X
Moisture Content
1 x 1
x
Mass Spectra
X
X
Chromatograms
x 1 x 1 X
Raw Data
X
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Procedure No.: M2-S VOA
Revision: 1
Date: 06/30/1995
Page 3 of 39-
2. Quality ControI 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 in a
standardized report form.
The semivolatile data requirements to be checked-afe 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:
• 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, Lei , M2
Major and minor problems associated with the analysis
Highlight issues that may have affected detection limits
• Include the following attachments
- List,of data validation qualifjpn
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
The data qualifiers assigned in this review are as follows:
Codes Relating To Identification (Confidence concerning presence ~4r 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 of 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.:
SPG No.:
Data Reviewer ¦ 6
Site: _
Table M2-SVOA-2. SVOA Qualifier Summary (Calibrations, Blanks, Holding Time, Surrogates, Internal Standards)
Analysis
Datefs):
Analyzed Within
12 Hours Of
Tune?
Yes No
Inst. ID:
Tune OK?
* _Yes No
MBlnkID:
Ext. Dales:
spccm
cccm
Initial Cal. *
ContuminzCal.
Blanks
' OuaCflers.
Acidic (A)
Base/Neutral (BN) ;
RRF<.05
*RSD>30
RRF<.05
«D>25
'lab •
Field
(+/-) -
Phenol
; fttfAY-
bisf2-CSiloroethvr>ether
fBW
fAA
(BHS
.
-
I
t*\(Bm
¦' •
s
(BN1
#
2-Methvlnhenol
--
1
2.2'-orvbisn -ChloroorooaneV
(BN)
4-Methvlohenol
fAI
N-Nhroso-di-n-ofODvlamine
fBNVtt
Hexachloroethane
raw
.
Nitrobenzene
rero
¦
Isoohorone
fBNi
2-Nitroohenol
(AW)
2.4-Dimethvlnhenol
fAI
I
bi sf2-Chloroethoxv1metha ne
AW
...
s
2.4-DichIoronhenol
(M
v,
tt
1.2.4-Trichtorobenzene
(BNt
2
Naphthalene
fBNrt
• -
4-Chloroaniline
(BN)
Hexachlorobutadiene
fBNIW
4-Chloro-3-methvlnhenol
2-Methvlnaohthalene
fBNV
Hexachlorocvclooentadiene
(BNHfl
2.4.6-Trichloroohenol
(AM*)
. ¦ *
2.4.5-TrichloroDhenol
(A)
'
-
2-Chloronanhthalene
fBN>
2-Nitroaniline
fBN>
I
Dimethvlnhthalate
IBM
S
Acenaohthvlene
fBN)
' H
2.6-Dinitratoluene
(BN)
3
3-Nitroaniline
(BN>
Acenaohthene
WfBNl
'
2.4-DinitroohenoI
) 1
Surrogate
Internal (IS)
Ex
An
1
2
3
4
5
6
7
8
1
2
3
'••'4
5
6
1.
¦
2. v. '
3. '
.s :
4.
••
- ¦
5.
,
6.'
. , •• •¦
, . ;;
7. " ' '
¦ -
8.
. - .•
* N
•. y •
¦- .
9. ' •
¦•'Vr
¦ •
io.' ¦-.-A
' i*' •
• / ' V
"4
• ; • ¦;'
' DatB^ .. .Tune:
-------
Case No.: ; Procedure No^: M2-SVOA
SDG No.: ; ¦ Revision: I
Data Reviewer: ¦ Date: 06/30/1995
Site: ;
Table M2-SVOA-2
(contd.)
Analysis Date:
Instalment ID:
Date: ¦ Time:
Cwnpwdt
spccin
mcccw
,v-'-Initial CaL
ContimdmE CaL
Blanks
Qualifiers
' . %i'AijidiC'(A);
. Base/Neutral (BN)
RRF<.05
«KSD>.30
RRFC.05
%D>25
Lab
FWd
(+/-V
. mwi
" YBN) -
^•
fBNV
.
I
J* *
is
(AY
s
fBNVh
4
(m
-flBNV
¦ ¦ ¦' .¦
: fAV*i
' .v.-. ¦-
' %
¦ . ¦
.
s
Benzo(a)anthracene
fBN)
# •
bisf2-ethvlhexvno1itha1ate
fBhn
N
5
Chrvsene
Di-n-OctvIohthalate
fBNIW
• (
Benzoflrifluoranthiene
fBN>
I
mm
. 1
S
BenzofaWrene
#
Indenofl .2.3-c
¦
Benzofe.h.rtoervlene
ffiNi
Reported as: RT Cue/kg. us/Vi
TlCs.Reported In Blank(s):
-------
Case No...
SPG No.:
Data Reviewer:
Site:
Procedure No.: M2-SVOA
- Revision: 1
_ Date: 06/30/1995
Table M2-SVOA-3. SVOA Soil Surrogate and Matrix Spike Quality Control Summary
Surrogate Onta Summary
Sample Identifier:
Soil Sample Recoveries. %R
Qualifiers (+/.)
SI
S2
S3
S4 "
S5
S6
S7
S8
(Acceptance Ranee. %R):
23-120
30-115
18-137
24-113
25-121
19-122
20-130
20-130
-•
1
j
•
3^ -
¦ . •
1
:
SI «= Nitrobenzene-d5, S2 = 2-fluorobiphenyl, S3 = tetphenyl-dl4,S4 = phcnol-d5, S5 = 2-fluorophenol, S6 = 2,4,6-tribromopheool, S7 = 2-
chlorophenol-d4, S8 = l^iddonbenuuHM-
MS/MSD Data Summary
SPCCtf)
CCC (»)
Spike Compound: Aromatic (AR)
Matrix Spike, Recovery,
«R
Matrix Spike Duplicate,
Recovery. %R
MS/MSD
Precision. RPD
Qualifiers
(+/•)
Range
Actual
Range
Actual
Range
Actual
SOIL SAMPLES
Phenol
26-90
26-90
35
2-Chlorophenol
25-102
25-102
50
1,4-Dichlorobenzene
28-104
. 28-104
27 .
N-Nitroso-di-n-propylamine
41-126
41-126
38
1,2,4-Trichlorobenzene
38-107
38-107
23
4-Chloro-3-methylphenoI
26-103
26-103
33
, Acenaphthene
31-137
31-137
19
4-Nitrophenol
11-114
11-114
50
2,4-Dinitrotoluene
28-89
28-89
47
Pentachlorophenol
17-109
17-109
47
Pyrene
35-142
35-142
36
-------
Case No.: Procedure No.: M2-SVOA
• SDG No.: : Revision: 1
Data Reviewer: • Date: 06/30/1995
Site: j -
Table M2-SVOA-3. SVOA Aqueous Surrogate and Matrix Spike Quality Control Summary
•¦Surrogate Data Summary
Sample Identifier:
Aqueous Sample Recoveries, %R
Qualifiers (+/-)
SI
S2
S3
S4
S5
S6
S7
S8
- fAcceptance Ranee. 56R):
35-114
43-116
33-141
10-110
21-110
10-123
33-110
16-110
I.
2.
:¦ , \
3. .
4.
.i
5.
•-
• '
6.
-
¦ ¦
7.
S.
ir 1
4
9.
10.
SI " Nitrobenzeno-<15, S2 «= 2-fluorobiphenyl, S3 *> tcqphenyl-dl4, S4 «= phenol-dS, S5 «¦ 2-fluorophenol, S6 ¦= 2,4,6-tribromophenol, S7 = 2-
chlorophenol-d4.S8 «= 1.2-dichloroberaene-d4. NOTE: Surrogates S7 and S8 lutve advsUory limits only. ¦ ' ~
MS/MSP Data Snmmarv
SPCC (#)
CCC (~)
Spike Compound: Aromatic (AR)
Matrix Spike, Recovety,
«R
Matrix Spike Duplicate,
Recovery, %R
MS/MSD
Precision, RPD :
Qualifiers
(+/-)
Range
Actual
Range
Actual
Range
" Actual
• AOUEOUS SAMPLES
Phenol
12-110
12-110
42
2-ChIorophenol
27-123
27-123
40
1,4-Dichlorobenzene
36-97
36-97
28
N-Nitroso-d i-n-p ropy lami ne
41-116
41-116
38
1,2.4-Trichlorobenzene
39-98
39-98
28
4-Chloro-3-methylphenoI
23-97
23-97
42
Acenaphthene
46-118
46-118
31
4-Nitrophenol
10-80
10-80
50
2,4-Dinitrotoluene
24-96
24-96
38
Pentachlorophenol
•9-103
. 9-103
so
-
Pyrene 1
26-127
,
26-127 -
31
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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 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 exceedingthe 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-SVOA
Revision: 1
Date: 06/30/1995
Page 10 of 39
EPA RPM or SPO
EPA Section Chiefs:
- Site Investigation (SI)
—- Remedial
—: IMorcement
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 M2-SVOA-4
SEMTVOLATILE ORGANIC ANALYTES AND ACTION LEVELS
•
Action
Action
Compound
Level*
Compound
Level*
1,3-Dichldrobenzene
8,930
1,4-Dichlorobenzene
10,700
Pentachlorophenol
300
—
—
*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 levd
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 (@ 4°Q 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 semivolatiie compounds in 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 ISV-1 and SV-2, EPA Sample Shipping Log 4nd/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 woe 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 woe 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
Dale: 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 on the resulting data in the data review narrative.
6. When contractual and/or technical holding times are exceeded, this should be noted
on the ORDAS form.
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
Qas 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 (DFIPP) for semivolatile
analysis, must meet the ion abundance criteria given below.
Decafluorotriphenylphosphine (DFIPP)
mlz 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 1.0% 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 abundancerof m/z 442 may be up to 110 percent that of
m/z 198.
3.3.2 Review Items
Form V SV.
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.v 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
Revision: 1
Date: 06/30/1995
Page 15 of 39 -
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.
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 coelution problems, background
subtraction should be done in accordance with the following procedure. Three
scans (the peak apex scan and the scansimmediately 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.
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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Procedure No.: M2-SVOA
Revision: 1
Date: 06/30/1995
Page 16 of 39
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 ion the chfoniatographic profile.
b. For the ions at m/z 3l, 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 Ifrelative 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
Revision: 1
Date: 06/30/1995
Page 17 of 39
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 ch&k.
2. Minimum Relative Response Factor (RRF) criteriamust be greater than or equal to
0.05. Contractual RRF criteria are listed4nr'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 VISV-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
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Procedure No.: M2-SVOA
Revision: 1
Date: 06/30/1995
Page 18 of 39
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 all semivolatile compounds.
Semivolatile Target Compounds Exhibiting Poor Response
• 2,2'-oxybis(l-Chloropropane)
• 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 +. 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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3.4.4 Action
1. All semivoktile 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 wilh "J" using professional judgment, and rion-
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 ifeliminating either the high or the low point of the curve does,
not restore the %RSD to less than or equal to 30.0%:
1. 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
"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.
ii. Qualify low level positive results in the area of non-linearity with
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iii. 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 in 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 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 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 VIISV-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 foil 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 +. 25.0%
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. If the %D is outside the ±_ 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 +. 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 tailed to provide adequate calibration information, the
designated representative should contact the laboratory and request the necessary
^formation. 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 IPO action on
the ORDAS.
5. When it is suspected that relative response factors were incorrectly generated trom
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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method blanks, instrument blanks, trip blanks, and equipment blanks). If problems with
anv 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 toe 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 ISV-1 and SV-2, Form IV SV and chromatograms.
3.6.3 Evaluatidn 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. Hie 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
fidd 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 fidd blank has a highest concentration of a
contaminant, thai all samples in the associated case are qualified "B", using the 5x and
lOx rule. Other fidd blanks associated with the case are not qualified.
Specific actions are as follows:
1. If a semivolatile compound is found in a blank but as1 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 (5x) the blank;.concentration.
For phthalate contaminants, the results are qualified "B" who! 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 levds 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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analytical step are identical (i.e., same final extract volumes, injection
volumes, and extract dilution factors for sample versus blank):
• In this case, it is acceptable ana equivaieni io compare eiiner
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 levds is appropriate. For 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
• un tne outer nana, if it is highly probable that the contamination
originated before the dilution step, thai 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 BNA 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 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 "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 conjfemination 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.
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 blank(s). (See Section 3^11 for TIC guidance.).
6. If an instrument blank was not analyzed following a sample analysis which-
contained an amdyte(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(s). If instrument cross-
contamination is suggested, thai 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/10X 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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• 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 Sx orlOx multiple of the blank
result.
. Rule
lOx 5x
Blank Result 7, 7
CRQL 5 5
Sample Result 60 30
Qualified 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 M5x" rule, sample
resets 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.
Rule
lOx 5x
Blank Result 6 6
CRQL 5 5
Sample Result 4J 4J
Qualified Sample Result 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
lOx
Blank Result 10
cr$l
Sample Result
Qualified.Sample Result
For both the "lOx" and "5x" rules, sample results exceeded the
adjusted blank results of—100 (or 10x10) and 50 (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 arid blanks to
measure their recovery in sample and blank matrices.
2. Surrogate spike recoveries for semivoiatiie samples ana blanks must be within the
limits specified on Form II SV-1 and SV-2.
3.7.2 Review Items
10
5 5
120. 60
120* 60
Form IISV-1 and SV-2 and chromatograms.
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3.7.3 Evaluation Procedures
1. Review cnromaiograms to check the surrogate spike recoveries on the Surrogate
Recovery Form n SV-1 and SV-2.
2. Hie following should be determined from the Surrogate Recovery form(s):
a. If any two base/neutral & acid surrogates are out of specification, or if any
one base/neutral or acid retractable surrogate has a recovery of less than
10%, thai there should be a reanalysis to confirm that the non-compliance is
because of sample matrix effects rather than laboratory deficiencies.
NOTE: When there are unacceptable surrogate recoveries followed by successful re-
analyses,the laboratories are required to report only the successful run.
b. The laboratory has Med to perform satisfactorily if surrogate recoveries are
out of. specification and there is no evidence of reinjection of the extract, or
xeextraction and reanalysis (if reinjection Ms to resolve the problem).
c. Verify that 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.
) r "
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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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 add fraction), are outnof 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 implied 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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3. If any surrogate in either sefnivolatile 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 Umits are not met, use professional judgment to
qualify non-detected compounds).
table M2-SVOA-5
QUALIFICATION OF SEMTVOLA1JLE ANALYTES BASED QN
SURROGATE RECOVERIES
2 or 3
All High
2 or 3
All Low
2 or 3
Mixed High/Low
1 or More
< 10% Rec.
Detected analytes
K
L
J
L
Non-detected analytes
None
UL
UJ
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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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/method accuracy cannot be verified.
9 Although semivolatile surrogate recoveries cannot usually be correlated with
specific analytes, in the following cases sgpdfic action will be allowed based upon
a particular sunogate:
a. What a semivoiatue surrogate is the deuterated analog of a TCL analyte (for
example^ ^phenol and phenol), 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 other surrogates are biased high instead of low.)
b. When a,2-terpnenyi is oiasea low, positive results and quantitation limits for
the heavier polyaromatic hydrocarbons (those which elute 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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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.
2. Matrix spite and matrix spike duplicate recoveries should be within the advisory
limits established on Form m SV-1 and SV-2.
3. The Relative Percent Differences (RPDs) between matrix spike and matrix spike
duplicate recoveries should be within the advisory limits listed on Form in SV-1
and SV-2.
3.8.2 Data Requirements and Data Retrieval
Form m SV-1 and SV-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.
2. Inspect results for the MS/MSD Recovery on Form HI 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 profesisional
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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having a systematic problem in the analysis of one or more ahalytes, 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 VIIISV-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 VIII SV-1, VUI SV-2).
2. Verify that all retention times and IS areas are within the required criteria.
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Procedure No.-: M2-SVOA
Revision: 1
Date: 06/30/1995
Page 35 of 39-
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 die values of the target compounds reported in each fraction.
3.9.4 Action
1. If an IS area count for a sample or blanfris-'outside - 50% or + 100% of the area
for the associated standard:
a. Positive results for compounds quantitated using that. IS should be qualified'
with "J".
b. Non-detected compounds quantitated using an 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 3U 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
Revision: 1
Date: 06/30/1995
Page 36 of 39
3.10 Reported CRQLS
The objective is to ensure that the reported quantitation results and Contract Required
Quantitation Limits (CRQLs) for seiiiivolatile 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 wdght 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 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
Revision: 1
Date: 06/30/1995
Page 37 of 39
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 Acceptance Criteria
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 iiedght of the nearest internal standard. TIC results are
reported for each sample on the^d^eanic Analyses Data Sheet (Fopn I SV-HC).
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 property reported in another fraction. For example, late eluting
volatile target compounas should not be reported ais semivolatile TICs.
3.11.2 Review Items
Form I SV-HC, chromatograms.
3.11.3 Evaluation Procedures
1. Guidelines for tentative identification are as follows:
Ensure that TIC results are reported on Form I's.
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
Revision: 1
Date: 06/30/1995
Page 38 of 39
a. Common laboratory ^contaminants: C02 (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-dimethyl-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
false 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
Form I-UCs.
2. Blank Results
Form I-HC 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
Revision: 1
Date: 06/30/1995
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-HC 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.: Ml-PEST
Revision: 1
Date: 06/30/1995
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
at Level Ml.
The procedure is applicable to the Pesticide/PQB
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Procedure No.: Ml -PEST
Revision: 1
Date: 06/30/1995
Page 2 of 20
Table Ml-PEST-1
QC CHECKLIST FOR LEVEL Ml
I
CLP RAS PESTICIDES/POLYCHLORINATED B]
[PHENYLS
Manual
QG MEASURES
1 Ml |
M2
M3
Action Level Notification
HH
X
X
GC/ECD Performance Check
X
X
Initial Calibration (CF)
JX
x
Initial Calibration (%RSD)
X
X
Continuing Calibration (RPD)
X
X
Laboratory Blank
1 * J
X
X
MS/MSD (%R,HPD)
X
X
Field Quality Control (dup., blnk.. PE samp.)
1—J
X
X
Sample Paperwork
rn
X
X
Holding Time
X
X
Retention Time
x
X
X
Surrogate Recovery
¦
X
X
Dilution Factor
X
x
Moisture Content
X
Pesticide Cleanup Checks
X
Chromatograms
x '
X
X
Raw Data
X
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Procedure No.: Ml-PEST
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Date: 06/30/1995
Page 3 of 20
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 ai the
site. In accordance with the Region III Hazardous Waste Division policy, the EPA RPM
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:
i •
• 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.: Ml-PEST
Revision: 1
Date: 06/30/1995
Page 4 of 20 ....
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.
Table Ml-PEST-2
PESTICIDES AND POLYCHLORINATED BIPHENYLS AND ACTION
LEVELS
Action
Action
Compound
Level*
Compound
Level*
Chlordane
63
Endrin
5
Heptachlor
10
Lindane
1,200
Methoxychlor
2,000
Toxaphene
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 T"s with the action levels presented in Table Ml-PEST-2.
Following the identification of the contaminants exceeding die 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 leyels, 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.: Ml-PEST
Revision: 1
Date: 06/30/1995
Page 6 of 20
3.2.1 Acceptance Criteria
TjTie retention time acceptance criteria have been established by the EPA and Region m as
fpllows:
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 ±0.05 minutes for
compounds eluting before heptachlor epoxide and ±0.07 minutes for
compounds eluting after and including heptachlor epoxide. The retention
time for the surrogate tetrachloro-m-xylene (TCX) must be within ±0.05
minutes of the mean retention time determined from the initial calibration
and that for decachlorobiphenyl (DCB) must be within ±0.10 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 VDI 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
tijie 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 confirmied 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.: Ml-PEST
Revision: 1
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 nondetected. 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.
• If the misidentified peak was sufficiently outside the target pestibide
retention time' window, then the repotted values may. be a false positive; and
should be replaced with the sample CRQL Value.
• 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 negative.^ 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.
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.: Procedure No.: Ml-rPEST
SPG No.: Revision: 1
Data Reviewer: Date: 06/30/1995
Site: Page 8 of 20
Dates' Analyzed: Instrument ID:
Pes
tirides/Polychlorw
Table Ml-PEST-3
a ted Bipbenyls Retention time Windo
ws
Retention Time
Window in
Minnies
Primary Column
Secondary Column
Compound
Std. Ret Time
Range
Std. Ret. Time
Range
alpha-BHC
±0.05
1 "
. I
beta-BHC
±0sQ5 :
'
• '' •
detta-BHC
±005
gaffima-BHC (Lindane)
±0.05; :
1
Heptachlor
±0.05
• '
v
Heptachlor epoxide
. ±0.07
r
EndoauUanl
±0.07
, -
V . -
Diddrin
±0.07.
¦ ~ ¦
• 1
. . .
4,4'-DDB .
±0/>7r
Endrin
. ±0.07
EodosulfanII
±0.07
4,4'-DDD
±0.07
Eodowlfan sulfate
±0.07
.¦ j
4,4'-DDT
±0.07
j
i
Methoxychlor -
±0.07 .
'V
1
1
Endrin ketone
±0.07
- -
v ! .
Endrin aldehyde
±0.07
1
alpha-Chlordane
±0.07
1
gamma-Chlordane
±0.07
Toxaphene
±0.07
Aroclor 1016
±0.07
Aroclor 1221
±0.07
Aroclor 1232
±0.07
Aroclor 1242
±0.07
•
Aroclor 1248
±0.07
Aroclor 1254
±0.07
Aroclor 1260
±0.07
Tetrachloro-m-xylene (Surr.)
±0.05
Decachlorobiphenyl (Surr.)
±0.10
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Case No. • Procedure No.: Ml-PEST
SDG No.: Revision: 1
Data Reviewer:. Date: 06/30/1995
Site: ; Page 9 of 20
•Table Ml-PEST-4
PEST/PCB Retention Time Evaluation Summary
Dales 'Analyzed:
Instrument ID:
Column (1);
Column ©:
Sample Identifier:
Comments
1.
1.
2.
2.
3.
3. • • -
4.
4.
5.
5. •
«.
6- "
7. ¦
7. • .
8.
8. . ¦
9. • ¦
9. ¦
10.
10.
Sample Identifier & Retention Times for Primary Column (1) and Secondaiy Column (2)
1
2
3
4
5 .
6
7
8
9
10
Compound:
-
(1)
O)
a)
0)
ft)
0)
a)
C)
av
a)
a)
a>
a)
a)
a>
(!)
a>
a>
0)
alpha-BHC
*
beta-BHC
deha-BHC
gamma-BHC (lindane)
Heptachlor
1
Heptachlor epoxide
EadosulfanI
- ¦
Dieldrin
¦
4,4'-DDE
Endrin
Endoailfan P
4,4'-DDD
Endosulfan sulfate
4,4'-DDT
-
Methoxychlor
Endrin ketone
Endrin aldehyde
alpha-chlordane
,
gamma-chlordane
Toxaphene
Peak 1
r
Peak 2
Peak 3
Aroclor 1016
Peak 1
Peak 2
Peak 3
Aroclor 1221
Peak 1
Peak 2
Peak 3
Aroclor 1232
Peak 1
Peak 2
Peak 3
Aroclor 1242
Peak I
Peak 2
Peak 3
Aroclor 1248
Peak 1
Peak 2
Peak 3
Aroclor 1254
Peak 1
Peak 2
Peak 3
Aroclor 1260
Peak 1
Peak 2
Peak 3
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Procedure No.: Ml-PEST
Revision: 1
Date: 06/30/1995
Page 10 of 20
njiass 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
cjould be the reasons for erroneous reporting. The gas chromatographic profiles are the
primary tool used for the false negative evaluation under Level Ml.
3.3.1 Acceptance Criteria
There are no EPArestablished 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:
• Chromatograms must display single 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 and 100 percent of full scale.
• For any sample, the baseline of the chromatogram must return to below 50
percent of full scale before the elution time of alpha-BHC, arid 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.: Ml-PEST
Revision: 1
Date: 06/30/1995
Page 11 of 20-
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 quantitation
report for each sample is also necessary to retrieve the retention times since! 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 vistially
comparing the sample traces for fingerprint features.
3.3.3 Evaluation Procedures
Note: It is important to emphasize that the evaluatirii of the chromatograms goes hand-in-
hand with the retention time evaluations. Duriilg 'the evaluation of any one of these QC
measures, a substantial use of the other QC measure is involved. Therefore, it ma; r be
beneficial to carry out these two evaluations together.
• Visually inspect the primary and the secondary column chromatogramsj 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" (Le., 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,
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Procedure Noj Ml-PEST
Revision: 1
Date: 06/30/1995
Page 12 of 20
there should be at least 90 percent valley between the neighboring peaks.
This criteria is important for detectors such as the electron capture detector
(ECD) that do not allow for unequivocal identification. Poor peak resolution
between the adjacent peaks may results in estimated quantitation of both for
both compounds.
• Inspect the ECD 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 ECD profile for abrupt shifts in the baseline. Such shifts are
indicative of problems with. instruiq^U 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.
• 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 ECD profile wjll 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
ahd 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 riot 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.: Ml-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, "Ui" if
the ability to detect at low concentrations is also deemed to be jeopardped
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 bay
also be interfered with. Using professional discretion, the positive and
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.
• 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 some
fluctuation in the instrument electronics which may lead to drastic changes in
the sensitivity of the instrument to detect the compounds. As a ijote,
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.: Ml-PEST
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3.3.5 Reporting
Keeps notes of the problems and substantiate them with copies of both chromatograms and
other 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
ally 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
njot 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 in 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 Blanks—A 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 Blanks—An 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.: Ml-PEST
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Page 15 of 20 -
V
either the performance evaluation mixture or Individual Standard
Mixtures A and B. depending on the place in the analysis sequence.
• Sulfur Cleanup Blanks—A 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 sarfiples 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, etcC 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 blank, 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.: Ml-PEST
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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 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.
3.4.4 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
T^O.
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 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.
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Procedure No. : Ml-PEST
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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 qualificatitin 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 sotirce
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."
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.* Ml-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.
5*
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.
Sl
Blank Result 1.0
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.
5x
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.: Ml-PEST
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Page 19 of 20
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
not be defensible or enforceable.
Under the current CLP contracts, the original paperwork (i.e., the purge package orj the
administrative record) is included in the data package from the laboratory. It is assupied
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. TTiese documents are the chain-of-custody forms
and Region m Shipping Record.
3.5.1 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:
• 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.: Ml-PEST
Revision: 1
Date: 06/30/1995
Page 20 of 20
the Region III 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
Ensurethat 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 III Shipping Record correctly reflects the information on the chain-
ojf-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
against 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 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.
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I .
Procedure No.: M2-PEST
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Date: 06/30/<995
Page 1 ojf 31-
Appendix C-2
Validation of Pesticide/PCB Organic Analyte Data
Manual Level M2
1. Purpose and Applicability
This procedure provides step-oy-step instructions to manually validate the pesticide analyte
organic 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 reviey of
chromatograms as summarized in Table M2-PEST-1.
The procedure is applicable to.fhe Pesticide/PCB obtained using the. Contract Laboratory
program Statement of Work (CLP SOW). Hard copy data conforming to the applicable
CLP sow specifications are essential in order to-carry out the procedure.
Data validated using this procedure are considered, usable for the following typefc 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-PEST
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Page 2 of 31
Table M2-PEST-1
QC CHECKLIST FOR LEVEL M2
CLP RAS PESTICIDES-POLYCHLORINATED BIPHENYLS
QC MEASURES
. . * ... 1
Manual
Ml | M2
M3
Action Level Notification
X
X
X
GC/ECD Performance Check
X
X
Initial Calibration (CF)
X
x
Initial Cahbration(96RSD)
x;
X
Continuing Calibration (RPD)
X
X
Laboratory Blank
X
X
X
MS/MSD (%R, RPD)
X
X
Field Quality Control (dup.,blnk., PE samp.)
X
X
X
Sample Paperwork
X
X
X
Holding Time
X
X
Retention Time
X
X
X
Surrogate Recovery
X
X
Dilution Factor
X
X
Moisture Content
X
X
Pesticide Cleanup Checks
X
Chromatograms
X
X
X
Raw Data
X
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Procedure No.; M2-PEST
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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. 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 sue 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 (CCS—Contractual holding times only)
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
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Page 4 of 31
• Hand annotate the Fonn 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 andminor problems associated with the analysis
- Highlight issues that may.have affected detection limits
• Include the following attachments:
- List 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
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.
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Method 608/8080 Procedure No. i, M2-PEST
Case No: Revision: 1
SDG No: ! Date: j06/30/1995
. I^age 5 of 31
TABLE M2-PEST-2 ,
PESTICIDE/PCBS QUALIFIER SUMMARY (CALIBRATIONS, BLANKS, HOLDING TIME, SURROGATES, INTERNAL
STANDARDS) r
Date Analyzed:
ImtniomtlD:
Method Blank ID:
Extraction Date:
Matrix
Samole Identifier:
Hold Time
Out. davs
Last IND Standard before Analysis
Anal.
1
2
3
' 4 '¦
5:
6
i
..
•'W»>
-
• V': :i . '•
•A'
v.
mm
'i:l ..
-¦ ¦ •
,
t
• i
Column: Prixnsiy
V-i;'
Q
lalifiers
(+/¦)
Secondary
Compound:
Init CaL -
- Conti
>>15% or 20%° ft
«RSD>10
' * '
gWahlr*
1 Oont Cal.date/monlh
¦ Tinie
V ;• »
'¦ >.
• -•
'¦mm
afoha-BHC
. »
i: •*.: ••.
'
be?a-BHC
" ' •
>••/•<.:
¦ / •.
detta-BHC
*
1 •
••
.s _ .
••»
!
[
Endosulfan I
1
Dieldrin
.
4.4'-DDE
i.
Endrin
Endosulfan II
4.4*-DDD
Endosulfan sulfate
4.4--DDT
Methoxvchlor
Endrin ketone
alnha-chlordane
eamma-chlordane
Toxanhene
-
Aroclor-1016 fPCB-10161
Aroclor-1221 fPCB-122n
Aroctor-1232 fPCB-12321
Aroclor-1242 fPCB-12421
Arocjor-1248 CPCB-12481
Aroclor-1254 fPCB-12541
'
' Aroclor-1260 fPCB-12601
Dihutvlchlorendate fDBCl Surr.
Validation Criteria: Primary Column Secondary Column
Detected compounds ' %D < 15 and %D < 20
Undetected compounds %D <20 or %D < 20
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Method 608/8080 Procedure No.: M2-PEST
Revision: 1
Case No: Date: 06/30/1995
Page 6 of 31
SDG No:_
i auic iru*rco l O
PESTICIDE/PCBS SURROGATE AND MATRIX SPIKE QUALITY CONTROL
SUMMARY
Surrogate Data Summary
Sample Identifier.
Surrogate Recoveries, %R
Qualifiers (+M
Aqueous
SoU
(Acceptance Range, SSR):
(24-154)
<2045$
'-fr.
v."
x
, ¦ :
. r-
;
..
.........
;;
, . . . .
'
. . ¦
.
- *
Surrogate = Dibutylchlorendate (DBC)
MS/MSP Summary
Matrix Spike, Recovery,
%R
Matrix Spike Duplicate,
Recovery. %R
MS/MSD
Precision. RPD
Spike Compound:
Range
Actual
Range
Actual
Range
Actual
Qualifiers
(+/-)
AQUEOUS SAMPLES ,
eamma-BHC (Lindane)
56-123
56-123
14
Heptachlor
40-131
40-131
20
Aldrin
40-120
40-120
22
Dieldrin
52-126
52-126
18
Endrin
56-121
56-121
21
4.4'-DDT
38-127
38-127
27
SOIL SAMPLES •
eamma-BHC (Lindane)
46-127
46-127
50
Heptachlor
35-130
35-130
31
' ¦ j
Aldrin
34-132
34-132
43
'
Dieldrin
31-134
31-134
38
Endrin
42-139
42-139
45
4.4'-DDT
23-134
23-134
50
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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.
UL = Not detected, quantitation limit is probably higher.
Other Codes
Q = No analytical result.
* = Results reported firom 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 III 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 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
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Date: 06/30/1995
Page 8 of 31
EPA RPM or SPO
— EPA Section CMefs:
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 M2-PEST-4
PESTICIDES AND POLYCHLORINATED BIFHENYLS AND ACTION
''
LEVELS
Compound
Action
Compound
Action
Level*
Level*
Chlordane
63
Endrin
5
Heptachlor
10
Lindane
1,200
Methoxychlor
2,000
Toxaphene
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
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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 jierformed usine 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. Hie
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 Ps.- The marked
up forms should be clarified, that they represent validation of only die 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 Aroclors in cooled (@ 4°C) 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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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, thai-
discrepancies in the sample condition xauld affect the data.
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, V exceot 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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3.3 GC/ECD Instrument Performance Check
Performance checks on the gas chromatograph 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 each' GC column, and instrument used for
analysis. Hie Resolution Check Mixture contains the following pesticides
and surrogates: '
• gamma-C—
• Endosulfan I
• 4,4'-DDE
• Dieldrin
• Endosulfan sulfate
• Endrin ketone
• 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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• Endrin
• Methoxychior
• Tetrachloro-m-xylene
• Decachlorobiphenyl
b. The resolution of adjacent peaks for the PEM injections inv«Kucb calibration
(initial and continuing) must be 100 percent for both GC columns.
c. The absoluteretention times of each of the single componeat.pesticides and
surrogates in all PEM analyses must be within the -spetiffc^reteatidn time
windows centered around the mean retention times detenfiin& from the
three-point initial calibration using the individual Standard Mixtures. „ A list
of the retention time windows is found in Attachment .1, Table 1»:
For sample, for a given pesticide the mean, retention time is first
determined from the initial calibration and found to be 12.i& minutes. The
retention time window for this pesticide is ±0.05 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 -
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 VII PEST-1 Form VIII PEST, and chromatograms.
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3.3.3 Evaluation Procedure
1. Resolution Check Mixture
a. Verify from the Form VIE PEST that the resolution check mixture was
analyzed at the beginning of the initial calibration sequence on each GC
column andinstrum&i used for analysis.
b. Check the resolution check mixture data and Form VIPEST-4 to verify that
the resolution. criterion between two adjacent peaks for the required
compounds is^less'than or equal to 60percent.
2. Performance Eyjd^tidtflifiirture
Verify ^m tfe ;FotbFIH^EST that the Performance Evaluation Mixture (PEM)
was analyzed ai i^rinic^lfrequai^ and position sequence.
ia. Check the PEM diria from the initial and continuing calibrations to verify
that the resolution between adjacent peaks is 100 percent on both GC
columns.
b. Check the PEM data from the initial and continuing calibrations and Form
VD 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
1. 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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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 fell within the retention time windows, the associated sample results should
be carefully evaluated. Allsamples injected after the last in-contrpl standard are
potentially affected. It should be noted for TPO action if the PEM retention time
criteria are grossly exceeded^
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 dose 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 consider
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 whicb may De or
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.
iii. 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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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. Noiidetected 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 used to qualify data as unusable (R).
4. If RPD criteria are not met, qualify all associated positive results generated during
the analytical sequence witlrf'J" and the^ample quantitation limits for nondetected
target compounds with "UJ."
5. 4,4'-DDT/Endrin Breakdown:
a. If 4,4'-DDT breakdownis greater than 20.0 percent:
i. Qualify all positive results for DDT as "I/' biased low. If DDT
was not detected, but DDD and DDE are detected, thai 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 Endiin 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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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).
6. Potential effects on the sample data resulting from the initial calibration problems
should be noted in the data review narrative.
3.4 Initial Calibration
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 acceptableperformance at the beginning of the analytical sequence
and of producing a linear calibration curve.
3.4,1 Acceptance Criteria
1. 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 ot each ot 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 each 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 %R§D miist be less than
or equal to 30.0 percent. Calculation is included in Attachment 1,
Equation D.
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-^and 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 ±0.07 minutes is used to
determine retention time windows for all multi-component analyte peaks.
c. Calibration lactor 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, iForm Vm 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 VIII 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 ana
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. Nohdetected
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 B must bracket the other aid
of the 12-hour period.
2. The resolution between any two adjacent peaks in the midpoint concentration of
Individual Standard Mixtures A and B must be greater than* or: equal to
90.0 percent
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 amount for each of the
pesticides and surrogates in die midpoint concentration of the Individual Standard
Mixtures A and B must not exceed 25.0 percent.
3.5.2 Review Items
Form VIIPEST-1 and 2, Form VIII PEST, and chromatograms.
3.5.3 Evaluation Procedure
1. Check the Form VIII 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 VII 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 ihe continuing calibration sequence wore
not met, thai this should lie noted for TPQ action. If the noncompliance 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 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
limits 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 Med 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 fidd) activities. Th&
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 Blanks—A 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 Blanks—An 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 Blanks—A 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 Duroose 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 report^ per SDG, per matrix, per
concentration level, for each GC system used to analyze samples*-and for each
extraction batch.
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^), 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.
Specific actions are as follows:
1. 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.
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 "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 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) 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 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:
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.
' 5x
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
In this case, the sample result exceeded the adjusted blank result (5x
1.0) and the sample result is not qualified.
3.7 Surrogate Spikes;
Laboratory performanoe on individual samples is established by means of spiking samples
prior to extraction and analysis io determine surrogate spike recoveries. All samples are
spiked with surrogate compounds prior to sample extraction. The evaluation of the
recovery results of these surrogate spikes is not necessarily straightforward. Tlie sample
itself may produce effects due to such factors as interferences and high concentrations of
target and/or nontarget 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. 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 ±0.05 minutes, and DGB must be within ±0.10 minutes of the
- mean retention time determined from the initial calibration.
3.7.2 Review Items
Form II PEST, Form VIII PEST, and chromatograms.
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Procedure No*: M2-PEST
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3.7.3 Evaluation Procedures
1. Verify that the recoveries on the Surrogate Recovery Form n PEST arfe 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
the 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 basicconcern is whether the blank problems representan 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 thesecriteria.
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 "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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Procedure No.: M2-PEST
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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).
2. If surrogate retention times in PEMs, individual standards; and ^samples are outade
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.
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 III
PEST-1 and PEST-2 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 Hi 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 HI 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 MSand MSD results in conjunction with
other QC criteria imd determine the need for some qualification of the data.
2. The data reviewershould 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 a 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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Procedure No.: M2-PEST
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cleanup columns and cartridges, and verifying the 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-trichlorophenol 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 aire within 80 to
120 percent, if the recovery of 2,4,5-trichlorophenol is less than 5 percent,
and if no pieaks 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 Jflonsii cartridge solution analyses and the Form IX 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 IX 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 am similar to those ofjujevious 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 aunng
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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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.
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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Attachment 1 to Appendix C-2
Multi-Media, Multi-Concentration
Contractual Requirements and Equations
for Pesticide Data Review
GC/ECD Instrument Performance Check
Check the Performance Evaluation Mixture calculations using equations n.2, 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.
% BrtMnmDDT - "? (DDD+DDB) « 100 (A)
Amount in ng of DDT injected,
% Breakdown Endrin =
Amount found in ng (Endrin aldehyde + Endrin ketone) x 100
Amount of Endrin injected in ng
(B)
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.
RPD = F— ~ Cc<^ x 100 (D)
C
. nom
Where:
Cnom = True concentration of each analyte
Cede = Calculated concentration of each analyte from the analysis of the
standard
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Procedure No.: M2-PEST
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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 ±0.05 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
Retention Time Windows in Minutes
alpha-BHC
±005
beta-BHC
±0.05
gamma-BHC
±0.05
delta-BHC
±0.05
Heptachlor
±0.05
Aldrin
±0.05
alpha-Chlordane
±0.07
gamma-Chlordane
±0.07
Heptachlor epoxide
±0.07
Dieldrin
±0.07
Endrin
±0.07
Endrin aldehyde
±0.07
Endrin ketone
±0.07
DDD
±0.07
DDE
±0.07
DDT
±0.07
Endosulfan I
±0.07
Endosulfan n
±0.07
Endosulfan sulfate
±0.07
Methoxychlor
±0.07
Aroclors
±0.07
Toxaphene
±0.07
Tetrachloro-m-xylene
±0.05
Decachlorobiphenyl
±0.10
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
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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 x ^
Mean
where:
£ (*/ - (F)
Standard Deviation - I— 1'/2
w—1
Where: .
Zi — each individual value used to calculate the mean
x = the mean of n values
n — the total number of values
CF = ^>efl*^reg (V Height) of the Standard ^
Mass injected (ng)
n PF
CF=T tfj. H)
i-i n
Where:
CF = Mean calibration factor of n values
CFj = i"1 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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XPD .-F—Ccofcl x 100 (I)
^bobi
Where:
Cnom ' ¦ —' True concentration of each analyte
Ccj,. = 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
calcukted retention time windows, i.e., TCX must be within ±0.05 minutes of the mean
retention time determined from the initial calibration and DCB must be within ±0.10 minutes
of the mean retention timfe determined from the initial calibration.
Q
Surrogate Percent Recovery - -pr 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
% Recovery
RPD
% Recovery
RPD
Compound
Water
Water
Soil
SoU
gamma-BHC (Lindane)
56-123
15
46-127
50
Heptachlor
40-131
20
35-130
31
Aldrin
40-120
22
34-132
43
Dieldrin
52-126
18
31-134
38
Endrin
56-121
21
42-139
45
4,4'-DDT
38-127
27
23-134
50
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Procedure No.: M2-PEST
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Spike Recovery = x 100 (K)
SA .
Where:
SSR = Spike sample result
SR = Sample result
SA = Spike added
RPD = 1^ - MSDR\ x 100 CL)
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)
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
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..Reported CRQLs
The CRQL of the single component pesticides is calculated using equations N and O, as
appropriate.
CRQL for waters:
Sample CRQ% « Reference CRQfc x Ef (N)
Df = Dilution factor
CRQL for soils/sediments (dry weight basis):
Sample CRQL = Reference CRQL x % (O)
D = 100 - % moisture
100
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Appendix D
Validation of Inorganic Analyte Data
• Level IM-1
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Procedure No.: IM-1-INORG
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VALIDATION OF TARGET ANALYTE LIST METALS
AND CYANIDE DATA
MANUAL APPROACH IM-1
1. PURPOSE AND APPLICABILITY
This procedure provides instructions to manually validate the target analyte list
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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 tne tecnnicai aata quauiy cniena;
however, there are certain contracbialcriteria 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 tedinical criteria. It is incumbeait upon a data
validator to point out the
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Table IM-1-INORG-QC
QC CHECKLIST FOR LEVEL IM-1
CLP RAS TARGET ANALYTE LIST INORGANICS
• ...
QC MEASURES
IM-1 .
M2
Action Level Notification
X
X
Holding Times
X
x
Initial Calibration
x
X
Initial Calibration Verification
X
X
Continuing Calibration Verification
X
X
Instrument Blanks
x
X
Laboratory Blank
X
X
ICP Interference Check
X
X
Laboratory Control Sample
X
X
Duplicate Precision
X
X
Matrix Spike Recovery
X
X
Furnace QC (MSA)
X
x
ICP Serial Dilution
X
x
Field Duplicates
X
x
Reporting Limit Verification
X
x
Sample Paperwork
X
X
Raw Data
X
1M-1-INORO
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• Matrix Spike Sample-(CCS)
• Graphite Furnace Atomic Absoiption QC (CCS)
• Method of Standard Addition (MSA)
• ICP Serial Dilution (CCS)
• Field Duplicates (if included)
• Reporting Limit Verification (DDLs, linear range, dilution factors and
moisture content)
• Sample Paperwork
22 REPORTING REQUIREMENTS
Several forms have been developed to assist in the performance evaluation ana in Keeping,
trade 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. Hie fourth form,
IM-1-INORG-QL is used for summarizing all qualifiers for the samples. This EPA Region
m Inorganic Regional Data Assessment form is used by the data validatorto summarize
contractual deficiencies for the laboratory's CLP Technical Project Officer (IPO). 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 wirn
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-INORG
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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 ibrm(s)
GLOSSARY OF DATA QUALIFIER CODES (INORGANIC)
The codes described below are those recommended in the EPA's national Functional
Guidelines and the Region Hi's modifications.
Codes Relating to Identification
(confidence concerningpr^^ce W'^absenceof analytes):
U =' associated number indicatesapproximate
sanrolecdncentration necessary to.be detected.'
940 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.
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.
lM-l-INORO
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Other Codes
Q = No analytical result.
* — Results reported from diluted analysis.
Hie following subsections describe for each of the QC indicators the acceptance criteria,
location and retrieval of QC data, evaluation of the <^1 data, actions taken in the event the
QC acceptance criteria are exceeded, and documentation of the QC violations in a
standardized report form.
2.3 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 ef the potential human health nsk at the
site. In accordance with the Region m Hazardous Waste Division policy,the EPA RPM
or SPO must be promptly notified pf any contaminant exceeding the established action levd
or die 10-day health ad visory 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
EPA's Office of Solid Waste and Emergency Response has established -10-day advisory
limits and action levels for several organic compounds and dements of special health ride
concerns based on the Safe Drinking Water Act The target analytes and their 10-day
health advisory limits are listed in Table IM-1-INQRG-AL. The criteria for action levd
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.
IM-l-INORa
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• 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.
=========-=1 1 1 ,
Table IM-1-INORG-AL
TARGET ANALYTE LIST METALS AND ACTION LEVELS
Compound
Action
Level*
Compound
1 Action
Level*
Arsenic
50
Cadmium
40
1
Chromium
1000
Laid
15"
Nickd.
1000 :
Cyanide
200
•All units are ug/1.
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-1-INORO
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Procedure No.: 1M-14N0RG
- 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 fVTSRl at the laboratory.
2.4.1 Acceptance Criteria
Technical requirementsfor sample holding tunes 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 (Clean Water Act), and are
found in Volume 49, Number 209 of the Federal Register, page 43260, issued on
October 26< 1984;
• Metals: 6 months; preserved to pH < 2
• Mercury: 28 xlays; preserved to pH < 2
• Cyanide: 14 days; preserved to pH > 12
Contractual holding times havebeen 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 uie uaics 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-INORG
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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, thai 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 (EDL) 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 (fesults < 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).
4. Although the technical holding times for soil samples have not beat 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 analytic «i««
• Mercurv Analysis
• A blank and at least four standards must be used in establishing the
analytical curve.
• The conelatioa coefficient must be ^ 0.995. (This is a technical
criterion and not a contractual one.)
• Cyanide Analysis
• A blank rod at least three standards must be used in establishing the
analytical curye.
• The correlation coefficient must be ^ 0.995. (This is a technical
criterion and not a contractual one.)
Initial and Continuing Calibration Verification (ICV and CCV>.
• 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
115%R.
CRDL Standards for ICP (CRD and AA (CRA1.
• 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, Ns
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.
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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 and 14.
2.5.3 Evaluation Procedure
1. Verify that the instrumentwas calibrated daily and each time the instrument was set
up using the correct number of standards and blank.
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 fall within 1 percent of the contract windows (e.g.*
80 to 111 percent),
%R = x 100
Tmia
where:
Found = Concentration (in ug/L) of each analyte measured in the analysis of
the ICV or CCV solution
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 2XIDL, 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 defmed 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 m Inorganic Regional Data Assessment
Form.
1M-1-INORO
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 12 of 26
2. If the ICV or CCV %R falls: outside the acceptance windowns, using the following
guidelines for qualifying the data.
| Percent Recovery (%R)
Qualifier
1 Metals
Cyanide
Mercury
> IDL
< IDL
90-110
85-115
80-120
None
None
75-89
70-84
65-79
L
UL
>110
>115
>120
K
None
<75
<70
<65
L
R
• If the ICV or CCV^%R falls outside the acceptance windows; but within the
ranges of 75tb 89 perceit (metals) or 70-84(GN) or 65-7903g),-. qualify
results > IDL~as biased low (L), and results < IDL as biased low (UL).
• If the ICV or CCV %R is >110 (metals) or >115 (CN) or > 120 (Hg),
results < IDL are acceptable. Results > IDL should be qualified as biased
high (K).
• If the ICV or CCV %R is <75 percent (metals) or <70;peicent (CN) or
< 65 percent (Hg), qualify all positive results as unusable (R).
3. 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 >IDL, 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 dement is <50%, qualify the results > IDL, but <
2X CRDL as biased extremely low (L). Qualify results < IDL as unusable
(R).
1M-1-1NORG
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 13 of 26
2.6 BLANKS
TOanV 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 ah isolated occurrence notafiecting
other data.
2. 6.1 Acceptance Criteria
No contaminants should be in the blank(s) at concentrations, > IDL.
2.6.2 Data ReguirementsandRetrieval of Data
Forms 1 and 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 th£t 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
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-1-INORG
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 14 of 26
• 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 jnay 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
The ICP Interference Check Sample (ICS) verifies the contract laboratoiy's interelement
and background correction factors.
2.7.1 Acceptance Criteria
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).
2. Results for the ICS solution AB analysis must fall within the control limits of ±
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:
ICS %R - Found'Solution AB x 1(x)
True Solution AB
where:
Found Solution AB = Concentration (in ng/l) of each analyte measured in the
analysis of solution AB
True'Solution AB •= Concentration (in /xg/1) of each analyte in solution AB
2. Check the results with an absolute value > IDL for those analytes which are not
present in the ICS solution.
1M-1-INORG
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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 dement 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).
• If sample results are < IDL, and the ICS recovery for that analyte falls
within the range t>f 50 to 79 .percent, the possibility of false negatives may
exist. Qualifythe data for these samples as detection limits biased low
(UL).
• If ICS recovery results for. an dement is < 50 percent, qualify results >
IDL as biased low (L)r and results < IDL as unusable (R).
2. If results > IDL are observed for dements 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 levds 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 levds of interferents, qualify results for the affected analytes
< IDL as biased low (UL), qualify results for the affected analytes > IDL 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
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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 poctoimance 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 YE and verify that results fall within the control limits.
2. Randomly verify the reported recoveries on Form VII using the following equation:
LCS %R = LCS Found x 100
LCS True
where:
LCS Found = Concentration (in pig/1 for aqueous; mg/kg for solid) of each
analyte measured in the analysis of LCS solution
LCS True = Concentration (in jtg/1 for aqueous; mg/kg for solid) of each
analyte in the LCS source
2.8.4 Action
1. Aqueous LCS:
1M-1-INORG
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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 50 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 < ;0L smd LCS recovery Ms within the range of 50 to
79 percent, qualifythedatafar die affected analytesas biased low (UL).
• If LCS recovery results are <50 percent, qualify results > IDL as biased
low (L), and results < IDL a$ unusable (R).
2. Solid LCS:
• If the splid I^iiecqwegrjbr any analyte is below tiie tower acceptable
control limit, qualify all sample results > IDL as biased bw (L). If the
LCS recovery is uppa control lindt, qualify the results > IDL as
biased high (K) ;
• 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 ±20 percent (35 percent for soil) for the Relative Percent
Difference (RPD) shall be used for sample values >5X CRDL.
j. A control limit of ± CRDL (±2X 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
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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 verify that results fall within the control limits.
2. Recalculate one or more RED using the following equation to verify that results
have been correctly reported on Form 6.
RPD = x 100
(S+D)/2*.
wftere:
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 > DDL, for that analyte in all associated samples
of the same matrix as estimated (J), and results < DDL as estimated (UJ).
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 III 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-1-1NORa
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Procedure No.: IM-1-4NORG
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 die 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)** 2X CRDL,
whichever is greater.
2.10.2 Data Requirements and Retrieval of Data
Forms 1, and 5A and 5B.
2.10.3 Evaluation Procedure
1. Review sForm SA and verify that results fall within the specified limits.
2. Recalculate one or more %R using the following equation to verify thai-results were
correctly reported on Form 5A.
%R = (SSR"SR) x 100
SA
Spiked sample result
Sample result
Spite added
3. Verify that the field blank was not used'for spite analysis.
4. Verify that a post-digestion spike was performed when required, and at specified
spike concentrations.
2.10.4 Action
1. If the spike recovery is > 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).
where:
SSR =
SR =
SA =
1M-MNORG
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Procedure No.: IM-1-INORG
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
(UL).
5. If spike recovery result* fall < 30 percent and the sample result Aie < 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 onthe EPA Regioa.ni Inorganic Regional Data Assessment
form.
7. If a post-digestion spite-was not performed wnen required, or the recoveries fall
outside the matrix spike recovery limits, document this in the narrative. CTh© post- „
digestion recovery (lata', sue 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-1-INORG
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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 hieh YK). samole results < IDL are acceotable.
3. If the analytical spite recovery is less than 10% and the results are < IDL, die data
should be qualified usable (R). Sample results > IDL should be qualified biased
extrememly low (L).
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.
2.12.2 Data Requirements and Retrieval of Data
Forms 1 and 9.
1M-1-INORG
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 22 of 26
2.12.3 Evaluation Procedure
1. Recalculate at random the %Ds using the following equation to verify the dilution
analysis results reported on Form 9.
%D = X 100
where:
I = Initial sample result
S = Serial dilution resuk .(instrument reacting X 5)
2. Determine whether there % amative interference. Generally; , 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. Hie apparent negative interference may be
related to sample concentrations in the less accurate .regions of the ICP
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, When 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
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
There are no review criteria for field duplicate analyses comparability.
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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 PmceSufe
Samples which are field duplicates should be identified usingEPA Sample Traffic Reports
or sample field sheets.Thereviewer should compare the results reported for each sample
and calculate theRelative Percent Di£ference (RPD), if appropriate.
2.13.4 Action
Any evaluation of the fidd 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
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 H must be greater than 5X IDL.
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.
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
Page: 24 of 26
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.
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 lDLs 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.
2. Verify that the linear ranges for the ICP metals are reported on Form 12, and no
undiluted sanrole data are reported above the linear ranges.
3. Verify on the Form is that tne uRDLs have been adjusted for any dilution factors
and moisture content, as applicable.
4. Verify that the sample results are >5X 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 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.
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, die evaluation
criteria and procedures described below apply only to the documents that are generally
1M-1-INORG
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Procedure No.: IM-HNORG
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.
2.15.1 Acceptance Criteria
Criteria for acceptability or authenticity or die sampling paperwork, document control and
chain-of-custody have been established by the National Enforcement Investigations Center
(NEIC), to support the CLP. Overall criteria are too numerous and robjebtive to be
discussed here, but the criteria that iq>ply 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 sue minimally required to confirm the authenticity of die sample and its
data.
• Tlie 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.
2.15.3 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 m 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-INORQ
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Procedure No.: IM-1-INORG
Revision: 2
Date: 06/30/95
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-1-1NORG
-------
Case No.: ¦
SDG No.! ^
Data Reviewer/Date:,
Site: ' •0 * • ^ '
' !^1jb^^]-IHPG-HI . Holding Time: Summary
Sample
;,„- AA (180 Days)
Hg (28 Days)
CN (14 Days)
Number
Date
Coll.
Date
Reed. -V
Lab.
41
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Date
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Anal.
Hold.
Time,
Days
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Date
Prep.
Anal.
Hold.
Time,
Days
Qual.
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Procedure No.: 1M-1-INORG
Revision: 2
• / Date: 06/30/1995
-------
Case No.: ¦ ' ¦' Procedure No.: IM-1-IN0RG
SDG No.: _ •' ' - Revision: 2
Data Reviewer/Date: / ; Date: 06/30/1995
Site: ¦
Table IM-1—INORG—CAL. TAL Metals and Cyanide Calibration and Blank Qualifier Summary
ICP Instrument ID:
Instrument Calibrated? , Yes No
ICP Date Started:
Sample Identifier:
Sanmle Identifier:
ICP Date Ended:
AAInstrument IDs: As Pb
1. •
11-
2.
12.
3. - • - ^
13.
14.
TI *
¦;
15. "•
Instruments Calibrated? 'i
a
AA Date Started: %
AA Date Ended:
16. :•¦¦¦ ¦ . :
&%&!&&&?s--: ¦
18-
¦ ¦¦¦¦¦<¦¦ ¦ - ...
19-
10..
20. r
-wV ' ' 'It
1CV
gERM*
1
jtjcb"
CCB
FB
Rdd
Bl.
Analyte
(Criteria)
<90410
yj:*:'--*..?.
,rf~~r-r"-T
Qual.
-------
Procedure No.: XM-1-IN0RG
Revision: 2
/ . Date: 06/30/1QQS
| Table IM-1-
INORG-SPK. TAL Metals and Cyai
tide Matrix Spike, Duplicate and ICP Serial Dilution Qnality Control Summary
1
Matrix Spike/Duplicate
Post Digest/Anal. Spike*,
Analyte
Rec, %R
RPD
ICP Ser. Dil. .
ICP
AA
LCSRecovwv
(Criteria):
7S-125
2S(3S)»
" Quals.
+/-109&
Quals."
75-125%
85-115%
Quale.
80-120%-
Quals.
Aluminum At
; '
Anthnoinr Sb
* ¦ '"/S-v-**?',V- ;.-r V-..
Anente;£?-%;As •'
i
)
"""!
;•
Barim :V ' Bt
1
Berydhnn fie:
-
¦; *
Cfedminm • Qtf
cud
Cbraminm ' :Cr
t
1
i
i
Copper-" ^ Ob ¦
i'
bn •••''
•><
Lead 'v* Tb '
-
•*
Magnesium Me
1
• I-".' • •
Manganese Mn
ifeteutr- He
.¦
•
Nickel Ni
¦ ¦>'
Potassium K
• •
Selenium Se
• •
Silver Ag
Sodium Na
¦
. .
Thallium T1
*
Vanadium V
Zinc 2a
Cyanide CN
Note: See the SOP for the exact criteria under special situations.
"There are no criteria at the present time to qualify the ICP metals or Cyanide based on the post-digestion soike remuMi's,
' The precision RPD for soil samples is 35..
•Therange of 80-120% R is used only for the aqueous LCSs. Solid LCS samples hav
'e specific recovery ranges for each analyte.
«-ase no.:
SDG No.:_
Data Reviewer/Date:,
Site:
-------
Case No.:_
SDG No.:
TT
Data Reviewer/Date:.
Site: -
' . ''"-.I.
Procedure No.: IM-1-1N0RG
Revision: 2
Date: 06/30/1995
Table IM-l-INORG-QL. Summary of Data Qualifiers
Sample
Number
. Analyte
Al
Sb
As
Ba
Be
Cd
Ca
Cr
Co
Cu
Fe
Fb
Mg
Mn
Hg
m
K
Se
Ag
Na
n
V
Zn
CN
i
;
-
' V.
--
.-V
' i
J
,,
i
¦w
I
1
i
: |
i
i ;
i
'i
v.
* ?
. •
»
s
J
:> ..
: ~
/
«•
• .
-
,
t
' -
-
, >
\
. 1
v
¦-v:< ,
.. . •.
•i.l ¦
.
¦
. : ¦
i
-
• .
'
* .
1
•i
-------
Case No.:_
SDG No.:"
Data Reviewer/Date:_
Site: '
-Procedure No: IM-1-INORG
—- Revision: 2
Date: 06/30/1995
Case No.
Laboratory.
SDG No. _
SOW No. _
IPO: Action .
Table IM-1-IN0RG-IRDA
EPA Region HI
Inorganic Regional Data Assessment
Site
FYI.
Number of Samples/Matrix
Reviewer (if not CRL)
Reviewer's Name .
¦ . Completion Date
Data Assessment Summary
ICP AA
Hg
Cyanide
HoldingTimes.
Calibrations
•Blanks
ICS-
LCS
Duplicate Analysis
Matrix Spike
Post Digestion/Analytical Spike
MSA
Serial Dilution
Field Duplicates
. Reporting Limit Verification
Sample Paperwork
O = Data had no problems/or qualified due to minor problems.
M = Data qualified due to major problems.
Z = Data unacceptable.
X = Problems, but do not affect data.
Action Items:
Areas of Concern:
Notable Performance:
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