Region I, EPA-New England Data Validation Functional Guidelines for Evaluating Environmental Analyses


              PART II

Volatile/Semivolatile Data Validation
        Functional Guidelines
             December 1996

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VOLATILE/SEMIVOLATTLE DATA VALIDATION FUNCTiONAL GUIDELINES - PART II
The requirements to be checked in validation are listed below. “CCS indicates that the contractual requirements for these
items will also be checked by Contract Compliance Screening (CCS). CCS requirements are not always the same as data
validation criteria. ‘CADRE” indicates that CADRE checks for these items in CLP-Low/Mediuni Organic electronic data
and provides a CADRE printout. Additional manual evaluation may be required Refer to the Guidance Document for
Completing Region I Data Validation Utilizing CADRE Data Review , February 1995, or most recent revision (Auachment
L of Part I, Data Validation Manual).
I. . (CADRE) VOAIS V-i-i
I I. . (CADRE) ... VOA/SV-lI-1
III. .. (CADRE) .... VOAISV-lIj-1
IV. (CADRE).. . . VQAJSV4V.. 1
V. (CADRE) .... VOA/SV-V-1
vi. (CADRE) VOA/SV-V1-1
V I I. (CADRE) ... VOA/SV-VII-1
VIII. (CADRE) ... VOA/SV-VIII-1
IX. .. . VOAJSV-IX-l
X. . .. VOAJSV-X-i
xi. ... . VOA/SV-XI-1
XII. .... VOA/SV-X1I-i
x l i i. ... VOA/SV-XIiI-i
XIV. . VOA/SV-XIV-l
XV. ... VOA/SV-XV -1
xv’.
XVII.
Appendices
Appendix A
Appendix B
Appendix C
Appendix D
Appendix E
Preservation and Technical Holding Times (CCS) .
GC/MS instrument Performance Check (Tuning) (CCS)
Initial Calibration (CCS) .
Continuing Calibration (CCS)
Blanks (Method Blanks Only) (CCS)
Surrogate Compounds (CCS)
Internal StandMcls (CCS)
Matrix Spike/Matrix Spike Duplicate (CCS)
Field Duplicates
Sensitivity Check
FE Samples/Accuracy Check
Target Compound Identification
Compound Quantitation and Reported Quantitacion Limits
Tentatively Identified Compounds
Seniivolanle Cleanup
System Performance
Overall Evaluation of Data
CL? SOW OLMO3.2fVolatile Organic Analysis
CLP SOW OLMO3.2/Semivolatile Organic Analysis
CL? SOW OLCO2.OILow Concentration Volatile Organic Analysis
CL? SOW OLCO2.O/Low Concentration Semivolatile Organic Analysis
VOA/SV Functional Guidelines Action Tables
(CADRE)
VOA/SV-XV I-1
VOA/SV-XVII-1
VOAISV- I
DRAFT 12/96

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PART ll-VOA/SV Preservation and Technical Holding Times
I. PRESERVATION AND TECHNICAL HOLDING TIMES
A. OBJECTIVE
The objective is to ascertain the validity of the analytical results based on the preservation techniques which
were used and the holding time of the sample from time of collection to time of sample preparation and
sample analysis, as appropriate.
B. CRITERIA
The ReQion I. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region I Organic data. The CLP-Volatile/Semivol tiie method QC
acceptance criteria listed in Appendices A and B should be used as the default criteria ‘ . lien none exist for
the VolaLile/Semjvo latjje analytical method utilized and when similar QC parameters are required by the
non-CLP method and acceptance criteria have not been specified. Deviations, modifications or non-CLP
method-specific QC acceptance criteria may be used but must be explicitly defined in tabular format in the
site-specific EPA approved QAPJ P/SAP or aniendnient to the QAPj P/SAP.
1. REGION I PRESERVATION CRITERIA
SAMPLE TYPE
PRESERVATION
Volatile Aqueous a
CODE
Volatile SoilfScdjnient b
1,2,3
Semivolatile Aqueous a
1,3
Semjvolatj le Soil/Sediment b
1,3
VOAJSV Sludge b
— 1,3
VOAJSV Oily Waste b
1,3
VOAJSV Biological Tissue
1,3
VOA Air (Canister) C
3.4
VOA Air (Adsorbent Tubes) C
35
—
SV Air (PUF, Filters) C
1,3
SVWipesC
1,3
SvFlyAshb
1,3
Preservation Code: References:
1. Cool @ 4°C (± 20) a. 40 CFR, Part 136, Appendix A, 600 Series
2. Preserve with HCI to at least pH 2
3. Protect from light b. SW-846, 8000 Series
4. Freeze
5. Roon Temperature (Avoid excessive heat) C Region I policy
VOA/S v-I- i DRAFF 12/96

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PART ll-VOA/SV Preservation and Technical Holding Times
2. REGION I TECHNICAL HOLDING TIME CRITERIA
SAMPLE TYPE
CRITERIA
Volatile Aqueous a
If the sample was not properly preserved with HCI but was
protected from light and scored at 4°C (± 2°), aromatic
volatiles must be analyzed within 7 days and non-aromatic
volatiles within 14 days of sample collection.
If the sample was properly preserved, then both aromatic and
non-aromatic volanles must be analyzed within 14 days of
sample collection.
Volatile
Soil/Sediment b
Properly preserved soil/sediment samples must be analyzed
within 14 days of sample collection.
Semivolacile a
Aqueous
Extraction of properly preserved aqueous samples by liquid-
liquid procedures must be started within 7 days of sample
collection.
Extraction of properly preserved aqueous samples by
separatory funnel or solid phase extraction (SPE) must be
completed within 7 days of sample collection.
Extracts must be analyzed within 40 days following sample
extraction.
Semivolatile
Soil/Sediment b
Extraction of properly preserved soil/sediment samples by
sonication or soxhiet procedures must be completed Within 14
days of sample collection.
Extracts must be analyzed within 40 days following sample
extraction.
VOA/SV Sludge b
Purae and trap or extraction of properly preserved sludge
samples by sonication or soxhiet procedures must be
completed within 14 days of sample collection.
Extracts must be analyzed within 40 days following sample
extraction.
VOA/SV
Oily Waste b
Purge and trap or extraction of properly preserved oily waste
samples by sonication or soxhlet procedures must be
completed within 14 days of sample collection.
Extracts must be analyzed within 40 days following sample
extraction
VOA1SV-I-2 DRAFI’ 12/96

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PART U-VOAISV Preservation and Technical Holding Times
SAMPLE TYPE
.1 CRITERIA
VOA/SV
Biological Tissue C
Extraction and analysis of frozen tissue
must be completed within 60 days of
Sample collection. Tissue must remain
frozen until homogenizanon is completed.
Extrac:ion andlor analysis must be initiated
irrunediately after
VOA Air C
homogenization.
Analyses of properly preserved VOA air
samples must be completed within 14 days
of sample collection.
Pre-cleaned and cerufjed volatile air
collection devices, i.e., Tenax and charcoal
cartridges and SUMMA canisters, must be
utilized for sample collection within the
method-specified time frame.
SV Air C
Analyses of properly preserved SV air
samples must be completed within 14 days
of sample collection.
Pre-cleaneti and certified sernivolatile air
collection devices, i.e., PUFS, and filters,
must be utilized for sample collection
within the
SV Wipes C
method-specified_time_frame.
Extraction of properly preserved SV Wipe
samples by sonicacion or soxhlet procedures
must be completed within 14 days of
sample collection.
Extracts must be analyzed within 40
days
SV Fly Ash b
Extraction of properly preserved SV fly ash
samples by sonication or soxhlec procedures
must be completed within 14 days of
sample cdllectiori.
Extracts must be analyzed within 40 days
following sample extraction
VOA1SV-1-3
DRA.FF 12/96

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PART II-VOA/SV
Preservation and Technical Holding Times
C. EVALUATION! D. ACTION
C. EVALUATION
D. ACTION
I. Volatile Samples
a. Preservation
Examine the sample records (EPA Traffic
Reports andJor COC Forms), Sample
Receipt forms (DC-i Form), laboratory
tracking/storage forms, and the data
package narrative to verify that samples
were properly preserved by the sampler and
the laboratory maintained preservation. If
adequate documentation on field sample
preservation is not present in the data
package, then the validator must contact the
sampler and/or laboratory to obtain the
missing information.
i. Verify that volatile samples were
refrigerated or frozen (as required) and
protected from light according to
Region I preservation criteria.
All potential impacts on the sample data
resulting from preservation andJor holding time
anomalies should be noted in the Data
Validation Memorandum. The validator should
also document and justify all technical decisions
made based on professional judgment in the.
Data Validation Memorandum.
I. Volatile Samples
a. Preservation
If the sampler cannot be contacted or
cannot produce adequate preservation
documentation, then the validator should
assume the samples were not preserved and
should document on the holding time
worksheet the date that sampler contact was
attempted andlor established. If the
laborator ’ cannot provide adequate sample
preservation information, then the validator
should use professional judgment to accept,
qualify or reject the sample data.
If the samples were not preserved properly
in the field and/or if the laboratory failed to
properly maintain sample preservation, then
the validator should take the following
actions:
1. If volatile samples for aqueous and
soilisediment matrices were not
refrigerated andIor protected from light
according to Region I preservation
criteria, then the validator should
estimate (1) positive detects and reject
(R) non-detects for the affected
samples, regardless of whether or not
technical holding time criteria were
met and regardless of whether or not
the sample (aqueous) was acid
preserved.
For other matrices, the validator
should estimate (J) positive detects and
should use professional judgment to
qualify or reject non-detects when
temperature and light protection
preservation critena were not met.
Professional judgment should be used
when the laboratory has reported
transportation cooler temperatures that
slightly exceed the upper limits of the
preservation criteria (> +6°C). In
this case, the laboratory procedure for
monitoring cooler temperature may be
in question. In this event, the validator
should document all justifications for
qualifying or not qualifying sample
data in the Data Validation
Memorandum.
VOAJSV-I-4
DRAFI’ 12/96

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PART rI-VOAJsv
Preservation and Technical Holding Times
Verify from the EPA Traffic Report
and/or COC Form and the data
package narrative that aqueous volatile
samples were preserved with HCI
according to Region I preservation
criteria.
iii. Review sample records (CCC Forms,
Sample Receipt and/or Login Forms,
DC-I, etc.) to determine if excessive
headspace in any aqueous sample was
noted by the laboratory.
b. Technical Holding Times
Verify that volatile samples were
analyzed within the technical holding
time criteria. Establish technical
holding times by comparing san pling
dates reported on the EPA Trafffc
Report and/or COC Forms with dates
of analysis on tabulated result forms.
If data package documentation does not
list the pH of each aaueous VOA
sample, then the validator should
contact the laborator to obtain any
omitted information. If aqueous
volatile samples were not preserved
with HCI according to Region I
preservation criteria, then the validator
must evaluate holding times to
determine if qualification of sample
data is necessary for detected and non-
detected aromatic and non-aromatic
compounds.
iii. If volatile aqueous samples contain
excessive headspace (bubbles greater
than 2 mm diameter should not be
present), then the validator should
estimate (J) positive detects and reject
(R) non-detects.
b. Technical Holding Times
If aqueous volatile samples were not
preserved with HCI (but refrigeration
and light protection criteria were met)
and the samples were not analyzed
within 7 days, then the validator
should:
- Estimate (I) aromatic positive
detects analyzed within 14 days
- Reject (R) aromatIc non-detects.
- Accept non-aromatic positive
detects analyzed within 14 days
- Accept non-aromatic non-detects
analyzed within 14 days.
- Estimate (J) aromatic positive
detects analyzed after 14 days.
- Estimate (J) non-aromatic positive
detects analyzed after 14 days.
- Estimate (UJ) non-aromatic non-
detects analyzed after 14 days.
If volatile samples for aqueous and
soil/sediment matrices were properly
preserved, but the technical holding
time criteria were exceeded yet
samples were analyzed within 28 days,
then the validator should estimate (J)
positive detects and (UJ) non-detects.
For other matrices, the validator
should estimate (J) positive detects and
should use professional judgment to
qualify or reject non-detects when
technical holding time criteria are
exceeded.
For all matrices, if technical holding
times for volatile samples were grossly
exceeded (> 28 days), then the
validator should estimate (I) positive
detects and retect (R) non-detects .
1. a. ii.
C. EVALUATION U. ACTION
1. a. ii.
VOA/SV-I-5
DRAFT 12/96

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PART fl-VOAJSV
Preservation and Technical Holding Times
l. b. ii. Check the raw data including
instrument run and extraction logs to
verify reported sample extraction and
analysis dates.
2. Sermvolatile Samples
a. Preservation
Examine the sample records (EPA Traffic
Reports and/or COC Forms), Sample
Receipt forms (DC-i Form), laboratory
tracking/storage forms, and the data
package narrative to verify that samples
were properly preserved by the sampler and
the laboratory maintained preservation. If
adequate documentation on field sample
preservation is not present in the data
package, then the validator must contact the
sampler and/or laboratory to obain the
missing information.
i. Verify that semivolatile samples were
refrigerated or frozen (as required) and
protected from light according to
Region I preservation criteria.
If discrepancies between the raw data
and reported data are found, then the
validator should contact the laboratory
to obtain corrected raw data and
forms. If a discrepancy remains
unresolved, the validator must use
professional judgment to decide which
value is accurate. Under these
circumstances, the validator may
determine that the sample data should
be qualified or rejected. A discussion
of the rationale for data qualification
and the qualifiers used should be
documented in the Data Validation
Memorandum.
2. Semivolatile Samples
a. Preservation
If the sampler cannot be contacted or
cannot produce adequate preservation
documentation, then the validator should
assume the samples were not preserved and
should document on the holding time
worksheet the date that sampler contact was
attempted and/or established. If the
laboratory cannot provide adequate sample
preservation information, then the validator
should use professional judgment to accept,
qualify or reject the sample data.
If the samples were not preserved properly
in the field and/or if the laboratory failed to
properly maintain sample preservation, then
the validator should take the following
actions:
I. If seniivolatile samples for aqueous and
soil/sediment macrices were not
refrigerated and/or protected from light
according to Region I preservation
criteria, then the validator should
estimate (.1) positive detects and
estimate (UJ) non-detects for the
affected samples, regardless of whether
or not technical holding time criteria
were met.
For other matrices, the validator
should estimate (J) positive detects and
should use professional judgment to
qualify or reject non-detects when
temperature and light protection
preservation criteria were not met.
Professional judgment should be used
when the laboratory has reported
transportation cooler temperatures that
slightly exceed the upper limits of the
preservation criteria (> +6°C). In
this case, the laboratory procedure for
monitoring cooler temperature may be
in question. In this event, the validator
should document all justifications for
qualifying or not qualifying sample
data in the Data Validation
MemnrinrIa ryl
C. EVALUATION
D. ACTION
1. b. ii.
YOA/SV-I-
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PART II-VOA/SV
Preservation and Technical Holding Times
C. EVALUATION
2. b. Technical Holding Times
Verify that sernivolatile samples were
extracted within technical holding urne
criteria. Establish extraction holding
times by comparing sampling dates
reported on the EPA Traffic Report
and/or COC Forms with dates of
extraction reported on tabulated result
forms.
1. Verify that liquid-liquid extract ions
for semivolatile aqueous samples
were begun within 7 days of
sample collection.
2. Verify that aqueous semivolatile
extractions by separatory funnel
were completed within 7 days of
sample collection. (Note:
OLMO3.2 does not allow
separatoiy funnel extraction of
semivolatiles.)
3. Verify that aqueous semivolatile
extractions by solid phase
extraction (SPE) or other
extraction technique were
completed within 7 days of sample
collection.
4 Verify that sernivolatile
soil/sediment sample extractions by
sorucation or soxhiec procedures
were completed within 14 days of
sample collection.
5. Verify that samples of other
matrices, i.e., wipes, biological
tissue, were extracted within the
Region I holding time cnteria.
Verify that semivolacile samples and/or
extracts (as required) were analyzed
within technical holding time cntena
for analysis. Establish analytical
holding times by comparing collection
and/or extraction dates (as required)
and analysis dates reported on tabulated
result forms.
D. ACTION
2. b. Technical Holding Times
If aqueous and soil/sediment
semivolazile samples were properly
preserved, but the technical extraction
and/or analytical holding time criteria
were exceeded, then the validaor
should esmnate (J) positive detects and
estimate (UJ) non-detects.
For other matrices, the validator
should estimate (J) positive detects and
should use professional judgment to
qualify or reject non-detects when
technical holding time criteria are
exceeded.
For all matrices, if seniivojatile
extraction technical holding time
criteria were grossly exceeded (> 28
days) and/or analytical technical
holding time criteria were grossly
exceeded (> 60 days), then the
validator should estimate (3) positive
detects and reject (R) non-detects.
VOA/SV-I-7
DRAFT 12/96

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PART [ I-VOA/SV Preservation and Technical Holding Times
C. EVALUATION D. ACTION
*2. b. ii. Check the raw data including extraction 2. b. ii. If discrepancies between the raw data
and instrument run logs to verify and reported data are found, then the
reported sample extraction and analysis validator should contact the laborawry
dates. to obtain corrected raw data and
forms. If a discrepancy remains
unresolved, the validacor must use
professional judgment to decide which
value is accurate. Under these
circumstances, the validacor may
determine that the sample data should
be qualified or rejected. A discussion
of the rationale for data qualification
and the qualifiers used should be
documented in the Data Validation
Memorandum.
* Note: The following subsections are applicable only to a Tier Ill data validation:
C.1.b.ii, C.2.b.ii
VOA/SV-l-8 DRAF 12196

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PART ff-VOA/SV Preservation and Technical Holding Times
Table VOA/SV.I- [ :
QUALIFICATION OF VOLATILE ANALYTES BASED ON
PRESERVATION & TECHNICAL HOLDING TIMES
I PRESERVATION
Mathx Refrig. Acid
& Light Preserved
Protected
TECHNICAL HOLDING TIMES 1
 7 Days
7 < UT  14
Days
14 < HT 28
Days
> 28 Days
AQ
No
Yes or No
J - detects
R - non-detects
J - detects
R - non-detects
J - detects
R - non-detects
J - detects
R - non-detects
AQ
Yes
Yes
A
A
J - detects
Ui - non-detects
J - detects
R - non-detects
AQ
Yes
No
A
Aromatics
J - detects
R - non-detects
Non-aromatjcs
A - detects
A - non-detects
Aromatics
J - detects
R - non-detects
Non-aromatjcs
I - detects
Ui - non-detects
I - detects
R - non-detects
S/S
No
N/A
I- detects
R - non-detects
J - detects
R - non-detects
I - detects
R - non-detects
I - detects
R - non-detects
S/S
Yes
N/A
A
A
J - detects
UI - non-detects
I - detects
R - non-detects
Note: AQ = Aqueous, S/S = Soil/Sediment
For other matrices, the validator should estimate (J) positive detects and use professional judgment to qualify or
reject non-detects when Region I preservation and/or technical holding time criteria are not met.
For VOA aqueous samples containing excessive headspace (bubbles greater than 2 mm diameter); i-detects, R-non-
detects
VOA/SV-I-9 DRAFF 12/96

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PART II-vOA/Sv Preservation and Technical Holding Times
Table VOA/SV- [ .2
qUALIFICATION OF SEMIVOLATILE ANALYTES BASED ON
PRESERVATION & TECHNICAL HOLDING TIMES
PRESERVATION
TECHNICAL HOLDING TIMES
Matrix
Refrig. & Light
Protected
Extracted
andfor
Analyzed
Within H.T.
Ectracied
and/or
Analyzed
Outside H.T.
If Extraction HT > 28 days
and/or
Analytical HI> 60 days
AQ and S1S
Yes
A
J - detects
UJ - non-detects
J - detects
R - non-detects
AQ and S/S
No
J - detects
UJ - non-detects
J - detects
UJ - non-detects
J - detects
R - non-detects
Note: AQ = Aqueous, S/S = Soil/Sediment
For other matrices, the validator should estimate (J) positive detects and use professional judgment to qualify or
reject non-detects when Region I preservation and/or technical holding time criteria are not met.
REFERENCES
a - 4OCFR, Part 136, Appendix A, 600 Series
b - SW-84 , 8000 Series
VOAISV-I-I0 DRAFT 12 /96

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PART II-VOA/SV Preservation and Technical Holding Times
E. EXAMPLES
Example #1 : (Improper preservation (without acid); Analysis holding time exceeded)
Aqueous volatile sample SAA99 was analyzed by routine analysis following CLP SOW
OLMO3.2. The validator examines the data package narrative and determines that the
laboratory did not report the pH. The validator contacts the laboratory to determine whether
the pH was checked by the laboratory and notes that it was not checked. The validator then
examines the Traffic Report contained in the data package and notes that the sampler failed
to record what, if any, preservation techniques were utilized. The validator attempts, but
fails, to contact the sampler. It cannot be determined if the sample was preserved by the
sampler with HC1.
The sampling date for SAA99 was 6/1/95 and the analysis date was 6/21/95, 20 days from
sampling. The aqueous volatile samples exceeded the technical holding time critena for
aromaiics and non-aromatics. The validator examines the Form I and notes that benzene,
toluene, ethylbenzene, chlorobenzene, and xylenes (aromatics) are not detected and that
acetone (non-aromatic) is reported at 30 ugIL. The validator reports the benzene, toluene,
ethylbenzene, chlorobenzene. and xylenes non-detects as rejected (R). the non-aromatic non-
detects as (UI), and acetone as 301 on the Data Summary Table. The validator notes in the
Data Validation Memorandum that the sample data are qualified based on improper
preservation (without acid) and exceeded technical holding times.
Exarnole #2 : (Improper preservation (refrigeration); Holding times met)
Volatile air samples SAAI 1-SAA22 were analyzed by the most recent Region I analytical
specification for Method TO-i. The laboratory noted in the data package narrative that the
samples were received on a Friday afternoon and remained unrefrigerated in the shipping area
for over 2 days. The laboratory further noted that this area has no climate control and that
temperatures routinely exceed that of the sample storage area by 15-20°C. The validator uses
professional judgment to estimate (I) positive detects and reject (R) non-detects in all samples
on the Data Summary Table due to the exposure to excessive heat over the 2 day penod and
discusses this problem in the Data Validation Memorandum.
Examole #3 : (Proper preservation; Analysis holding time exceeded)
Volatile soil sample SAA33 was sampled on 8/1/95 and was received at the laboratory on
8/2/95. Upon examination of the Traffic Report and the laboratory sample receipt and
tracking information, the validator determines that the sample was shipped and stored at 4°C
and was light protected. As noted in the data package narrative, due to a laboratory trackmg
error, the laboratory analyzed the sample following CLP SOW OLMO3.2 on 8/18/95, 17 days
from the sampling date. The validator estimates (I ) the positive detects of sample SAA33 and
estimates (UI) the non-detects on the Data Summary Table and discusses this problem in the
Data Validation Memorandum.
Exarnole 4 . (Proper preservation: Extraction holding time grossly exceeded)
Semivolatile soil sample SAA44 was sampled on 8/1/95 1.nd received at the laboratory on
8/2/95. Upon examination of the Traffic Report, laboratory receipt information, and sample
tracking records, the validator determines that the sample was properly preserved at 4°C and
was light protected. The sample was not extracted until 9/1/95, 31 days from sampling date.
due to a laboratory tracking error and extraction holding times were grossly exceeded. The
validator estimates (J) the positive detects of sample SAA44 and rejects (R) the non-detects
on the Data Summary Table and discusses this problem in the Data Validation Memorandum.
VOAIS V-I-Il DRAFT 12/96

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PART l1-VOAJSV GCIMS Instrument Performance Check (Tuning)
II. GCIMS INSTRUMENT PERFORMANCE CHECK CFtJNING)
A. OBJECTIVE
Gas chromatograph/ma.ss spectrometer (GC/MS) instrument performance (tuning) checks are performed
to ensure proper mass calibration and resoluuori, ideutiticanon and to some degree, sensitivity.
B. CRITERIA
GC/MS instrument performance (tuning) criteria are not sample specific. Since conformance is
determined using standard materials, these criteria should be met under all circumstances. The CLP-
Volatjle/Semjvolacile method QC acceptance criteria listed in Appendices A and B should be used as
the default criteria when none exist for the Volanle/Sexnivolarile analytical method utilized and when
similar QC parameters are required by the non-CLP method and acceptance criteria have not been
specified. Deviations, modifications or non-CLP method-specific QC acceptance criteria may be used
but must be explicitly defined in tabular format in the site-specific EPA approved QAPjP/SAP or
amendment to the QAPJP/SAP.
C. EVALUATION! D. ACTION
C.
EVALUATION
D. ACTION
All
potential impacts on the sample data
from
resulting
tuning anomalies should be noted
in the
Validation Memorandum. The
validator should
document and justify all
technical
made based on professional
judgment in the Data Validation Memorandum.
1
Verify from the reported results that the mass
scale is correct (amu assignments are accurate)
and that the ion abundance QC acceptance
criteria specified in the method were met for
1. a. If tabulated result forms are not
present for each 12-hour period for
which samples are analyzed, then the
validator should
each 12-hour period that samples were
contact the laboratory
to obtain the tabulated forms.
analyzed.
b. If the mass scale is incorrect and amu
assignments are inaccurate, then the
validator should reject (R) all data
associated with that tune. The data
should be returned to the laboratory
and payment denied.
c If ton abundance QC acceptance
criteria are not met, then professional
judgment should be used to determine
to what extent the data may be utilized.
The most important factors to consider
are the empirical results that are
unrelated to retention time and type of
Instrumentation.
VOA/SV-II-1 DRAFT’ 12/96

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Pu T u-vo tjsv GC/MS Instrument Performance Check (Tuning)
C. EVALUATION
D. ACTION
*2. Compare the reported tuning results on each
GC/MS Tuning and Mass Calibration Form
with each raw data mass listing and mass
spectrum submitted Venfy that the laboratory
has no made any transcription or calculation
errors.
2. If any transcnpuon and/or calculauon errors are
detected, perform a more comprehensive review
to determine the magnitude of the problem. If
the problem is extensive, then the validator
should have the laboratory requantitate and
resubmit all corrected raw data and forms. Ef a
discrepancy remains unresolved, the validator
must use professional judgment to decide which
value is accurate. Under these circumstances,
the validator may determine that the sample
data should be qualified or rejected. A
discussion of the rationale for data qualification
and the qualifiers used should be documented in
the Data Validation Memorandum.
*3• If possible, verjf ’ that spectra were generated
using appropriate background subtraction
techniques. Since the spectra are obtained from
chromatographic peaks that should be free from
coelucion problems, background subtraction
actions resulting in spectral distortions for the
sole purpose of meeting the contract or method
specifications are concraiy to quality assurance
objectives and are, therefore, unacceptable.
3. If the validator has reason to believe that
tuning/instrument performance checks were
achieved using non-compliant techniques, then
the performance and procedures of the
laboratory merit further investigation.
•
* Note: The following subsections are applicable only to a Tier III data validation:
C.2, C.3
VOAJSV-I1-2 DRAFr 12/96

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PART ll-VOA/SV GC/MS Instrument Performance Check (Tuning)
E. EXAMPLES
Example #1 : (Ion abundance criteria not met for several ions)
The validator examines tabulated and raw tuning data generated under CLP SOW OLMO3.2 to
check for calculation and transcription errors. The validator compares the BFB mass spectrum
and mass listing with Form V-A. The ion abundances have not been normalized to ion 95 as
per the SOW and, when normalized by the validacor, do not meet the SOW ion abundance
criteria. The validacor notes that the abundance criteria for ions 50, 75, 96, and 174 are
exceeded by 25%. The validator uses professional judgment to estimate (J) all positive detects
and estimate (Ui) all non-detects on the Data Summary Table for samples associated with that
tune and discusses this problem in the Data Validation Memorandum.
Example #2 (Ion abundance criteria not met for one ion)
The validator examines tabulated and raw tuning data generated under CLP SOW OLMO3.2 to
check for calculation and transcription errors. The validator compares the DFTPP mass
spectrum and mass listing with Form V-B. The % Relative Abundance for ion 275 is 35% of
ion 198 (OLMO3.2 criteria for ion 198 is 10.0 - 30.0% of mass 198). The validator uses
professional judgment to accept the tune since only one ion abundance slightly exceeds criteria.
The validacor reviews the mass spectra for all positive hits in samples in accordance with
Section X II, Target Compound Identification and determines that all ion abundance ratios are
acceptable. The validator discusses the non-compliant tune and justifies the decision to accept
the sample data in the Data Validation Memorandum.
Example #3 : (Mass calibration error)
The validator examines tabulated and raw DFTPP tumng data generated following method 625
to check for calculation and transcription errors. The validator notes that the tabulated tuning
results were acceptable, however, the raw data do not agree with the tabulated results. Upon
further review of the raw data, the validacor notes that the mass calibration is off by 1 amu.
In addition, surrogate recoveries and internal standard areas were unacceptably low. The
validator rejects (R) all associaceu data, returns the data package to the laboratory, and
payment is denied. The EPA Site Manager is informed by letter and resampling is
subsequently scheduled.
VOA/SV-H-3 DRAFI’ 12/96

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PART [ I-VOA/SV Initial Calibration
m. INITIAL CALthRA11ON
A. OBJtCTIVE
Compliance requirements for initial calibration are established to ensure that the instrument is capable of
producing acceptable qualitative and quantitative data. Initial calibration data demonstrate that the
instrument is capable of satisfactory performance at the beginning of the analytical sequence by producing
a linear calibration curve.
B. CRiTERIA
The Region I. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region I Organic data. The CLP-Volatile/Semivolatile method QC
acceptance criteria listed in Appendices A and B should be used as the default criteria when none exist for
the Volatile/Semivolatile analytical method utilized and when similar QC parameters are required by the
non-CLP method and acceptance criteria have not been specified. Deviations, modifications or non-CLP
method-specific QC acceptance criteria may be used but must be explicitly defined in tabular format in the
site-specific EPA approved QAPJP/SAP or amendment to the QAPj P/SAP.
1. Initial calibration standards containing volatile and sernivolacile target and surrogate compounds
at method-specific concentrations are analyzed prior to the analysis of any field samples, QC
samples, and blanks, or as necessary if the continuing calibration method acceptance criteria are
not met. The initial calibration and any associated field samples, QC samples, and blanks must
be analyzed within 12 hours of the associated GC/MS instrument performance check.
2. Initial calibration standards must be analyzed using the same instrumental conditions that will be
used to analyze field samples, QC samples, and blanks.
3. The mean Relative Response Factors (RRFs) for all volatile and semivolatile target and surrogate
compounds in each initial calibration must be greater than or equal to 0.05.
The Percent Relative Standard Deviation (%RSD) for all volatile and semivolatile target and
surrogate compound RRFs in each initial calibration must be less than or equal to 30.0 percent.
VOA/S V-ill-I DRAFT 12/96

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PART LI-VOA/SV Initial Calibration
C. EVALUATION! D. ACTION
EVALUATION
D. ACTION
All potential impacts on the sample data
resulting from initial calibration anomalies
should be noted in the Data Validation
Memorandum. The validator should also
document and justify all wchnical decisions
made based on professional Judgment in the
Data Validation Memorandum.
initial calibration standards
the method-required
frequency, and that the
I.
a. If the laboratory did not use the required
concentrations and/or frequency when
analyzing the initial calibration standards,
analyzed within 12 hours of
GC/MS instrument
or the standards were not analyzed withui
12 hours of the associated GC/MS
instrument performance check, then the
validator should use professional judgment
to determine whether the associated sample
data should be qualified or rejected.
method-required calibration
b. If the correct method-required calibration
used for calculating sample
results were calculated
calibration,
standard(s) was not used to quancicace
sample results, then the validator should
have the laboratory requamitate and
resubmit all corrected raw data and forms.
If a discrepancy remains unresolved, the
validaior must use professional judgment me
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
instrument parameters
and calibration analyses,
2.
If correct instrument parameters (i.e., purge
and crap conditions, etc.) were not used for the
parameters which were
requirements.
initial calibration standards and sample
analyses, then the validator should contact the
laboratory to obtain corrected data and forms
a. If the laboratory is unable to submit a
correct initial calibration, then the validacor
should determine whether a qualitative
analysis is of any benefit by reviewing the
project Data Quality Objectives.
b. If the data are deemed unusable, then the
validaror should reject (R) all associated
data. The data should be returned to the
laboratory and payment denied.
vOA/sv-m-2 DRAFI’ 12/96

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PART II-VOAISV
Initial Calibration
C. EVALUATION
D. ACTION
3. Verify that the s for all volatile and
semivolatile target and surrogate compounds are
greater than or equal to 0.05 in the initial
calibration.
Verify that the %RSDs for all volatile and
semivolatile target and surrogate compound
RRFs do not exceed 30.0% in the initial
calibration.
Evaluate co pQunds that fail to meet both
%RSD and RRF criteria.
Note:
The CLP SOW OLMO3.2 minimum response
factor method acceptance criterion differs
from the Region I FunctIonal Guidelines
Initial and continuing calibration minimum
response factor validation criterion. If data
quality objectives allow for grelter variability
of data, then an expanded minimum response
factor validation criterion should be
documented in the EPA-approved site-specific
QAPjP or amendment to the QAPJP. If
response factors less than 0.05 are allowed,
then the validator should ensure that there is
sufficient QC data to support the use of low
response factors in sample calculations.
3. Situation 1: If any target compound has a_
%RSD less than or equal to 30.0% and an RRF
less than 0.05, then the validacor should:
a. Estimate (J) positive detects for that
affected compound that have acceptable
mass spectral identification for all samples
associated with the initial calibration.
b. Reject (R) non-detects for that affected
compound for an samples associated with
the initial calibration.
Situation 2: If any target compound has a
%RSD greater than 30.0% and an RRF greater
than or equal to 0.05, then the validator should:
a. Estimate (J) positive detects for that
affected compound for all samples
associated with the initial calibration.
b. Estimate (Ui) non-detects for that affected
compound for all samples associated with
the initial calibration.
c. See D.4, Situation 2 Expanded for
additional guidance.
Situation 3: If any target compound has a
%RSD greater than 30.0% and an RRF less
than 0.05, then the validator should:
a. Estimate (J) positive detects for that
affected compound that have acceptable
mass spectral identification for all samples
associated with the initial calibration.
b. Reject (R) non-detects for that affected
compound for all samples associated with
the initial calibration.
Surrogates: If afly.. urrogate compound fails to
meet minimum RRF cnteria andior %RSD
cneria, then the validator should use
professional judgment to assess the impact of
surrogate compound calibration data on the
sample results.
See Table VOA/SV-ffl-1
VOA/SV-m-3
DRAFF 12/96

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PART rI-VOA/Sv Initial Calibration
C. EVAJ. UATION
D. ACTION
4. Evaluate the cause of a non-linear calibration 4. Situation 2 Expanded: If the %RSD is greater
curve based on 5 or more concentration points, than 30.0%, and all the initial calibration RRFs
for a target compound are greater than or equal
to 0.05, then the validator should use
professional judgment o determine the need to
c!ieck the calibration points for the cause of the
non-linearity. This is checked by eliminating
either the high or the low calibration points and
recalculating the %RSD. Ac the validator’s
discretion, a more in-depth review to minimize
data qualification can be accomplished by
considering the following:
a. If any target compound has a %RSD
greater than 30.0%, and if eliminating
either the high point or the low point of the
curve does not restore the %RSD to less
than or equal to 30.0%, then the validator
should:
- Estimate (J) positive detects for that
affected compound for all samples
associated with the initial calibration.
- Estimate (UJ) non-detects for that affected
compound for all samples associated with
the initial calibration.
b. If eliminating the high point of the curie
restores the %RSD to less than 30.0%,
then the validator should:
- Accept (A) positive detects in the linear
portion of the curve for that affected
compound for all samples associated with
the initial calibration.
Estimate (J) positive detects at the high end
of curve outside of the linear portion for
that affected compound for all samples
associated with the initial calibration.
Accept (A) non-detects for that affected
compound for all samples associated with
the initial calibration.
VOA/SV-ffl-4 DRAFT 12196

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PART fl-VOAJSV Initial Calibration
C. EVALUATION
D. ACTION
4. Continued from above.
4. c. If eliminating the low point of the curve
restores the %RSD to less than 30.0%.
then the valicLator should:
- Accept (A) positive detects in the linear
portion of the curve for that affected
compound for all samples associated with
the initial calibration.
- Estimate (J) positive detects at the low end
of curve outside linear portion for that
affected compound for all samples
associated with the initial calibration.
- Estimate (UJ) non-detects for that affected
compound for all samples associated with
the initial calibration.
See Table VOAJSV-ffl-2
5. Check and recalculate the RRF and RRF for at
least one volatile and semivolacile target
compound associated with each internal
standard. Verify that the recalculated values
agree within 10% of the laboratory reported
values,
5. If errors greater than 10% are detected in the
RRF calculations, then the validator should
perform a more Comprehensive review to
determine the magnitude of the problem. If the
problem is extensive, then the validator should
have the laboratory requanticate and resubmit all
corrected raw data and forms. If a discrepancy
remains unresolved, the validator must use
professional judgment to decide which value is
accurate. Under these circumstances, the
validator may determine that the sample data
sh ‘uld be qualified or rejected. A dis ussion of
the rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
*6. Check and recalculate the %RSD for at least
one volatile and semivolatile target compound
associated with each internal standard. Verify
that the recalculated values agree within 10% of
the laboratory reported values,
6. If errors greater than 10% are detected in the
%RSD calculations, then the validator should
perform a more comprehensive review to
determine the magnitude of the problem. If the
problem is extensive, then the validator should
have the laboratory requarniate and resubmit all
corrected raw data and forms. If a discrepancy
remains unresolved, the validator must use
professional judgment to decide which value is
accurate. Under these circumstances, the
validacor may determine that the sample data
should be qualified or rejected. A discussion of
the rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
VOAISV-ffl-5 DRAFF 12/96

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PART II-VOA/SV Initial Calibration
C.
EVALUATION
D.
ACTION
*7• a.
Review Standard Preparation Logs (if
7. a. If standards preparation data have not been
provided in the data package) to ensure that
submitted with the data package, then the
primary and secondary initial calibration
validator should use professional judgment
standard concentrations are accurate and
to determine if standards preparation data
traceable to NIST standards.
are necessary to facilitate the validation of
sample data. If necessary, the validator
should contact the laboratory to obtain
standards preparation information.
* b.
Check and recalculate the initial calibration
b. If errors greater than 10% are detected in
standard concentration for one volatile and
the standard concentration calculations,
one semivolatile target compound (if
then the validajor should perform a more
standards preparation documentation was
comprehensive review to determine the
provided in the data package). Venfy that
magnitude of the problem. If the problem
the calculated values agree within 10% of
is extensive, then the validator should have
the laboratory reported values,
the laboratory requantitate and resubmit all
corrected raw data and forms. If a
discrepancy remains unresolved, the
validator must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
* Note: The following subsections are applicable only to a Tier ifi data validation:
C., C.5, C.6, C.7.a, C.7.b
VOA/SV-ffl-6 DRAFF 12/96

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PART ll-VOA/SV
Table VOAJSV-!II- 1.
UALWICATION OF VOA/SV ANALYTES BASED ON THE INiTIAL CALIBRATION
Initial Calibration
Sample Results
QC Criterion
0.05
%RSD  30.0%
Situation 1
RRF <0.05
%RSD  30.0%
Situation 2 *
RRF  0.05
%RSD >30.0%
Situation 3
RRF < 0.05
%RSD > 30.0%
Detects
A
J
J
I
Non-detects
A
R
Ui
R
** See Table VOA/SV-III-2 for additional guidance.
Table VOAJSV-III-2:
EXPANDED INITIAL CALIBRATION VOA/SV ANALYTE qUALIFICATIONS
Sample Results
Elimination of
High or Low
Calibration
Points
%RSD > 30.0%
Elimination of
High
Calibration
Points
%  30.0%
RRF 0.05
Elimination of
Low
Calibration
Points
%RSD  30.0%
RRF  0.05
Detects
J
A: On linear portion of
curve
3: On high end of
curve outside linear
portion
A: On linear portion of
curve
3. On low end of
curve outside linear
portion
Non-detects
UJ
A
UI
VOA/SV-m-7
DRAFT 12/96

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PART II-VOA/SV Initial Calibration
E. EXAMPLES
Example #1 : Situation 1 (Low i ; Acceptable linearity)
The RRF of an initial calibration for benzerie is 0.035 which does not meet the 0.05
acceptance critena. The %RSD of the calibration points for benzene is 19.0%. Due to the
low instrument response for benzene, the validacor estimates (J) all the positive beazene
deects and rejects (R) the benzene non-detects on the Data Summary Table and notes this
problem in the Data Validation Memorandum.
Examole #2 : (Low RRF; Acceptable linearity; Modified Region IRRF criteria)
The RRF of an initial calibration for acetone is 0.035 and the %RSD is 120%. The site-
specific EPA-approved QAPJP documents that modified Region I minimum RRF criteria will
be used to validate project data. The modified criteria are:
• The mean initial calibration RRF and the continuing calibration RRF for all volatile and
seinivolatile target and surrogate compounds must be greater than o gual to 0.05 except
for the following compounds which must have an initial calibration RRF and a continuing
calibration RRF greater than or equal to 0.01: chloromethane, chioroethane, methylene
chloride, acetone, carbon disulfide, 1,2-dichioroethane (total). 2-buranone, 1,2-
dichloropropane, 4-methyl-2-pentanone, 2-hexanone and surrogates, toluene-d8 and 1,2-
dichloroethane-d4.
The validator accepts all acetone positive detects and non-detects in the samples associated
with the initial calibration and reports the sample results unqualified on the Data Summary
Table. The validator documents the modified data validation criteria in the Data Validation
Memorandum.
Example #3 : Situation 2 (Acceptable High RSD - Elimination of high point)
The validacor examines the initi L... alibration data and notes that the %RSD for
tetrachloroethene was 60.0% and the RRF was 0.07. Elimination of the high calibration point
restored the %RSD to 18.0%. Since linearity was verified for a portion of the
tetrachloroethane curve, the validator accepts all positive tetrachioroethene detects on the
linear portion of the curve and estimates (J) the positive tetrachloroethene detects on the non-
linear portion of the curve. Tetrachloroethene non-detects are accepted. All results are
reported on the Data Summary Table and the qualifications are discussed in the Data
Validation Memorandum.
Examole / 4 Situation 2 (Acceptable RRF; High RSD - Elimination of low point)
The validator examines the initial calibration data and notes that the %RSD for acetone was
70.0% and the RRF was 0.07. Elimination of the low calibration point restored the %RSD
to 20.0%. Since linearity was verified for a portion of the acetone curve, the validator
accepts all positive acetone detects on the linear portion of the curve and estimates (J) the
positive acetone detects on the non-linear portion of the curve. Acetone non-detects are
estimated (UJ). All results are reported on the Data Summary Table and the qualifications
are discussed in the Data Validation Memorandum.
voA/SV-m-8 DRAFT 12/96

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PART ll-VOA/SV Initial Calibration
E. EXAMPLES
Example #5 : Situation 3 (Low RRF; High RSD)
The RRF for trichloroethene is 0.029 which is well below the 0 05 acceptance cruet-ia and
the %RSD for trichioroethene is 65.0% which is well above the acceptance critena. Linearity
cannot be achieved by eliminating the high or low points. Due 10 erratic instrument
performance, the validator uses professional judgment to estimate (J) positive crichioroethene
detects and reject (R) trichioroethene non-detects on the Data Summary Table and discusses
sample qualifications in the Data Validation Memorandum.
VOA/SV-ffl-9 DRAFT 12/96

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PART U-VOA/SV Continuing Calibration
Iv. CONTINUING CALIBRATION
A. OBJECTIVE
Compliance requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable qualitative and quantitative data. Continuing calibration
establishes the daily relative response factors on which target compound quanutanon is based and
checks the stability of instrument response on a day-o -day basis.
B. CRITERIA
The Region I. EPA- 4E Data Validation Functional Guidelines for Evaluatine Environmental Analyses
should be used to validate all Region I Organic data. The CLP-VolatileiScmivolatile method QC
acceptance criteria listed in Appendices A and B should be used as the default criteria when none ex si
for the VolaxileiSemivolaiile analytical method utilized and when similar QC parameters are required by
the non-CLP method and acceptance criteria have not been specified. Deviations. modifications or
non-CL? method-specific QC acceptance criteria may be used but must be explicitly defined in tabular
format in the site-specific EPA approved QAPJPISAP or amendment to the QAPJPISAP
1. Continuing calibration standards containing volatile and semivolaule target and surrogate
compounds at method-specified concentrations 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 field samples, QC samples, and blanks.
2. Continuing calibration standards must be analyzed using the same instrumental conditions
which were used to analyze the initial calibration and that will be used to analyze field
samples, QC samples, and blanks.
3. The continuing calibration Relative Response Factors (RRFS) for all volatile and semivolaule
target and surrogate compounds must be greater than or equal to 0.05.
The Percent Difference (%D) between the most recent initial calibranon i and the
continuing calibration RRF for all volatile and semivolaule target compounds and surrogate
compounds must not exceed ± 25.0 percent.
VOAJSV - 1V -1 DRAFI 12/96

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PART ll-VOA/SV
Continuing Calibration
C. EVALUATION/ D. ACTION
C. EVALUATION
D. ACTION
1. a. Verify that the continuing calibration
standard was analyzed at the required
concentration and frequency, and that the
standard was analyzed within 12 hours of
the associated GCIMS instrument
performance check.
b. Verify that quantitanon was performed
using a continuing calibration analyzed
within 12 hours of the field samples.
*2. Ver fy that the same instrument parameters
were used for sample and calibration analyses,
and that instrument parameters which were
utilized met method requirements.
All potential impacts on the sample data
resulting from continuing calibration
anomalies should be noted in the Data
Validation Memorandum. The validator
should also document and justify all
technical decisions made based on
professional judgment in the Data
Validation Memorandum.
1. a. If the laboratory did not use the required
concentration and/or frequency when
analyzing the continuing calibration
standard or the standard was not analyzed
within 12 hours of the associated GC/MS
instrument performance check, then the
validator should use professional judgment
to determine whether the associated sample
data should be qualified or rejected.
b. If the correct continuing calibration
standard was not used to quantitace sample
results, then the validator should have the
laboratory requantitace and resubmit all
corrected raw data and forms. If a
discrepancy remains unresolved, the
validacor must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
2. If the same method-required instrument
parameters (i.e., purge and trap conditions,
etc.) were not used for the continuing
calibration standards and field sample analyses,
then the validator should contact the laboratory.
a. If the laboratory is unable to submit a
correct continuing calibration, then the
validator should determine whether a
qualitative analysis is of any benefit by
reviewing the project Data Quality
Objectives.
b If the data are deemed unusable, then the
validator should reject (R) all associated
data. The data should be returned to the
laboratory and payment denied
VOA/SV-IV-2
DRAFF 12/96

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PART fl-VOAJSV
Continuing Calibration
3. Verify that the continuing calibration was
compared to the most recent initial calibration.
Verify that RRFs for all volatile and
semivolatile target and surrogate compounds are
greater than or equal to 0.05 in the continuing
calibration.
j fy that the %D beween initial calibration
RRF and continuing calibration RRF for all
volatile and semivolatile target and surrogate
compounds is less than or equal to ± 2.5.0%.
Evaluate compounds that fail to meet both %D
and RRF criteria.
Note:
The CLP SOW OLMO3.2 minimum response
factor method acceptance criterion differs
from the Region I Functional Guidelines
initial and continuing calibration minimum
response factor validation criterion. If data
quality objectives allow for greater variability
of data, then an expanded minimum response
factor validation criterion should be
documented in the EPA-approved site-specific
QAPJP or amendment to the QAPJP. If
response factors less than 0.05 are allowed,
then the vaiidator should ensure that there is
sufficient QC data to support the use of low
response (actors in sample calculations.
3. If the continuing calibration was not compared
to the most recent initial calibration, then the
validator should have the laboratory recalculate
%Ds based on the correct initial calibration and
resubmit all affected data and forms.
Situation 1: If any target compound has a %D
between the initial calibration and the
continuing calibration which is less than or
equal to ± 25.0% and a continuing calibration
RRF less than 0.05, then the validacor should:
a. Estimate (J) positive detects for that
affected compound that have acceptable
mass spectral identification for all samples
associated with the continuing calibration.
b. Reject CR) nOn-detects for that affected
compound for all samples associated with
the continumg calibration.
Situation 2: If any target compound has a %D
between the initial and continuing calibration of
g:eacer than ± 25.0% and a continuing
calibration RRF greater than or equal to 0.05,
then the validator should:
a. Estimate (J) positive detects for that
affected compound for all samples
associated with the continuing calibration.
b. Estimate (Ui) non-detects for that affected
compound for all samples associated with
the continuing calibration.
Situation 3: If any target compound has a %D
between the initial and continuing calibration of
greater than ± 25.0% and a continuing
calibration RRF less than 0,05, then the
validator should:
a. Estimate (J) positive detec:s for that
affected compound that have acceptable
mass spectral identification for all samples
associated with the continuing calibration.
b Reject (R) non-detects for that affected
compound for all samples associated with
the_continuing calibration.
C. EVALUATION D. ACTION
VOA/SV-IV-3
DRA.Fl’ 12/96

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PART II-VOA/SV Continuing Calibration
C. EVALUATION
D. ACTION
3. Continued from above.
‘-
‘
3. Continued from above.
Surrogates: If any surrogate compound fails to
rn ec minimum RRF criteria and/or %D
criteria, then the % surrogate recoveries in the
samples, QC samples and blanks associated
with the continuing calibration may be biased
lugh or low resulting in unacceptable surrogate
recoveries. In this case, the validator should
use professional judgment to assess the impact
of surrogate compound calibration data on the
sample results.
See Table VOAISV-1V-1
*4, Check and recalculate the RRF for at least one
volatile and seniivolatile target compound
associated with each internal standard. Verify
that the recalculated values agree within 10% of
the Iaboratozy reported values,
4. If errors greater than 10% are detected in the
RRF calculations, then the validator should
perform a more comprehensive review to
determine the magnitude of the problem. If the
problem is extensive, then the validator should
have the laborato iy requanticate and resubmit all
corrected raw data and forms. If a discrepancy
remains unresolved, the validator must use
professional judgment to decide which value is
accurate. Under these circumstances, the
validator may determine that the sample data
should be qualified or rejected. A discussion of
the rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
5. Check and recalculate the %D for at least one
volatile and semivolacile target compound
associated with each internal standard. Verify
that the recalculated values agree within 10% of
the laboratory reported values,
S. If errors greater than 10% are detected in the
%D calculations, then the validator should
perform a more comprehensive review to
determine the magnitude of the problem. If the
problem is extensive, then the validator should
have the laboratory requantitate and resubmit all
corrected raw data and forms. If a discrepancy
remains unresolved, the validator must use
professional judgment to decide which value is
accurate. Under these circumstances, the
validator may determine that the sample data
should be qualified or rejected. A discussion of
the rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandttn,
VOA/SV-IV-4 DRAFT 12/96

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PART ll-VOAJSV Continuing Calibration
C.
EVALUATION
D.
ACTION
*6.
a.
Review Standard Preparation Logs (if
6.
a.
If Standards preparation data have not been
available in the data package) to ensure that
submitted with the data package, then the
primary and secondary continuing
validator should use professional judgment
calibration concentrations are accurate and
to determine if standards preparation data
traceable to NIST standards.
are necessary to validate sample data. If
necessary, the validator should contact the
.
laboratory to obtain standards preparation
information.
b.
Check and recalculate the continuing
b.
If errors greater than [ 0% are detected in
calibration standard concentration for one
the standard concentration calculations,
volatile and one semivolatile target
then the validator should perform a more
compound (if standards preparation
comprehensive review to determine the
docwnentation was provided in the data
package). Verify that the calculated values
magnitude of the problem. If the problem
is extensive, then the validator should have
agree within 10% of the laboratory reported
the laboratory requanutate and resubmit all
values,
corrected raw data and forms. If a
discrepancy remains unresolved, the
validator must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
S Note: The following subsections are applicable only to a Tier III data validation:
C.2, C.4, C.5, C.6,a, C.6.b
VOA/SV-IV-5 DRAFT 12/96

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PART ff-VOA/SV Continuing Calibration
Table VOAJSV-LV- 1:
QUALIFICATION OF VOA/SV ANALYTES BASED ON THE CONTINUING CALIBRATION
Sample Results
QC Criteria
RRF 0.05
%D ± 25.0%
Situation 1
RRF <0.05
%D ± 25.0%
Situation 2
RRF 0.05
%D> ± 25.0%
Situation 3
RRF <0.05
%D> ± 25.0%
Detects
A
J
J
J
Non-Detects
A
R
UJ
R
E. EXA MPLES
Example #1 : Situation 1 (Low RRF; Acceptable %D)
The RRF for 2-butanone in a conthuingcalibration is 0.035 and the %D is 10.0%. Due
to the low response, the validator estimates (J) all 2-butanone positive detects and rejects
(R) all 2-butanone non-detects that are associated with this continuing calibration on the
Data Summary Table. The validator discusses the qualification of sample data in the Data
Validation Memorandum.
Example #2 : (Low RRF; Acceptable %D; Modified Region I RRF criteria)
The RRF for acetone in a continuing calibration is 0.025 and the %D is 12.0%. The site-
specific EPA-approved QAPjP documents that modified Region I minimum RRF
continuing calibration data validation criteria will be used to validate project data. The
modified criteria are:
• The mean initial calibration RRF and the continuing calibration RRF for all volatile
and semivolatile target and surrogate compounds must be greater than or eaual to 0.05
exce r for the following compounds which must have an initial calibration RRF and a
continuing calibration RRF greater than or equal to 0.01: chloromethane,
chloroethane, methylene chloride, acetone, carbon disulfide, I ,2-dichloroethane
(total), 2-butanone, I ,2-dichloropropane. 4 -methyl-2-pentanone, 2-hexanone and
surrogates, Toluene-d8 and 1 ,2-dichloroethane-d4.
The validator reviews the acetone mass spectra for positive detects in samples and
determines that all mass spectral identification criteria are met. The validator accepts all
acetone positive detects and non-detects in the samples associated with the continuing
calibration and reports the sample results unqualified on the Data Summary Table. The
validator documents the modified data validation criteria in the Data Validation
Memorandum.
VOA/SV-lV-6 DRAFT 12/96

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PART 1I-VOA/SV Continuing Calibration
E. EXAMPLES
Example #3 Sicuarion 2 (Acceptable RRF; High %D)
The RRF for methyletie chloride in a continuing calibration is greater than 0.05 and the
%D between the initial and continuing calibraiion for niethytene chloride is 45.0%. The
validator reviews the insual calibration, continuing calibration, and blank data, and
determines that an intermittent methylene chloride contamination problem exists in the
laboratory which may contribute to the high %D. The validator estimates (J) all
rnethylene chloride positive detects and estimates (UJ) the methylene chloride non-detects
in the associated samples on the Data Summary Table. The validator discusses this
problem in the Data Validation Memorandum.
Example #4 : Situation 3 (Low RRF; High %D)
The RRF for N-aitroso-di-n-propylamine in a continuing calibration is 0.001 and the %D
is 110.0%. Due to low and unstable instrument response to N-nitroso-di.n-propylamine,
the validator determines that both the quantitation limits and positive detects for N-airroso-
di-n-propylathine are unusable. Therefore, the validator rejects (R) all N-nitroso-di-n-
propylantine results that are associated with this continuing calibration on the Data
Summary Table. The validator discusses the qualification of sample data in the Data
Validation Memoraj dum.
VOA/SV-IV-7 DRAFT 12/96

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PART U-VOAISV Blanks
V. BLANKS
A. OBJECTWE
The purpose of blank analyses is to determine the existence and magnitude of contamination problems
resulting from laboratory and/or field activities and to subsequently assess their contribution to
measurement error. The criteria for evaluation of laboratory blanks (method blanks and instrument blanks)
may be applied to any blank associated with the samples. If problems with blank exist, all associated
data must be carefully evaluated to determine whether or not there is an inherent measurement error
associated with the entire data set, or if the problem is an isolated occurrence limited to specific samples.
B. CRITERIA
The Renion I. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region I Organic data. The CLP-Volatile/Semivolatile method QC
acceptance criteria listed in Appendices A and B should be used as the default cnteria when none exist for
the Volatile/Semivolatile analytical method utilized and when similar QC parameters are required by the
non-CLP method and acceptance criteria have not been specified. Deviations, modifications or non-CLP
method-specific QC acceptance criteria may be used but must be explicitly defined in tabular format in the
site .specific EPA approved QAPjP/SAP or amendment to the QAPjP/SAP.
1. The frequency and types of blanks collected and analyzed must support the site-specific Data
Quality Objectives (DQOs) as documented in the EPA approved QAP 1 P or SAP. Different types
of blanks may be used to identify the source of potential contamination resulting in analytical
and/or sampling measurement error. The following table lists types of blanks, the environment
of those blanks, and the possible sources of contamination associated with those blanks:
BLANK
LABORATORY/FIELD
IDENTIFIES
CONTAMINATION FROM
Method Blank
Laboratory
Laboratory and Reagents
Instrument Blank
Laboratory
Instrumentation
—
Storage Blank
Laboratory
Storage Environment
Trip Blank
Field
Transit Environment
Bottle Blank
Field
Sample Container
Equipment Blank
(Rinsate)
Field
Sampling Equipment
Note: Aqueous equipment (rinsace) blank results, bottle blank results and trip blank results will be used
to determine blank action levels for aqueous samples based on a volume of 1 liter of blank sample.
Ideally soil/sediment blanks should be used to determine soil/sediment blank actions for
soil/sediment samples based on a known weight of blank sample. However, often aqueous
equipment blanks, bottle blanks and trip blanks are collected to evaluate contamination associated
witn soil/sediment sampling. Aqueous eouioment (rinsate blank results. bottle blank results
VOA/S V-V-i DRAFT 12/96

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PART II-VOAJSV Blanks
and trip blank results will not be used to determine blank action levels for non-aqueous
samples . Compounds that are present in both the non-aqueous sample and the associated aqueous
equipment blank, bottle blank or trip blank will be flagged EB (Equipment Blank), BB (Bottle
Blank) or TB (Trip Blank), respectively. The degree of sampling error that this flagged sample
result represents will be left to the determination of the end user.
2. Method Blanks:
a. A volatile method blank must be analyzed after the continuing calibration and before any
samples, QC samples, or other types of blanks (i.e., storage blanks). The VOA method
blank must be analyzed at least once during every 12 hour time period on each GC/MS
system used to analyze samples.
b. A semivolatile method blank must be extracted with each sample delivery group or each
20 samples of similar matrix in each sample delivery group or whenever a sample extract
procedure is performed. The method blank must undergo all cleanup procedures
performed on samples, i.e., GPC, Silica Gel, etc. used in sample preparation. The
semivolatile method blank extract must be analyzed on each GCIMS system used to
analyze samples.
3. Instrument Blanks:
a. An instrument blank must be analyzed after any sample that exceeds the calibration range
to check that the blank is free of interference and the system is not contaminated.
b. For purge and trap volatile organic analysis, an instrument blank must be analyzed in the
same purging position as a sample that exceeds the calibration range to check that the
blank is free of interference and the purging position is not contaminated.
c. Instrument blanks and apparatus blanks for each cleanup procedure, including GPC and
Silica Gel, etc. used in sample preparation must be analyzed prior to sample analysis.
4. Storage Blanks:
• a. A volatile storage blank vial (in duplicate) must be prepared by the laboratory when the
first samples of the sample delivery group are received. The storage blank is stored with
the samples and analyzed after all the samples in the sample delivery group have been
analyzed.
5. All blanks should be spiked with surrogate compounds and internal standards according to the
method. Note: CLP OLMO3.2 does not require that the GPC instrument blank be spiked with
internal standards or surrogates.
a. Blank internal standards must meet method internal standard QC acceptance critena.
b. Blank surrogate compounds must meet method surrogate compound QC acceptance
criteria.
6. No contaminants should be present in the blanks.
VOA/SV-V-2 DRAFT 12/96

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PART II-VOA/SV
Blanks
C. EVALUATION/ D. ACTION
C. EVALUATION
D. ACTION
1. a. Verify that the correct number and type of
blanks have been collected and analyzed in
accordance with the EPA approved QAPjP
or SAP.
b. Ascertain if aqueous equipment (rinsate)
blanks, aqueous bottle blanks or aqueous
cnp blanks have been collected with non-
aqueous samples to identify sources of field
contamination.
All potential impacts on the sample data
resulting from blank anomalies should be noted
in the Data Validation Memorandum. The
validator should also document and justify all
technical decisions made based on professional
judgment in the Data Validation Memorandum.
Action regarding unsuitable blank results
depends on the circumstances and origin of the
blank. Qualification should be based upon a
comparison of the sample concentration(s)
with the highest blank concentration
associated with the sample delivery group.
However, in cases of specific instrument,
storage and/or method blank contamination, the
validator should use professional judgment to
qualify only those samples associated with that
isolated blank Contamination. Likewise, the
validator may need to apply blank qualifications
to a sample delivery group based on associated
equipment, trip, or bottle blank data that exists
in another sample group data package. Sample
results must not be corrected by subtractjnn
any blank values .
1. a. If the correct number and type of blanks
have not been collected and analyzed, then
the validator should note this deviation
from the EPA approved QAPjP or SAP in
the Data Validation Memorandum. The
validator should use professional judgment
to qualify sample data when blank data are
absent.
When required trip, equipment (rinsate) or
bottle blanks are not identified on the chain
of custody, then the validaor must contact
the sampler or site project manager to
obtain this information and note this contact
on the Blank Analysis validation worksheet.
b. If positive results are detected in the
aqueous equipment (rinsate) blanks, bottle
blanks and/or trip blanks and the associated
non-aoueous samples, then the validator
should flag (EB, RB or TB) those detected
compounds in the assoc aed non-aqueous
samples to indicate to the end user that an
indeterminate amount of samnpiing error has
potentially ffecred the sample results
(See examnule #4)
VOA/SV-V-3
DRAFT’ 12/96

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PA.RT II-VOA/SV
Blanks
2. a. Verify that a VOA method blank analysis
has been reported per matrix, per
concentration level, per extraction batch
(for medium-level VOAs only) after each
continuing calibration and for each 12-hour
time period on each GC/MS system used to
analyze samples.
b.; Verify that a semivolanle method blank
analysis has been reported once per matrix,
- per concentration level, per extraction
technique and SDG, and on each GCIMS
system used to analyze sample extracts.
* c. Verify from the raw data that the extraction
andlor analysis dates and times, sample
IDs, file IDs, instrument IDs, etc. are
accurately reported on the tabulated result
forms.
2. a. If VOA method blanks were not analyzed
at the required frequency and for each
matrix, concentration level, extraction
batch (for medium-level VOAs only), and
on each GCIMS system used to analyze
samples, then the validator should use
professional judgment to determine whether
the associated sample data should be
qualified.
b. If semivolatile method blanks were not
analyzed at least once for each matrix,
concentration level, extraction technique
and batch, and on each GCIMS system
used to analyze sample extracts, then the
validator should use professional judgment
to determine whether the associated data
should be qualified.
c. If review of the raw data reveals
discrepancies and/or transcription errors,
then the validator should have the
laboratory requancitate and resubmit all
corrected raw data and forms. If a
discrepancy remainc unresolved, the
validacor must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
C. EVALUATION
D. ACTION
VOA/SV-V-4
DRAFT 12/96

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PART I1-VOAJSV
Blanks
C. EVALUATION
D. ACTION
3. a. Verify from the Blank Summary form and
Form Is that a VOA instrument blank was
analyzed after each sample that exceeded
the uistruinent calibration range.
* b. Verify from the raw data, the Blank
Summary form, and Form Is that a VOA
instrument blank was analyzed in the same
purging/sparging vessel (i.e., same position
in the autosampler) as the sample that
exceeded the instrument calibration range.
* c. i. Verify from the raw GPC data that a
GPC instrument blank was analyzed
after the GPC calibration and prior to
sample analysis.
* ii. Verify from the raw Silica Gel data
that a Silica Gel Column reagent blank
was analyzed prior to sample analysis
3. a. If an instrument blank was not analyzed
following a sample analysis which
contained an analyte(s) at high
concentration(s), then sample analysis
results after the high concentration sample
must be evaluated for carryover.
Professional judgment should be used to
determine if instrument cross-contam ination
has affected any posiuve compound
idencificauon andJor quantication, and to
dete-imne whether the affected sample data
should be qualified or rejected. If cross-
contamination is suggested, then this should
be noted in the Data Validation
Memorandum.
b. If an instrument blank was not analyzed in
the same purging vessel used to analyze a
sample that exceeded the instrument
calibration range, then sample analysis
results generated in that purging vessel
after the high concentration sample must be
evaluated for carryover. Professional
judgment should be used to determine if
instrument CrOS$-COflt2I IOfl has affectec
any positive compound identification andJor
quantitauon, and to determine whether the
affected sample data should be qualified or
rejected. If cross-contam ination is
suggested, then this should be noted in the
Data Validation Memorandum.
c. I. If a GPC instrument blank was not
analyzed at the method-required
frequency, then the validator should
evaluate the method blanic data and use
professional judgment to qualify
sample data associated with that GPC
cleanup procedure.
ii. If a Silica Gel Column reagent blank
was not analyzed at the method-
required frequency, then the validator
should evaluate the method blank data
and use professional judgment to
qualify sample daa associated with that
Silica Gel Column cleanup procedure
VOA/SV-V-5
DRAFT 12/96

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PART fl-VOAJSV Blanks
C. EVALUATION
D.
ACTION
4. Verify that a VOA storage blank was analyzed
for each sample delivery group and that it was
analyzed after all field samples were analyzed.
4.
If a VOA storage blank was not analyzed at the
Correct frequency, then the validator should use
professional judgment to accept or qualify
sample data.
5. a. Verify that the blank internal standard areas
and retention times and surrogate compound
recoveries meet method QC acceptance
criteria,
5.
a. If blank internal standard areas and/or
retention times andlor surrogate compound
recoveries do not meet method QC
acceptance criteria, then the validator
should use professional judgment in
applying blank actions. The possibility of
false positives or false negatives being
incorrectly reported for the blank should be
evaluated.
*
b. Check 10% of the raw data for each blank
to verify that internal standard areas and
retention ume data, have been correctly
transcribed to tabulated forms and that
surrogate compound recovery data have
been correctly calculated and transcribed to
tabulated forms. Review the blank
chromatograms, quantitation reports, and
mass spectra to ensure that no false
positives or false negatives have been
reported,
b. If the laboratory has reported a false
positive or a false negative and/or has
incorrectly transcribed and/or calculated
data, then the validator should have the
laboratory requantitate and resubmit all
corrected raw data and forms. If a
discrepancy remains unresolved, the
validator must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation_Memorandum.
VOAISV-V-6 DRAFF 12/96

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PART II-VOAISV Blanks
C. EVALUATION
D. ACTION
6. Review the reported results of all associated 6. 11 a contaminant is found in a blank but not in
blanks on the tabulated forms. the sample, no action is taken. If a
contaminant is found in both a blank and a
sample, then the validator should note this
problem in the Data Validation Memorandum
and qualify the data according to the following
guidance:
Note: If the blank action level for a
compound is determined using the
value from a bottle blank, equipment
blank or trip blank, then the positive
values in the bottle, equipment, or
trip blank should be reported
unqualified on the Data Summary
Tables. However, if the blank action
Is determined using the value from a
laboratory blank (e.g., method,
storage, or instrument), then the
positive values in the trip, bottle, or
equipment blanks should be
qualified. (See example #6)
a. Determine if any target compounds are a. Target Compound Contaminants at or
present at or above the quantitation Above the Quantitation LImitJCRQL:
Iimii/CRQL in any of the blanks.
1. If positive sample results for a
compound are greater than 5 times the
concentration in any blank (with the
exception of the common laboratory
COntanhin2nIs in Section V.C.6.b), then
the compound’s concentration should
be reported as unqualified.
ii. If positive sample results for a
compound are less than or equal to 5
times the concentration of the
compound in any blank (with the
exception of the common laboratory
contaminants in Section V.C.6.b) but
are greater than the quantitation limit,
then the sample quantitation lirmt for
that compound should be elevated to
the concentration found in the sample
and reported as not detected (U). The
validator should use professional
judgment to determine if further
elevation of the quantitation hmir is
______ required. (See example #1 5x rule)
VOAJSV-V-7 DRAFT 12/96

-------
PART IFVOAISV
Blanks
C. EVALUATION
D. ACTION
6. Continued
b. Determine if any common volatile
laboratory contaminants (acetone,
methylene chloride, 2-butanone) or any
common semivolatile laboratory
cont2mIn nts (phthalates) are present at or
above the quantitation limitICRQL in any
of the blanks.
6. Continued
Noe:
The validacor should note that blank analyses
may not involve the same weights, volumes, or
dilution factors as the associated samples.
These factors must be taken into consideration
when appIyin the 5x ’ or 10x’ criteria, such
that a companson of the total amount of
contamination is actually made. (See example
#5).
Additionally, there may be instances where
little or no contamination was present in the
associated blanks, but qualification of the
sample data is deemed necessary. If the
validator determines that the contamination
originates from a source other than the sample,
the sample data should be qualified.
Contamination introduced through dilution
water is one example. Although it is not
always possible to determine, instances of this
occurrence can be detected when contaminants
are found in the diluted sample result, but are
absent in the undiluted sample result. Since
both results are not routinely reported, it may
be impossible to verify this source of
contamination. In this case, the 5x” rule may
not apply; the target compound should be
reported as not detected (U), and an explanation
er the data qualification rationale should be
provided in the Data Validation Memorandum.
b. Common Laboratory Contaminants at or
Above the Quantitation Limit/CRQL:
i. If positive sample results for a
common laboratory contaminant
compound are greater than 10 times
the concentration in any blank, then the
compound’s concentration should be
reported as unqualified (See example
#3 - lOx rule).
ii. If positive sample results for a
common laboratory contaminant
compound are less than or equal to 10
times the concentration of the
compound in the blank, then the
sample quanutation limit should be
elevated to the concentration found in
the samole and reported as not detected
(U). The validator should use
professional judgment to determine if
Ilirther elevation of the quantitation
limit is reauired.
VOAJSV-V-8
DRAFF 12/96

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PART II-VOA/SV Blanks
C. EVALUATION
D. ACTION
6. c. Determine if low level contamination below 6. c. Common Laboratory Contaminants and
the quantitation limit exists in any of the Target Compounds Below the
blanks. Quantitation Limit/CRQL:
I. If a positive sample result is reported
at less than the quancitacion limit and is
also less than the blank action level,
then the sample quancitacion limit
should be reported on the Data
Summary Tables (See example #2 - 5x
rule).
ii. If a positive sample result is reported
at less than the quantitation limit but is
greater than the blank action level,
then the estimated sample result should
be reported on the Data Summary
Tables.
iii. If several target compounds are found
at low levels, below the quancilation
limit, in the laboratory blank(s), it may
indicate a systemic problem in the
laboratory and should be noted in the
Data Validation Memorandum,
iv. If low level contamination exists solely
in the trip, bottle or equipment
(rinsate) blanks, then the validator
should notify the sampler. The call
should be documented in a telephone
log that is included in the Data
Validation Memorandum and the date
of contact should be noted on the
Blank Analysis Worksheet.
d. Determine if gross contamination, greater d. Gross Contamination
than lOx CRQL for any analyte, exists in
any of the blanks. i. If gross contamination, greater than
lOx CRQL for any analyte, exists in
any blank, then the validator should
reject (R) all affected compounds in
samples associated with that blank due
to the interference. This serious
problem should be discussed in the
Data Validation Memorandum.
ii. If gross contamination exists solely in
the tnp, bottle or equipment (rinsate)
blanks, then the validazor should notify
the sampler. The call should be
documented in a telephone log that is
included in the Data Validation
Memorandum and the date of contact
should be noted on the Blank Analysis
Worksheet.
e. Determine if instrument contamination is e. If contamination is limited to a few samples
isolated to specific sample runs. due to instrument concaminauori. then the
validator may use professional judgment in
qualifying sample data from isolated sample
runs.
VOAISV-V-9 DRAFr 12/96

-------
PART l1-VOA/SV Blanks
C. EVALUATION
D. ACTION
*6. f. Review the raw data (chromatograms, mass
spectra and quantication reports) to confirm
the presence of target and non-target
compounds in the blanks and to evaluate the
presence of additional contaminants.
,
6. f. If review of raw data suggests that
additional contaminants are present or,
conversely, the review indicates false
positives have been reported, then the
validator should contact the laboratory to
obtain additional information and/or have
the laboratory requanniate and resubmit all
corrected raw data and forms. If a
discrepancy remains unresolved, the
validator must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
q ualifiers used should be documented in the
Data Validation Memorandum.
7. Evaluate the overall contamination in each type
of blank to ascertain probable source(s) of
contamination. For example, a contaminated
equipment blank might indicate
decontamination problems if the method,
storage, instrument, and bottle blanks were all
clean,
7. If a review of the various types of blanks
identifies a potential source of blank
contamination, then the validator should discuss
this problem in the Data Validation
Memorandum. The validator should identi
whether the measurement error is a result o
either sampling or analytical error or both (see
Data Validation Manual_p.1).
* Note: The following subsections are applicable only to a Tier LU data validation.
C.2.c, C.3.b, C.3.c.i, C.3.c.ii, C.5.b, C.6.f
E. EXAMPLES
Examole #1 : (Bottle blank target compound contaminant CRQL, sample result <5x blank action level)
Carbon disulfice is detected in a water sample at greater than the CRQL, but less than 5x the
bottle blank concentration.
5x Rule
Bottle Blank Result 20
CRQL 10
Carbon disulfide Sample Result 80
Action Level 100
Qualified Sample Result 80 U
In this case, the laborawry sample result for carbon disulfide is less than 100 ug/L (5 x 20)
and the validacor reports the carbon disulfide result as non-detected at an elevated quanutacion
limit on the Data Summary Table. Carbon disulfide was not detected in the method blank but
was detected at 12 ppb in the trip blank. The validator notes in the Data Validation
Memorandum that the bottle blank was contaminated with carbon disulfide, documents the lot
number of the sample bottle, and alerts the site project manager regarding a contaminated lot
of bottles.
VOA/SV-V-10 DRAFf 12/96

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PART fl-VOAI V Blanks
E. EXAMPLES
Exaxny(e #2 (Instrument blank target compound contaminant < CRQL, sample result < 5x blank
action level)
Ethytbenzene is detected in a water sample at less than the CRQL and also less than 5x the
instrument blank concentration. The instrument blank contained the highest concentration of
ethylbenzene of all blanks analyzed. In addition, all field samples analyzed were associated with
the same contaminated instrument blank.
5x Rule
Instrument Blank Result 5
CRQL 10
Ethylbenzene Sample Result 8 J
Action Level
Qualified Sample Result 10 U
In this ca.se, the ethylbenzene sample result is less than 2.5 ugIL (5 x 5) and is reported non-
detected at the CRQL on the Data Summary Table. This problem is noted in the Data Validation
Memorandum.
Examole #3 (Common laboratory contaminarn  CRQL. sample result > lOx blank action level)
Bis(2-ethythexyl)phthalate is detected in a water sample at greater than lOx the method blank
concentration.
lOx Rule
u /L
Blank Result 20
CRQL 10
Bis(2-ethylhexyl)phthalaie
Sample Result 220
Action Level 200
Qualified Sample Result 220
In this case, the bis(2-ethylhexyl)phthalae sample result exceeded the blank action level of 200
ug/L (10 x 20) and the bis(2-ethylhexyl)phthalate sample result is reporteu unqualified on the Data
Summary Table.
Examole (Blank target compound contamination in aqueous equipment blank collected with soil
samples)
An equipment blank (rinsate) was included in a sample delivery group of soil samples. The
vaiidator exammes the data and finds that the equipment blank contains 40 ugfL of bis(2-ethyl
hexyl phtha1ate. The vahdator then reviews all other blank data and finds no further b is(2
ethythexyl)phthalae contamination. One soil sample contains 60 ug/kg of bis(2 .ethylhexy!)
phihalate. The vajidator reports the soil sample result on the Data Summary Table as 60 (EB) to
indicate to the end user that sampling error has potentially affected the sample results and rotes
this information in the Data Validation Memorndum.
VOA1SV-V-11 DRAVI’ 12/96

-------
PART l1-VOA/SV Blanks
E. EXAMPLES
Example 5• (Application of sample weights and volumes with 5x Rule)
Soil sample TAA35 was analyzed as a routine semivolatile soil sample under CL? SOW OLMO3.2
and contained 70% solids. The validacor reviewed the sample results and found naphthalene (560
ug/kg) and pyrene (460 ug/kg) in sample TAA35. The method blank was found to be
contaminated with pyrene (420 uglkg) and naphthalene (430 ug/kg). These blank results were
reported by the laboratory on a dry weight basis and were the maximum levels of contamjj ation
found for these compounds in this sample delivery group. The validator deter-mines the blank
action level by applying the 5x rule. The method blank action level for pyrene was calculated to
be 2100 ug/kg (420 x 5), and the action level for naphthalene was calculated to be 2150 uglkg
(430 x 5).
The validacor calculates the sample quancitatiori limits for naphchalene and pyrene for 30.0 g
extracted:
naphthalene QL = CROL = 330 ug/k = 471 ugfkg
% solids 0.7
pyrene QL = CROL = 330 u /kg = 471 ug/kg
% solids 0.7
The validacor applies the following action to the naphthalene and pyrene results for sample
TAA35:
Naphthalene Pvrene
5x Rule 5t Rule
Blank Result 430 Blank Result 420
CRQL 471 CRQL 471
Sample Result 560 Sample Result 460 1
Action Level 2150 Action Level 2100
Qualified Sample Result 560 U Qualified Sample Result 471 U
• The sample quantitation limit for naphthalene is elevated to the sample concentration result on the
Data Sunirnary Table and is reported as 560U. since the result falls between the sample
quantitarion limit and the blank action level.
• The pyrene sample result on the Data Summary Table is reolaced with the sample quanutacion
limit and is reported as 471U, since the positive sample detect of 460 ugfkg is below both the
sample quancitation limit and the blank acn on level.
The validator notes all actions taken in the Data Validation Memorandum.
VOA/SV-V-12 DRAFI’ 12/96

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PART EI-VOA/SV Blanks
E. EXAMPLES
Example #6 : (Application of laboratory blank action levels to trip blanks)
The method blank for an aqueous batch of volatile samples was contaminated with 25 ug/L of
trichloroethene. The trip blank for this batch of samples was Contaminated with 22 ug/L of
trichioroethene and 15 ug/L of ethylbenzene. Since trichloroechene was detected in both the
method blank and the trip blank. the highest detected concentration is used to determine the blank
action level. The method blank concentration is, therefore, used to determine the blank action
level for trichloroethene.
Trichloroethene Ethvlbenzene
Method Blank Result 25 Method Blank Result 10 U
Trip Blank Result 22 Trip Blank Result IS
CRQL 10 CRQL 10
Blank Action Level 125(5x25) Blank Action Level 75 (5x15)
The tnchloroethene positive detect in the trip blank is qualified and reported as 22U ug/L on the
Data S .rnn1 ry Table. The blank action level for ethylbenzene is determined using the value from
the trip blank arid, as a result, the ethylbeuzene positive detect in the trip blank is reported
unqualified as 15 ug/L on the Data Summary Table.
VOA1SV-V-13 DRAFF 12/96

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PART ll-VOA/SV Surrogate Compounds
VL SURROGATE COl vfPOUNDS
A. OBJECTiVE
Sample matrix effects and laboratory performance on individual samples are assessed by spiking the
samples with surrogate compounds prior to extraction and/or analysis and determining their recoveries.
Evaluation of surrogate recoveries is not necessarily straightforward. Interfering matrix effects, including
high concentrations of target and/or non-target analytes, are frequently outside control of the laboratory
and may present relatively unique problems. Therefore, the evaluation and review of the surrogate
compound results are frequently subjective, demanding extensive analytical experience and professional
judgment. Accordingly, this section consists primarily of guidance with several optional approaches
suggested.
B. CRITERIA
The Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region I Organic data. The CLP-Volatile/Semivolati le method QC
acceptance criteria listed in Appendices A and B should be used as the default criteria when none exist for
the Volatile/Sernjvolatj le analytical method utilized and when similar QC parameters are required by the
non-CLP method and acceptance criteria have not been specified. Deviations, modifications or non-CLP
method-specific QC acceptance criteria may be used but must be explicitly defined in tabular format m the
site-specific EPA approved QAPjP/SAP or amendment to the QAPJP/SAP.
1. The correct method-required surrogate compounds must be added to all samples, QC samples and
blanks at the proper concentrations.
2. a. Recoveries for surrogate compounds in samples, QC samples and blanks must be withm
the QC acceptance criteria specified in the method.
b. Recoveries for advisory surrogate compounds in samples, QC samples, and blanks must
be greater than or equal to 10%.
3. Volatile samples must be reanalyzed in accordance with method requiremeits if surrogate
compound recoveries are outside the method QC acceptance criteria.
4. Semivolatile samples must be reextracted andlor reanalyzed in accordance with method
requirements if surrogate compound recoveries are outside the method QC acceptance criteria.
VOA/SV-Vi-1 DRAFF 12/96

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PART II-VOA/SV Surrogate Compounds
C. EVALUATION! D. ACTION
C. EVALUATION
D. ACTION
All potential impacts the
sample
resulting from
surrogate compound anomalies
should be noted in the Data
Validation
Memorandum. The
should also
document and justify all technical
made based on professional
judgment the
Data Validation Memorandum.
1.
Verify that the correct compounds were used
surrogate compounds and were added at the
required concentrations and frequencies to all
samples, QC samples and blanks.
as
I.
a. If surrogate compounds were not added to
all samples, QC samples and blanks, were
added at the wrong concentration (for
example a sample was ‘doubles spiked) or
an incorrect compound was used, then the
validator should use professional judgment
to qualify or reject sample data.
b. If surrogate compounds were diluted out of
a sample, then the validator should use
professional judgment to qualify or reject
sample data. Greater than five-fold
dilutions result in surrogate recovery data
that may be analytically unusable.
VOAJSV-VI-2 DRAFT’ 12/96

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PART H-VOA/SV
Surrogate Compounds
C. EVALUATION
D. ACTION
2. a., b., c.
Verify that no surrogate compound recovery is
outside the method QC acceptance criteria for
volatile field and QC samples and verify that no
more than one base/neutral surrogate or one
acid surrogate is outside method QC acceptance
criteria for semivolatile field and QC samples.
2. a. If one surrogate in the VOA fraction or
two or more surrogates in the base/neutral
or acid fractions have recoveries greater
than the upper method QC acceptance
limit, then (he validator should:
i. Estimate (J) all volatile, base/neutral or
acid positive detects in the affected
sample fraction.
ii. Accept all volatile, base/neutral or acid
non-detects in the affected sample
fraction.
b. If one surrogate in the VOA fraction or
two or more surrogates in the base/neutral
or acid fractio:is have recoveries greater
than or equal to 10% but less than the
lower method QC acceptance limit, then
the validator should:
z. Estimate (J) all volatile, base!neutral or
acid positive detects in the affected
sample fraction.
ii. Estimate (UJ) all volatile, base/neutral
or acid non-detects in the affected
sample fraction.
c If any surrogate compound in a fraction
recovers at less that 10%, then the
valjdator should:
I. Estimate (J) all volatile, base/neutral or
acid positive detects in the affected
sample fraction.
ii. Reject (R) all volatile, base/neutral or
acid non-detects in the affected sample
fraction.
VOA/SV-VI-3
DRAFT 12/96

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PART II-VOA/SV
Surrogate Compounds
2. d. Verify that no advisory surrogate compound
recovers at less than 10%.
e. Determine if blanic surrogate recovery
results meet method QC acceptance criteria.
2. d. If any advisory surrogate compound m a
fraction recovers at less than 10%, then the
validator should use professional judgment
to qualify the sample data, taking into
account the recoveries of all other
surrogate compounds and the compounds of
concern at the site.
e. lii the special case of a blank analysis with
surrogate compound recoveries outside the
method QC acceptance criteria, the
validator must give special consideration to
the validity of the 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 most of the
samples including other types of blanks in
the batch show acceptable surrogate
compound recoveries, then the validator
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 in the Data Validation
Memorandum. All samples that were
extracted with or analyzed after an out of
control blank should be noted in the Data
Validation Memorandum. Also, note in
the Data Validation Memorandum if there
are potential contractual problems
associated with the failure to reextract
and/or reanalyze blanks that were outside
the method QC accentance criteria.
C. EVALUATION
D. ACTION
3. For at ueous and low/medium soil volatile
3. If a laooratory fails to reanalyze a sample
samples, verify that if surrogate compound
which is out of specification, then the sample
recoveries are outside the method QC
data should be qualified or rejected according to
acceptance criteria, then the required reanalysis
the guidelines above. The validator should note
was performed to confirm that the non-
this method deviation/contractuai deficiency in
compliance was due to sample matrix effects
the Data Validation Memorandum.
rather than poor laboratory performance.
VOAJSV-VI-4
DRAFT 12196

-------
PART I1-VOAJSV Surrogate Compounds
C. EVALUATION
D. ACTION
4. For semivolatile samples, verify jf
surrogate compound recoveries are outside the
method QC acceptance criteria, then the
required reextraction/reanalysis was performed
to confirm that the noncompliance was due to
sample matrix effects rather than poor
laboratory performance.
4. If a laboratory fails to reextract and reanalyze a
sample which is out of specification, then the
sample data should be qualified or rejected
according to the guidelines above. The
validator should note this method
deviation/contractual deficiency in the Data
Validation Memorandum.
*5 a. Check raw data (e.g., chromatograms and
quantitation reports) to verify that surrogate
recoveries were reported accurately on the
Surrogate Recovery Forms.
* b. Ten percent the surrogate compound
recovery data should be checked for
calculation and/or transcription errors. If
errors are detected in this ten percent, then
an additional ten percent of the data should
be checked. If errors are found in the
additional ten percent, then all surrogate
compound recovery calculations and
transcriptions in the data package should be
checked,
5. a. If there are any transcription errors, then
the validator should contact the laboratory
to obtain corrected raw data and forms.
b. If any transcription and/or calculation
errors are detected, perform a more
comprehensive review to determine the
magnitude of the problem. If the problem
is extensive, then the vaiidator should have
the laboratory requantitate and resubmit all
corrected raw data and forms. If a
discrepancy remains unresolved, the
validator must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
* Note: The following subsections are applicable only to a Tier III data validation:
C.5.a, C.5.b
VOAJSV-VI-5 DRAFT 12/96

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PART ff-VOAISV
Surrogate Compounds
Table VOAJSV -VI- 1:
QVALrFICATION OF VOLATILE/SEMIVOLATILE ANALYTES BASED ON
SURROGATE COI’4POUND RECOVERIES
one or more
surrogates < 10%
aU VOA, one B/N or
one acid surrogate
LL %Rec £ UL
Detects
I
J
Non-detects
R
W
LL- Lower Limit of method QC acceptance criteria
UL - Upper Limit of method QC acceptance criteria
A
A
1l
one VOA, two B/N or
two acid surrogates
> UL
I
A
E. EXAMPLES
Example #1 : (Two low acid surrogate recovenes - one of which recovered at less than 10%)
Seniivolatile aqueous sample SA125, analyzed by CLP SOW QLMO3.2, recovered two acid surrogate
compounds, phenol4 and 2-fluorophenol, below the method QC acceptance criteria. In addiuon, the
phenol4 recovered at less than 10%. All other surrogate recoveries met QC criteria. The following
table lists the surrogate spike recoveries and the method QC acceptance criteria:
Sample No.
Pheno l4
% Recovety
QC
Acceptance Criteria
(aqueous)
2-Fluorophenol
% Recovery
QC
Acceptance Criteria
(aqueous)
SA125
8
10-110
15
21-110
The sample was reextracted and reanalyzed with similar results. The validaor examines the PE
sample results, and determines that the laboratory accurately prepared and analyzed the QC samples.
Also, all internal standard areas were acceptable and the MS/MSD results for sample SA126 did not
show a low bias for acid compounds. Therefore, the validacor estimates (J) positive detects and rejects
(R) non-detects for the acid fraction of sample SA125 on the Data Summary Table. The validator
notes in the Data Validation Memorandum that the low recoveries may be due to matrix interferences
specific to sample SA125.
Sample
Results
Surrogate Compound Recovery
one VOA, two B/N or two acid
surrogates
10% %Rec < 1±
VOAJSV-VI-6
DRAFT 12/96

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PART ll-VOA/SV Surrogate Compounds
E. EXAMPLES
EXamDLe #2 : (One low volatile surrogate recovery)
Volatile drinking water sample SA925, analyzed by the Region 1 524.2 method-Reision 8.0, had one
surrogate compound, 1 ,2-dichtorobenzene-d , recover below the method QC acceptance criteria. The
other surrogate compound (1 ,2-dichloroethane4) recovered within the method QC acceptance cnteria.
The following table lists the surrogate spike recovery and the QC acceptance criteria:
Sample No.
I ,2-DichIorobenzene-d
% Recovery
QC
Acceptance Criteria
(drinking water) -
SA925
45
80-120
The sample was reanalyzed 22 days past the holding time. 1 ,2-Dichlorobenzene-c1 4 recovered at 52%
in the reanalysis. The validator reports SA925 sample results from the initial analysis because the
reanalysis results may be biased low due to the exceeded holding time. The validator reviews the
MSIMSD results for sample SA928 and determines that there is no indication of matrix bias in this
data set. The validator estimates (J) positive detects and estimates (Ui) non-detects in sample SA925
on the Data Summary Table and notes in the Data Validation Memorandum that the low recovery may
be due to matrix interferences specific to SA925.
Exanmle #3 : (One slightly low acid and one slightly low base/neutral surrogate recovery)
Semivolatile soil sample SA225, analyzed by CL? SOW OLMO3.2, had one acid surrogate compound,
2 ,4 ,6-tribromophenol, and one base/neutral surrogate compound, 2-fluorobiphenyl, recover below the
method QC acceatance criteria but above 10%. The following table lists the surrogate spike recoveries
and the method QC acceptance criteria:
Sample No.
2 ,4,6-Tribromophenol
% Recovery
QC
Acceptance
Criteria
(soil/sediment)
2-Fluorobiphenyl
% Recovery
QC
Acceptance
Criteria
(soil/sediment)
SA225
16
19-122
22
30-115
Reanalysis was not contractually required because only one acid surrogate and only one base/neutral
surrogate exceeded method QC acceptance criteria. The valithtor reviews the MS/MSD results for
sample SA228 and determines that there is no indication of matnx bias in this data set. The validator
examines all surrogate recoveries, including the advisory surrogates in the samDle, and determines that
validation criteria were met. The validator reports the sample results unqualified on the Data Summary
Table.
VOA/SV-V1-7 DRAFT 12/96

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PART fl-VOAJSV Surrogate Compounds
E. EXAMPLES
Example #4 : (Two slightly low acid surrogate recoveries)
Semivolatile soil sample SA882, analyzed by CLP SOW OLMO3.2, had two acid surrogate
compounds, phenol4 and 2-fluorophenol, recover below the method QC acceptance criteria. All
other surrogate recoveries met method QC acceptance criteria. The following table lists the surrogate
spike recoveries and the method QC acceptance criteria:
Sample No.
Phenol4
% Recovery
QC
Acceptance Criteria
(soil/sediment)
2-Fluorophenol
% Recovery
QC
Acceptance Criteria
(soil/sediment)
SA882
20
24-113
18
25-121
The sample was reextracted and reanalyzed with similar results. The validator reviews the MSIMSD
results for sample SA880 and determines that there is no indication of matrix bias in this data set. The
validator estimates (J) positive detects and estimates (TJJ) non-detects for the acid fraction of sample
SA882 on the Data Summary Table and notes in the Data Validation Memorandum that the low
recovery may be due to matrix interferences specific to sample SA882.
Example #5 : (One advisory base/neutral surrogate with 0% recovery)
1 ,2-dichlorobenzene is a contaminant of concern at Site XX. Seniivolatile water sample SA335,
analyzed by CLP SOW OLMO3 .2, had advisory surrogate compound, I ,2-dichlorobenzene-d 4 , recover
at 0%. All of the remaining surrogate compounds and advisory surrogate compounds had recoveries
which were within method QC acceptance criteria. The validator reviews the MSIMSD results for
sample SA336 and determines that there is no indication of matrix bias in this data set. The validator
uses professional judgment to reject (R) the analyte of concern, 1 ,2-dichlorobenzene, and to reject (R)
the other dichlorobenzene isomers in sample SA335, based upon their chemical similarity to the
advisory surrogate. The validator reports the qualified results on the Data Summary Table and notes
in the Data Validation Memorandum that the low recovery may be due to matrix interferences specific
to sample SA335 poor laboratory technique during the sample extraction and/or cleanup procedures.
VOA/SV-VI-8 DRAFT 12/96

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PART IT-voAlsv Surrogate Compounds
E. EXAMPLES
Example #6 : (One high volatile surrogate recoveiy)
Volatile soil sample SA966, analyzed using SW-846 Method 8260, recovered one surrogate above the
method QC acceptance criteria. The following table lists the surrogate percent recoveries and method
QC acceptance criteria:
Sample Number
% Recovery
Toluene-d
Criteria
QC Acceptance
SA966
128
8L- 117
The sample was reanalyzed within holding time with similar results. The validator reviews the
MSIMSD resuits for sample SA960 and determines that there is no indication of inatax bias in this
data set. The validator estimates (J) positive detects and accepts (A) non-derects in the associated
sample. The validacor reports qualified data on the Data Summary Table and notes sample
qualifications in the Data Validation Memorandum.
VOA/SV-V!-9 DRAFr 12/96

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PART ll-VOA/SV Internal Standards
VII. INTERNAL STAI 4DARDS
A. OBJtCTIVE
[ nstrumenc performance and stability and laboratory precision throughout an analytical sequence are
monitored by the addition of internal standard compounds. Internal standards (ISs) are added to every field
sample, QC sample, standard and blank just prior to analysis. Evaluation of the behavior of internal
standards is not necessarily straightforward. Interfering sample matrix effects, including high
concentrations of target and non-target analytes, are frequently outside of the laboratory’s control and may
adversely affect the analysis of internal standards.
B. CRiTERIA
The Region I. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region I Organic data. The CLP-VolaLile/Semjvola j1e method QC
acceptance criteria listed in Appendices A and B should be used as the default criteria when none exist for
the Volaule/Seniivolatile analytical method utilized and when similar QC parameters are required by the
non-CLP method and acceptance criteria have not been specified. Deviations, modifications or non-CLP
method-specific QC acceptance criteria may be used but must be explicitly defined in tabular format in the
site-specific EPA approved QAPjP/SAP or amendment to the QAPJPISAP.
1. The internal standard compounds specified in the method must be added to all samples, QC
samples, standards and blanks at the required concentrations.
2. Internal standard area counts must be within the method QC acceptance criteria.
3. The retention time of the internal standard must be within the method QC acceptance criteria.
4. Samples must be reanalyzed and/or reextracted in accordance with method requirements if internal
standard method QC acceptance criteria are not met.
VOAJSV-VU-l DRAYF 12/96

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PART H-VOA/SV Internal Standards
C. EVALUATIOt4/ D. ACTION
C. EVALUATION
D. ACTION
All potential impacts on the sample data
resulting from internal standard anomalies
should be noted in the Data Validation
Memorandum. The validator should also
document and justify all technical decisions
made based on professional judgment in the
Data Validation Memorandum.
1.
Verify that the correct compounds were added
to all samples. QC samples, standards and
blanks at the method-specified concentrations.
I.
If the laboratoiy did not add the required
internal standard compounds to all samples, QC
samples, standards and blanks at the correct
concentration, then the validator must use
professional judgment to determine how the
associated sample data should be qualified or
rejected.
2. Verify that all IS area counts are withm the 2. If an IS area count for a sample, QC sample,
method QC acceptance criteria, or blank is outside the method QC acceptance
criteria, then the validator should:
a. Estimate (J) positive detects for compounds
quantitated using an IS area count greater
than the upper limit of the method QC
acceptance criteria.
b. Accept (A) non-detects for compounds
quantitated using an IS area count greater
than the upper limit of the method QC
acceptance criteria.
c. Estimate (J) positive detects for compounds
quantitated using an IS area count less than
the lower linut of the method QC
acceptance criteria.
d. Estimate (UJ) non-detects for compounds
quanutaced using an IS area count less than
the lower limit of the method QC
acceptance criteria but greater than or equal
to 20% of the associated daily continuing
calibration standard area.
e. Reject (R) non-detects for compounds
quantitated using an IS area count less than
20% of the associated daily continuing
calibration standard area or if internal
standard performance exhibits a major
abrupt drop-off, indicating a severe loss of
sensiuvicv.
Alternatively, professional judgment may be
used to assess signal to noise ratios to qualify
or reject sarnule data
VOA/SV-VII-2 DRAY!’ 12/96

-------
PART II-YOA/SV Internal Standards
C. EVALUATION
D. ACTION
3. Verify that all IS retention times are within
method QC acceptance criteria,
3. If an IS retention time for a sample, QC
sample, or blank is outside the method QC
acceptance criteria, then the Va! idator should
examine the chromacographic profile for that
sample to determine if any false positives or
negatives exist. For shifts of a large
magnitude, the validator may consider partial or
total rejection of the data for that sample
fraction. The validator should use professional
judgment to determine if positive detects can be
reported based upon mass spectral identification
criteria being met. The validator should
consider, however, the possible presence of
non-target compounds that are isomers of target
compounds.
*4, Check raw data (e.g., chromatograms and
quanticacion reports) to verify that the internal
standard retention times and areas
accurately reported on the tabulated forms,
—
4. If any transcription and/or calculation errors are
detected, perform a more comprehensive review
to determine the magnitude of the problem. If
the problem is extensive, then the validator
should have the laboratory requancitace and
resubmit all corrected raw data and forms. If a
discrepancy remains unresolved, the validator
must use professional judgment to decide which
value is accurate. Under there circumstances,
the validacor may determine tnat the sample
data should be qualified or rejected. A
discussion of the rationale for data qualification
and the qualifiers used should be documented in
the Data Validation Memorandum.
5. a. Verify that if any internal standard
compound area cou-it or retention time is
outside the method QC acceptance criteria,
that the required reanalysis was performed
to confirm that the non-compliance was due
to sample matrix effects rather than poor
laboratory performance.
5. a. If a laboratory fails to reanalyze a sample
with an internal standard compound that is
outside the method QC acc:ptance criteria,
then the sample data should be qualified or
rejected according to the guidelines above.
The validacor should note this problem in
the Data Validation Memorandum.
VOA/SV-V1I-3 DRAFF 12/96

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PART II-VOA1SV Internal Standards
C. EVALUATION
D.
ACTION
5.
b. If there are two analyses for a paucular
fraction, then the validacor must determine
5. b. If a sample has been analyzed and reported
more than once, then the validacor should
which are the best data to report.
Considerations should include but are not
US professional judgment when considering
which analysis or portion of an analysis to
limited to:
report. The validacor must consider all
relevant QC information in making a
- Magnitude and direction of the IS area
decision.
shift;
- Magnitude and direction of the IS retention
tune shift;
-1: Technical holding times;
- - . Comparison of the values of the target
compounds reported in each analysis;
- Other relevant QC.
* Note: The following subsections are applicable only to a Tier ifi data validation:
C.4
Table VOA/SV-VII-I:
QUALIFICATION OF VOAJSV ANALYTES BASED ON INTERNAL STAI 1DARD AREA COUNTS
)__________ Internal Standard Area Counts
Sample
Results
Area Counts <20%
of assocIated
calibration std. area
20% Area Counts < U-
LL Area Counts UL
Area Counts > IJL
Detects
J
J
A
J
Non.dezects
R
UJ
A
A
LL - Lower Limit of method QC acceptance criteria based on associated calibration standard area
UL - Upper Linut of method QC acceptance criteria based on associated calibration standard area
VOAJSV-Vfl-4 DRAFF 12/96

-------
PART II-VOA/SV
Internal Standards
E. EXAMPLES
Example #l•
(Sequential instrumeat sensitivity loss for one volatile IS compound ending with sample
IS area < LL of method QC acceptance criteria based on associated daily continuing
calibration standard area)
IS = 1 ,4-difluorobenzerie
12 Hour STD
Upper Limit (+100%)
Lower Limit (50%)
27105
54210
13553
The validator re’tews the IS area counts for samples analyzed by CLI ’ SOW OLMO3 2 and notes that
the 1 ,4-dichlorcoenzene-d 4 area count in sample AAAO3 is less than 20% of the associated daily
continuing calibration standard area (20% = 15280). Upon rev ew of the sample data, the validacor
ascertains that phenol was the only target compound detected in the samples. Therefore, the validacor
estimates (J) the positive phenol detect in sample AAAO3 and rejects (R the quanutauon limits for all
other target analvces quantitated using I ,4-dichlorobenzene-d, in sample AAAO3 on the Data Summary
Table. The validacor notes the sample qualifications in the Data Validation Memorandum.
‘I
Sample AAAOI
Samole AAAO2
Samole AAAO3
Sample AAAO4
IS Area Count:
30000
22000
15000
10000
benzene concentration
24
32
38
45
(ug/kg)
The validator reviews the IS area counts for samples analyzed by CLP SOW OLMO3.2 and notes that
the 1 ,4-difluorobenzene area counts decrease sequentially over time and the area counts for sample
AAAO4 are below the lower method QC acceptance limit but greater than 20% of the associated daily
continuing calibration standard area. Upon review of the sample data, the validator ascertains that
benzene was the only target compound detected in the samples. Therefore, the validacor estimates (i)
the benzene positive detects in sample AAAO4 and estimates (UJ) quantitation limits for all other target
analytes quantitated using 1 ,4-difluorobenzene in sample AAAO4 on the Data Summary Table. The
validator discusses the instrument’s sensitivity loss and the sample qualifications in the Data Validation
Memorandum.
Example /12: (One semivolatjle IS compound with area counts < 20% of associated daily continuing
calibration standard)
IS = 1 ,4-dichlorobenzene-
-------
PART [ I-VOAISV Internal Standards
E. EXAI IPLES
Example #3 : (One seniivolacile IS compound with RT shift greater than method QC acceptance limit)
The validator reviews the IS data and determines that the retention time for chloroberizerie.d 5 has
shifted by + 60 seconds which exceeds the ± 30 second QC acceptance limit allowable under CLP
SOW OLMO3.2. Upon inspection of the chromatographic profile, the validator determines that the
mass spectral ideriuficanon criteria have been met for positive detects associated with chlorobenzene-d 5 .
The validator accepts the positive detects associated with chlorobenzcne4 and rejects (R) the
quantitation limits for all other target analytes quantitated using chlorobenzene.d 1 on the Data Summary
Table. The validator discusses the possibility of false negatives in this sample in the Data Validation
Memorandum.
VOA/SV-Vfl-6 DRAFF 12/96
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PART II-VOA/SV Matrix Spike/Matrix Spike Duplicate
VIII. MATRIX SPIKE/MATRIX SPIKE DUPLICATE
A. OBJECTIVE
Data for matrix spike/matrix spike duplicates (MS/MSDs) are generated to determine laboratory precision
and method bias for specific sample matrices at the time of sample preparation and analysis. MSIMSD
data can be used to determine long-term interlaboratory precision and bias of an analytical method for
‘ .‘arious matrices and are used in setting quality control acceptance criteria for spiking compounds.
MS/MSD data should be used in conjunction with other QC data, such as f ield duplicate data and surrogate
compound recoveries, to determine if a sample ot an entire sample group should be qualified.
B. CRITERIA
The Region I. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region I Organic data. The CLP-Volatile/Semivolatile method QC
acceptance criteria listed in Appendices A and B should be used as the default criteria when none exist for
the Volaxile/Seimvolatile analytical method utilized and when similar QC parameters are required by the
non-CLP method and acceptance criteria have not been specified. Deviations, modifications or non-CLP
method-specific QC acceptance criteria may be used but must be explicitly defined in tabular format in the
site-specific EPA approved QAPjP/SAP or amendment to the QAPJP/SAP.
1. In accordance with the SAP, QAPjP andlor method, a field sample of each matrix is spiked in
duplicate with known concentrations of specific target compounds to generate an MSIMSD pair.
Concurrently, the laboratory analyzes an unspiked aliquoc and the MS/MSD pair of the field
sample.
2. a. Field samples (not trip, equipment, or bottle blanks and not PE samples) must be spiked
to assess matrix effects.
b. Field samples chosen for MSIMSD analysis should not contain high levels of MSIMSD
spiking compounds prior to spiking. Preferably, field samples chosen for MS/MSD
analysis should contain low levels of the spiking compounds.
3. Spike recoveries must be within the QC acceptance criteria specified in the method, SAP or
QAPJP.
4. Relative percent differences (RPDs) between MS and MSD recoveries must be within the QC
acceptance criteria specified in the method.
5. The percent relative standard deviation (%RSD) between positively detected non-spike compounds
in the unspiked sample, MS, and MSD must be less than or equal to 50%.
VOA/SV-VflI-1 DRAFT 12/96
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PART ll-VOAJSV Matrix Spike/Matrix Spike Duplicate
C. EVALUATION/ D. ACTION
C. EVALUATION
D. ACTION
1. Verify that the correct compounds were added
at the required concentrations; that MS/MSD
samples were analyzed at the proper frequency;
and that MSIMSD results are provided for each
sample matrix,
All potential impacts on the sample data
resulting from matrix spike/matrix spike
duplicate anomalies should be noted in the Data
Validation Memorandum. The validator should
also document and justify all technical decisions
made based on professional judgment in the
Data Validation Memorandum.
1. If the laboratory did not use the required
compounds at the concentration and frequency
specified in the method for each sample matrix,
then the validator must use professional
judgment to determine whether the associated
sample data should be qualified.
2. a. Verify that a field sample was chosen for
the MS/MSD.
b. Determine if an inappropriate sample
containing high levels of the spiking
compounds is chosen for the MS/MSD
pair.
c. Ascertain if the MSIMSD analyses required
dtlutions.
2. a. If a trip, equipment or bottle blank or a PE
sample was used for the MS/MSD, then the
validator shouLd note this information in the
Data Validation Memorandum and discuss
the impact on assessing laboratory
precision, method bias, sample matrix
effects and ultimately data usability -
b. If the MSIMSD compounds were present in
the field sample at high concentrations
(e.g., 4x spike concentranon) before
spiking, then the validaror must use
professional judgment in assessing matnx
spike recoveries and RPDs.
c. If no MSIMSD data can be reported
because of sample dilution, then the
validator should note this problem in the
Data Validation Memorandum and discuss
the impact on assessing data usability in the
case where laboratory precision and method
bias information aie absent.
VOA/SV-VIII-2 DRAFF 12196
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PART fl-vOA/SV
Matrix Spike/Matrix Spike Duplicate
C. EVALUATION
D. ACTION
3. Verify that all spike recoveries are within the 3. a. If any spike recovery result is greater than
QC acceptance criteria specified in (he method. the upper limit of the method QC
acceptance criteria, then the validator
should:
1. Esiimace (I) the positive detect for that
affected compound in the unspiked
sample.
ii. Accept the non-detect for that affected
compound in the unspiked sample.
b. If any recovery result is greater than or
equal to 10%, but less than the lower limit
of the method QC acceptance criteria, then
the validator should:
i. Estimate (I) the positive detect for that
affected compound in the unspiked
sample.
ii. Estimate (UI) the non-detect for that
affected compound in the unspiked
sample.
c. If any recovery result is less than 10%,
then the validacor should:
i. Estimate (I) the positive detect for that
affected compound in the unspiked
sample.
ii. Reject (R) the non-detect for that
affected compound in the unspiked
sample.
d. If the majority of spike compound
recoveries are outside the method QC
acceptance criteria, then the validaor may
use professional judgment to estimate (3) or
resect (R) jj positive detects and estimate
(UI) or reject (R) non-detects in the
unspiked sample
VOA/SV-Vm-3
DRAFT 12/96
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PART H-VOAISV Matrix Spike/Matrix Spike Duplicate
C.
EVALUATION
D. ACTION
4.
Verify that all the RPDs
between the MS and
4.
If any RPD result is outside the method QC
MSD are within the QC
acceptance criteria
acceptance criteria, then the validator should:
specified in the method.
a. Estimate (I) the positive detect for that
affected compound in the urispiked sample.
b. Estimate (UI) the non-detect for that
affected compound in the unspiked sample.
c. If the majority of the matrix spike RPDs
are outside method QC acceptance criteria,
then the validator should use professional
judgment to estimate (J) positive detects
- and estimate (UI) or reject (R) j non-
detects in the unspiked sample. Refer to
Section VIII C. 8 and 9 for additional
guidance.
VOA/SV-Vlfl-4 DRAFT 12/96
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PART H-VOA/SV Matrix SpikelMatrix Spike Duplicate
C. EVALUATION
D. ACTION
5. a. Calculate the % R.SD for the non-spiked 5. a. If a non-detected result or a detect less than
target positive detects in the unspiked the quantitation limit is reported for a non-
sample, the MS and the MSD. spiked target compound in one of the
samples in the MS, MSD or unspiked
sample set, then the validator should use
the sample quancitation limit value for that
compound to calculate the %RSD.
If a non-detected result or a detect less than
the quanutation limit is reported for a non-
spiked target compound in two of the
samples in the MS, MSD or umispiked
sample set, then the validator should not
calculate the %RSD but should use
professional judgment to qualify sample
data.
b. The unspilced sample, MS, and MSD may b. If any %RSD is gre:uer than 50%, then the
be considered a triplicate in determining the validator should:
overall precision of the analytical method.
Therefore, evaluate the %RSD data for i. Estimaie (J) the positive detect for that
positive detects in the thplicate set. affected compound in the unspiked
sample.
ii. Use professional judgment to qualify or
accept the non-detect for that affected
compound in the unspiked sample.
If overall laboratory precision for the
unspiked field sample, MS, and MSD is
poor, then the validator may use
professional judgment to qualify j positive
detects and non-detects in the unspiked
sample. The Data Validation
Mernoranduni should include a discussion
of the potential impact of laboratory
precision on representauveness and
usability of the data in meeting the project
____ DQOs.
VOA/SV-VflI-S DRAFF 12/96
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PART ll-YO4JSV Matrix Spike/Matrix Spike Duplicate
EVALUATION
D. ACTION
the analytical
6. If any transcription and/or calculation
percent recovery for at least
errors are
detected, perform a more
per MS/MSD fraction.
comprehensive review
to determine the magnitude of the
value agrees within
problem. If
the problem is extensive, then the
value,
validator
should have the laboratory requantitate and
resubmit all corrected raw data and forms. Ef a
discrepancy remains unresolved, the validacor
must use professional judgment to decide which
value is xcurate. Under these circumstances,
the validator may determine that the sample
data should be qualified or rejected. A
discussion of the rationale for data qualification
and the qualifiers used should be documented in
the Data Validation Memorandum.
the RPD for at least one
7. If any transcription and/or calculation
MSIMSD fraction.
errors are
detected, perform a more
value agrees within
comprehensive
to determine the magnitude of the
value,
problem.
the problem is extensive, then the validacor
should have the laboratory requantitate and
resubmit all corrected raw data and forms. If a
discrepancy remains unresolved, the validacor
must use professional judgment to decide which
value is accurate. Under these circumstances,
the validator may determine that the sample
data should be qualified or rejected. A
discussion of the rationale for data qualification
and the qualifiers used should be documented in
the Data Validation Memorandum.
of qualifying the
8. Generally, no action is taken based
the
MS/MSD laboratory
on
MS/MSD data alone to qualify an entire
bias results.
case.
The qualification is limited to the unspiked
sample associated with the MS/MSD.
However, professional judgment may be used
to qualify sample results across a particular
aqueous matrix (i.e., all associated groundwater
samples) or a homogeneous soil matrix.
VOAJSV-Vffl-6 DRAFT 12/96
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PART II-VOA/SV
Matrix SpikefMatrix Spike Duplicate
C.
EVALUATION
D.
ACTION
9.
Evaluate MSIMSD precision data to confirm the
9.
If precision data for the laboratory MS/MSD
laboratory’s ability to generate precise data and
pair, surrogate compound recoveries and field
field duplicate precision data to assess overall
duplicate pair indicate a heterogenous matrix at
precision. Surrogate recovery data can also be
the site or potential sampling error, then the
evaluated to identify laboratory precision issues
validator may use professional judgment to
and overall matrix precision issues.
qualify j affected compounds and/or Li field
sample results. This problem should be noted
in the Data Validation Memorandum and the
potential impact on the representativeness and
usability of the data in meeting the project
DQOs should be discussed. Refer to Section
IX for additional guidance.
Note: The following subsections are applicable only to a Tier Ill data validation:
C.6, C.7
Table VOA/SV-Vm-1:
OUALWICATION OF ORGANIC ANALYTES IN THE UNSPIKED FIELD SAMPLE
BASED ON MATRIX SPIKE RECOVERIES AND RPDs
Sample Re3UJtl
Recovery < 10%
10% Recovery <
Lower QC Limit
Lower QC Limit
Recovery
Upper QC Limit
Recovery>
Upper QC
L -u 1
RPD> QC Limit

Detects
J
J
A
J
j
Nondetects
R
w
A
A
ui
** Note that qualification and rejection generally are limited to the spiking compounds, however, the validator may
use professional judgment to qualify or reject positive detects or non-detects in the unspiked sample if the
majority of spike compound recoveries and/or RPDs are outside the method QC acceptance criteria.
VOA/SV-VIfl-7
DRAFT 12/96
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PART n-voAJSv Matrix SpikefMatrjx Spike Duplicate
Table VOAJSV.Vjj1 -2•
QUALIFICATION OF ORGANIC ANALYTES IN THE UNSPIKED FIELD SAMPLE
BASED ON MS. MSD, AND UNSPEKED SAMPLE %RSD
Sample Results
%RSD 50%
%RSD > 50%
Two out of three sample
results reported as non-detects
Detects
A
I
Professional Judgment
ProfessIonal Judgment
Non-detects
A
Professional Judgment
* If a non-detect is reported for a compound in only one of the samples in the MS, MSD or unspiked sample set,
then the validator should use the sample quarnitation limit value for that compound to calculate the % RSD.
E. EXAMPLES
Example #1 (High MS/MSD RPD for one compound)
Soil QC samples SAA99MS and SAA99MSD, analyzed as medium level soil samples under CLP
SOW OLMO3.2, have unacceptable RPD results for acenaphthene. Acenaphthene was detected
in the unspiked sample, SAA99.
Sample No.
Compound
MSIMSD
%Rec
MS/MSD
%Rec Crieria
MSIMSD
RPD
MS/MSD
RPD
Criteria
SAA99MS
SAA99MSD
Acenaphthene
60/116
31-137
64
19
The validator evaluates the field duplicate pair and determines that the RPDs for all posidve
detects are less than 5O , indicating acceptable overall precision for this sampling event. The
validacor then concludes that the lack of laboratory precision in this sample is due to poor
laboratory technique. The vajidator estimates (J) the positive detect for acenaphthene in the
unspiked sample, SAA99, on the Data Summary’ Table. The validator discusses the lack of
laboratory precision for one compound, acenaphthene, in the Data Validation Memorandum and
notes that laboratory precision for the other sermvolaule matnx spike compounds was acceptable.
VOA/SV-Yffl-S DRAFT 12/96
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PART ll-VOA/SV Matrix Spike/Matrix Spike Duplicate
E. EXAMPLES
Example #2 (Low MSIMSD recoveries for one compound)
Aqueous QC samples SAA22MS and SAA22MSD, analyzed under CLP SOW OLMO3.2, have
low toluene recovery results but acceptable RPD results. Toluene was detected in the unspiked
sample. SAA22. Surrogate compound recovenes were acceptable for SAA22MS, SAA22MSD
and the unspiked sample, SAA22.
Sample No.
Compound
MS/MSD
%Rec
MS/MSD
%Rec Criteria
MS/MSD
RPD
MS/MSD
RPD Criteria
SAA22MS
SAA22MSD
Toluene
50/46
76-125
8
13
The validator evaluates the field duplicate pair and determines that the RPDs for all positive
detects are less than 30%. indicating acceptable overall precision for this sampling eveat. The
validator concludes that the sample matrix causes a reproducible negative bias for toluene in
aqueous samples SAA22MS and SAA22MSD. The validator estimates (J) the positive detec: for
toluene in the unspiked sample, SAA22, on. the Data Summary Table. The validator discusses the
low matrix spike recoveries in the Data Validation Memorandum and notes that recoveries for the
other volatile matrix spike compounds were acceptable.
Examole #3 : (High %RSD; High RID, poor laboratory precision)
Soil samples SAA55, SAA55MS and SAA5SMSD analyzed under CLP SOW OLMO3.2, had high
RIDs for two of the acid semivolatile matrix spike compounds in the MS/MSD, 2-chiorophenol
(53%) and 4-aitrophenol (92%) and two base/neutral semivolatile spike compounds, 1,2.4-
tnchlorobenzene (65%) and acenaphthene (76%). 2-chlorophenol, 4-nitrophenol, 1.2,4-
trichlorobenzene, and acenaphthene were not detected in the unspiked sample. The other
remaining matrix spike compound RPDs were acceptable. The following non-spike target
compound results were obtained for SAA5SMSIMSD and the unspiked sample SAA55.
Sample No.
Compound
MS Conc.
Dry Weight
(ug/kg)
MSD Conc.
Dry Weight
(uglkg)
Unspiked
Sample
Conc.
Dry Weight
(ug/kg)
% RSD
SAA5S
2,4-Dimethylphenol
1200 —
350
600
61
SAA55
2,4,6-Trichlorophenol
380
1030
33011
67
SAA S5 Hexach’ obenzene 920 330U J 400 59
The validator eva’uates the field duplicate pair and determines that the RPDs for all positive
detects are less than 50%. indicating acceptable overall precision for this sampling event. The
validator then concludes that the lack of precision is due to poor laboratory technique. The
validator uses professional judgment to estimate (.1) the positive detects for 2,4-dimethylphenol and
hexachlorobenzene in SAA55 and estimate (Ui) all non-detects in sample SAA55 on the Data
Summary Table. The validator discusses the poor laboratory precision and notes the sample
qualifications in the Data Validation Memorandum
VOA/SV-Vffl-9 DRAFT 12/96
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Piu T a-votisv Matrix Spike/Matrix Spike Duplicate
E. EXAMPLES
Example #4 : (Low MS/MSD recoveries for entire compound class)
Soil QC samples SAAO IMS and SAAOIMSD, analyzed under CL? SOW OLMO3.2, have low spike
recoveries for four of the five acid compounds in the matrix spike and the matnx spike duplicate (less
than the specified QC acceptance Criteria but greater than 10%); while base neutral matrix spike
compounds meet QC acceptance criteria. The phenol-d 5 and 2-Iluorophenol acid surrogate recoveries
are at the low end of the QC acceptance criteria in SAAO IMS and SAAO1MSD
Sample No.
,
Compound
MS %
Recovery
MSD %
Recovery
RPD
QC Acceptance
Criteria
-
%Rec
RPD
SAAO1MSIMSD
Phenol
21
21
0
26-90
35
2-Chlorophenol
15
18
18
-.25-102
50
4-Ch loro-3-methylpheno l
21
20
5
.26-103
33
Pentachiorophenol
14
14
0
17-109
47
Phenol-dS (surrogate)
26
28
NA
24-113
NA
2-Fluorophenol
(surrogate)
27
25
NA
25-121
NA
Upon review of the MSIMSD results and surrogate recoveries, the validator notes that the sample
matrix causes a reproducible negazive bias for acid compounds in soil QC samples SAAOIMS and
SAAO IMSD. The validaror reviews the surrogate recoveries for the unspiked sample and notes that
the acid surrogate recoveries are within the QC acceptance criteria (at the low end of the QC
acceptance range). The validator then reviews the surrogate recoveries for all samples associated with
the sample delivery group to ascertain if acid surrogate recoveries are also low in the remaimng
samples.
Several samples, including the field duplicates, show low acid surrogate recoveries that were greater
• - than 10%. The validator estimates (i) all positive acid detects in the unspiked MS/MSD sample and
estimates (UJ) all acid non-detects in the unspiked MS/MSD sample. The validator uses professional
judgment to estimate (J) the positive acid detects and estimate (UJ) the acid non-detects in all other
samples associated with this sample delivery group in which acid surrogates recovered low. The
validator reports qualified data on the Data Summary Table and discusses the low bias in the Data
Validation Memorandum.
VOA/SV-VIll-IO DRAFF 12/96
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PART II-VOA/SV Matrix Spike/Matrix Spike Duplicate
E. EXAMPLES
Example #5 (High MS/MSD RPDs for multiple compounds)
Aqueous QC samples SAAO8MS and SAAO8MSD, analyzed under CLP SOW OLMO3.2, have
high RPDs for 2 acid and 3 base neutral compounds in the matrix spikefmainx spike duplicate
pair. The matrix spike recoveries in the MS and MSD were all within QC acceptance criteria.
All surrogate recoveries for SAAO8MSD were acceptable except for the advisory surrogate, 2-
chlorophenol-d . All surrogate recoveries for SAAO8MS were acceptable except for nitrobenzene-
d and terohenyl-d 4 . Hexachlorobenzene and dibenzofuran were the only positive detects in the
unspiked sample, SAAO8. The validator calculates the %RSD for hexachlorobenzene (59%) and
dibenzofuran (70%).
Sample No.
Compound
MS %
Recovery
MSD %
Recovery
RPD
QC Acceptance
Criteria
%Rec
RPD
SAAO8MSIMSD
N-Nitroso-di-n-propylamine
43
80
60
41-116
38
1,2,4-Tnchlorobenzene
—__93
48
64
39-98
28
2,4-Dinitrotoluene
—__87
33
9()
24-96
38
Pentachiorophenol
— 15
78
135
9-103
50
2-Chlorophenol
96
40
82
27-123
40
Nirrobenzene4 (surrogate)
25
65
NA
35-114
NA
2-Chlorophenol-d 4 (surrogate)
70
30
NA
33-110
NA
Terphenyl-d 14 (surrogate)
— 30
83
NA
33-141
NA
Sample No.
Compound
MS Conc.
(ug/L)
MSD Conc.
(ug/L)
Unspiked
Sample
Conc.
(ug/L)
% RSD
SAA O8
Hexachlorobenzene
20 —
80
85
59
Dibenzofuran
57
22
110
70
Upon review of the MSIMSD results, surrogate recoveries, and the % RSDs, the validator notes
the laboratory imprecision and suspects that problems occurred during extraction and/or analysis
of the MS/MSD and/or unspiked sample. The validator then reviews the field duplicate data and
surrogate recoveries for the remaining samples in the sample delivery group to assess other
precision and bias data.
Surrogate recoveries in all other samples were acceptable. The field duplicate RPD data was also
acceptable. Therefore, the validator determines that poor precision was limited to the MS/MSD
pair. The validator uses professional judgment to estimate (J) jj positive de eczs and estimate
(UJ) all non-detects in the unspiked sample SAAO8 on the Data Summary Table. The validator
notes this problem in the Data Validation Memorandum.
VOA/SV-VllI-1 1 DRAFT 12/96
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PART ll-VOA/SV Field Duplicates
IX. FIELD DUPLICATES
A. OBJECTIVE
Field duplicates measure the cumulative effects of both field laboratory precision and hence provide
an indication of overall precision. Therefore, field duplicates may have greater variability than laboratory
duplicates which measure only laboratory precision. It is also expected that non-aqueous matrices will have
a greater variance than aqueous matrices due to the heterogeneity of most non-aqueous samples (such as
soil/sediment samples).
B. CRITERIA
1. The frequency of field duplicate analysis must support the site-specific Data Quality Objectives
(DQOs) and be documented in the EPA approved QAPJP or SAP.
2. a. The RPD for all compounds detected at concentrations greater than the sample
quandtation limit in aqueous matrices must be less than or equal to 30 percent.
b. The RPD for all compounds detected at concentrations greater than the sample
quancitation limit in non-aqueous matrices must be less than or equal to 50 percent.
C. EVALUATIONI D. ACTION
C.
EVALUATION
D.
ACTION
AU potential impacts on the sample data
resulting from field duplicate anomalies should
be noted in the Data Validation Memorandum.
The validacor should also document and justify
all technical decisions made based on
professional judgment in the Data Validation
Memorandum.
I.
a.
Identify which samples are field duplicates
1.
a. If field duplicates are not listed on the
from the Chain-of-Custody form andfor the
Chain-of-Custody form or the Traffic
Traffic Report.
Report, then the validator should contact
the sampler to ascertain if field duplicates
were collected. If the forms were
completed incorrectly or if field duplicates
were not collected, then the validator
should document this on the Data
Validation Worksheet and in the Data
Validation Memorandum.
b.
Verify that the appropriate number of field
duplicates per matrix sampled were
b. If field duplicates were not collected at the
required frequency to support project
collected and analyzed to support project
DQOs. then the validator should note the
DQOs.
absence of field precision data in the Data
Validation Memorandum and discuss how
the lack of field precision data might
potentially increase uncertainty surrounding
site decisions.
VOA/SV-IX-1 DRAFI’ 12/96
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PART II-VOAJSV
Field Duplicates
C. EVALUATION
D. ACTION
2. Calculate the RPD for all compounds detected 2. a. If any compound is detected at
at COrIcen(rations greater than or equal to the concentrations greater than or equal to
sample quanutacion limit in the field duplicate twice the sample quanutation limit in both
aqueous field duplicate samples and has an
RPD greater than 30%, then the validator
should estimate (J) the positive detects for
that compound in both samples.
If any compound is detected at
concentrations greater than or equal to the
sample quantitanon limit but less than twice
the sample quantitation limit in both
aqueous field duplicate samples and has an
RPD greater than 30%, then the validator
should use professional judgment to accept,
qualify, or reject the positive detects for
that compound in the field duplicate
samples taking into consideration the
increased variability of data near the
sample quantitation limit and the site-
spectfic DQOs.
b. If any compound is detec:ed at
concentrations greater than or equal to
twice the sample quantitation limit in both
non-aqueous field duplicate samples and
has an RPD greater than 50%, then the
validator should estimate (J) the positive
detects for that compound in both samples.
If any compound is detected at
concentrations greater than or equal to the
sample quantitazion limit but less than twice
the sample quantuation limit in both non-
aqueous field duplicate samples and has an
RPD greater than 50%, then the validator
should use professional judgment to accept,
qualify, or reject the positive detects for
that compound in the field duplicate
samples taking into consideration the
increased variability of data near the
sample quantitation lirrut and the site-
specific DQOs
VOA/SV-IX-2
DRAFT 12/96
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PART II-VOA/SV
Field Duplicates
2. c. If any compound in a field duplicate pair
has one positive detect chat is greater than
or equal to twice the sample quantication
limit and a duplicate positive detect that is
less than twice the sample quantitation
limit, and the RPD exceeds field duplicate
precision criteria for that matnx. then the
validator should use professional judgment
to qualify the positive detects for chat
compound in the field duplicate samples.
d. If any compound in a field duplicate pair
has one non-detect and a duplicate positive
detect that is greater than or equal to twice
the sample quantication limit, then the
validator should estimate (J) the positive
detect and (UJ) the non-detect for that
compound in the field duplicate samples.
(RPDs should not be evaluated for those
duplicate pairs.)
e. If any compound in a field duplicate pair
has one non-detect or a reported value
below the sample quantitation limit and a
duplicate positive detect chat is less than
twice the sample quanmation limit, then the
validator should use professional judgment
to qualify the positive detects and non-
detects for that compound in the field
duplicate samples caking into c: sideration
the increased variability of data at the
sample quanntation limit and the project
DQOs. (RPDs should not be evaluated for
those duplicate pairs.)
f. If any compound in a field duplicate pair
has one non-detect or a reported value
below the sample quantitation lirmt and a
duplicate positive detect that is less than the
sample quantitation limit, then the validator
should use professional judgment to qualify
the positive detects and non-detects for that
compound in the field duplicate sample pair
taking into consideration the increased
variability of data at the sample quantitation
limit and the project DQOs (RPDs should
not be evaluated for those duplicate pairs).
2. Continued from above.
C. EVALUATION
D. ACTION
VOA/SV-L’C-3
DRAFT 12/96
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PART EI-VOA/SV Field Duplicates
C. EVALUATION
D. ACTION
*3• Check and recalculate the analytical
3. If calculation and/or transcnpcion errors are
concentrations for at least one positive detect
detected, then the vaiidator should follow the
and one sample quantitacion limit (for a diluted
procedures outlined in Section VOA/Sv XIII,
sample or sod sample) for each fraction, in
D. I - D.3.
every field duplicate sample, in accordance with
Section VOA/SV-XflI, C.! - C.3.
4. Evaluate the appropriateness of qualifying the
4. If field duplicate data indicate poor field
entire data set based on field duplicate results.
precision and general sample heterogeneity
and/or possible sampling error, then
-.
professional judgment may be used to qualify
data for ik samples of the same matrix.
5. Evaluate field duplicate precision data to assess
5. If precision data for the field duplicate pair,
overall precision and to verify the field
surrogate compound recoveries and laboratory
sampler’s ability to collect representative
MSIMSD pair indicate a heterogeneous matrix
duplicate samples. MS/MSD precision data
at the site or potential sampling error, then the
should be evaluated to verify the laboratory’s
validator may use professional judgment to
ability to generate precise data. Surrogate
qualify affected compounds and/or all
recovery data can also be evaluated to identify
affected field sample results. This problem
laboratory precision issues and overall matrix
should be noted in the Data Validation
precision issues.
Memorandum and the potential impact on the
represencativeness and usability of the data in
meeting project DQOs should be discussed.
Refer to Section VIII for additional guidance.
Note: The following subsections are applicable only to a Tier III data validation:
C.3
Table VOA/SV-IX- I:
QUALIFICATION OF ORGANIC ANALYZES IN FIELD DUPLICATES -
SITUATION 1: POSITIVE DETECTS IN BOTH FIELD DUPLICATES
Relative
Percent
thiference
Aqueous > 30%
Non-Aqueous > 50%
Aqueous > 30%
Non-Aqueous > 50%
Aqueous> 30
Non-Aqueous> 50%
Sample Results
L
Both duplicate sample QL both duplicate samples
2XQL J cones. <2XQL
One sample cone. 2 X QL
QL Othersampleconc. <2XQL
Detects
j
Professional Judgment
Professional Judgment
Non-detects
NA
NA
NA
* QL = Sample Quantitacion Limit
Note Qualification refers to held duplicate sample results only Professional judgment may be utilized to apply
field duplicate actions to all samples of the same matrix
VOA/SV-IX-4 DRAFT 12/96
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PART fl-VOAISV
Field Duplicates
Table VOA/SV-IX-2.
QUALIFICATION OF ORGANIC ANALYTES IN FIELD DUPLICATES -
SITUATION 2: POSITIVE DETECT IN ONLY ONE FIELD DUPLICATE
Aqueous and Non-Aqueous
Sample Results
One Sample Conc. = ND (or value reported as
less than the QL)
QL Other SampleConc. 50%; Acceptable
laboratory precision)
Soil samples SAA1 1 and SAA12 are field duplicates, analyzed under CLP SOW OLMO3.2, and
they contain 89% and 85% solids, respectively. Sample SAA 11 has a detected concentration of
benzene of 100 uglkg. Sample SAA12 has a detected concentration of benzene of 250 ug/kg.
The validator calculates the Relative Percent Difference (RPD) and determines that the RPD equals
86%. The validator notes that both results are greater than twice the sanmie Quantitation Limit
(QL). The QL for benzene in sample SAA I1 is 11 uglkg and for sample SAA12 is 12 ug/kg.
The validazor reviews the MS!MSD data and determines that laboratory precision was acceptable.
As a result, the validator estimates (fl the positive benzene detects in the field duplicate samples
only, on the Data Summary Table, and notes the qualification and justification in the Data
Validation Memorandum. The validator also notes that poor field precision may be due to a
heterogenous matrix or a result of sampling error.
Compound
SAA1 I
SAA I2
RPD
Sample Conc.
(ugfkg)
Sample QL
(uglkg)
Sample Conc.
(ugfkg)
Sample QL
(uglkg)
benzene
100
11
—
250
12
86
VOA/SV-IX-5
DRAFF 12196
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PART u-vo JSv Field Duplicates
E. EXAMPLES
Example #2 : (QL both field duplicate sample concentrations < 2X QL; RPD > 50%; Acceptable
laboratory precision)
Soil samples SAA21 and SAA22 are field duplicates, analyzed under CLP SOW OLMO3.2, and
they contain 50% and 52% solids, respectively. Sample SAA21 has a detected concentration of
trichiorophenol of 690 ug/kg. Sample SAA22 has a detected concentration of trichlorophenol of
1220 uglkg. The validator determines that the RPD equals 56%. The sample QL for
trichiorophenol in sample SAA2I is 660 uglkg based on 50% solids and the sample QL for sample
SAA22 is 630 ugfkg based on 52% solids. The validator reviews the MS/MSD results and
determines that laboratory precision is acceptable. The validator notes that both field duplicate
results are between the sample QL and twice the sample QL. As a result, the validator uses
professional judgment to accept the trichiorophenol results in the field duplicate samples taking
into consideration the increased variability of data near the quantitation limit. The validator notes
in the Data Validation Memorandum that field duplicate precision was acceptable.
Compound
SAA2 I
SAA22
RPD
Sample Conc.
Sample QL
Sample Conc.
Sample QL
(ugIkg)
(uglkg)
(ug/kg)
(uglkg)
trichlorophenol 690 660 1220 630 [ 56
Example #3: (One sample concentration = ND; One sample concentration 2X QL; Acceptable
laboratory precision)
Aqueous samples SAA3I and SAA32 are field duplicates, analyzed under CLP SOW OLMO3.2.
Sample SAA3 1 has a detected concentration of trichloroethene of 25 ugIL. Trichioroethene was
not detected in sample SAA32. The validator notes that the positive cnchloroethene detect in
sample SAA3I is greater than twice the sample QL (10 ug/L). The validator reviews the
MSIMSD data and determines that laboratory precision was acceotable. The validator estimates
(J) the positive trichioroethene detect in sample SAA3 I and estimates (UJ) the quantitation limit
of the tricliloroethene non-detect in sample SAA32 on the Data Summary Table based on poor
field precision. The validator notes the qualification in the Data Validation Memorandum and also
suggests that poor field precision may be due to sampling error.
Compound
SAA3I
SAA32
RPD
Sample Conc.
Sample QL
Sample Conc.
Sample QL
(ug/L)
(ugIL)
(ugIL)
(ug/L)
[ trich1oroethene
25
10
ND [ 10 f
NA
VOA/SV-IX-6 DRAFF 12/96
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PART ll-VOA/SV Field Duplicates
E. EXAMPLES
Example #4 (One sample concentration = ND; One sample concentration < 2X QL; Acceptable
laboratory precision)
Soil samples SAA41 and SAA42 are field duplicates, analyzed under CLP SOW OLMO3.2, and
they contained 90% and 85% soLids, respectively. Sample SAA4 I has a detected conceritrauon
of chlorobenzene of 19 ugfkg. Chlorobenzene was not detected in sample SAA42. The validator
notes that the positive chlorobenzene detect is between the sample QL and twice the sample QL.
The sample QL for chlorobenzenc in sample SAA4L is 11 uglkg and in sample SAA42 is 12
ug/kg. The validator reviews the MS/MSD results and determines that RPD criteria were met for
chiorobenzene, indicating acceptable laboratory precision. As a result, the validator uses
professional judgment to accept the positive chlorobenzene detect in sample SAA41 and to accept
the chlorobenzene non-detect in sample SAA42, taking into consideration the increased variability
of data near the quantitation limit. The validator reports the results on the Data Summary Table
and notes this in the Data Validation Memorandum.
Compound
SAA4L
— SAA42
RPD
Sample Conc. Sample QL
Sample Conc.
Sample QL
(ug/kg) (ug/kg)
(ug/kg)
(ugfkg)
chlorobenzene 19 11 ND 12 NA
Examole #5: (Both duplicate concentrations 2X QL; Poor field laboratory precision)
Soil samples SAA34 and SAA35 are field duplicates, analyzed under CLP SOW QL.M03.2, and
they contain 90% and 95% solids, respectively. Sample SAA34 has a detected concentration of
pyrene of 1400 ug/kg. Sample SAA35 has a detected concentration of pyrene of 3500 ugfkg. The
validator calculates the Relative Percent Difference (RPD) and determines that the RPD equals
36%. The validator notes that both results are greater than twice the sample QL. The sample QL
for pyrene in sample SAA34 is 370 ugfkg and the sample QL for pyrene in sample SAA35 is 350
ug/kg. The validator reviews the MS/MSD data for samples SAA34 MS/MSD and determines
that the RPD for pyrene equals 61 %. The validator is unable to determine the source of the
imprecision since both the lab and field precision were poor; therefore, the validator uses
professional judgment to estimate (3) the positive pyrene detects in all samples associated with the
sample delivery group and estimates (UJ) the quantitation limits for pyrene non-detects in all
samples associated with the sample delivery group. The validator reports the qualified data on
the Data Summary Table and justifies the qualification in the Data Validation Memorandum. The
validator notes that the source of the imprecision cannot be determined.
Compound
pyrene
SAA34
Sample Conc. Sample QL
(ug/kg) (ug/kg)
1400 370
SAA35 RPD
Sample Conc. Sample QL
(u ’1cg) (ug/kg)
— 3500 [ 350 86
VOAISV-LX-7 DRAFT 12/96
-------
PART il-voAiSv Sensitivity Check
X. SENSITIVITY CHECK
A. OBJECTIVE
Although most CL? SOWs do not Incorporate the analysis of sensitivity checks, many EPA methods do
require that a Method Detection Limit (MDL) study be performed prior to sample analysis and/or that a
Laboratory Fortified Blanc (LFB) be analyzed at the time of sample analysis. The MDL study generates
statistically-based detection limits and can be used to assess method sensitivity, laboratory precision and
method bias for specific compounds within an analytical method on a specific instrument and column. An
LFB, a type of Laboratory Control Sample, is a reagent blank spiked with several or all of the target
compounds at or below their quantication linut.s. LFB data can be used to assess laboratory sensitivity and
bias for specific compounds at the quantitation limit within an analytical method on a specific instrument
and column at the time of sample preparation and analysis. To determine sample qualification, the MDL
study is evaluated prior to the LFB data.
Region I routinely uses MDL studies as a pre-qualification check to verify the laboratory’s ability to meet
the technical specification/method requirements prior to contract award and field sample receipt. Region
I also routinely includes LFB analyses to document the method sensitivity and bias associated with the day-
to-thy preparation and anal: s of field samples.
B. CRrrERIA
The Region I. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region I Organic data. The CLP-Volatile/Senuvolaule method QC
acceptance criteria listed in Appendices A and B should be used as the default criteria when none exist for
the Volanle/Seinivolatjje analytical method utilized and when similar QC parameters are required by the
non-CL? method and acceptance criteria have not been specified. Deviations, modifications or non-CLP
method-s: ecific QC acceptance criteria may be used but must be explicitly defined in tabular format in the
site-specific EPA approved QAPJP/SAP or amendment to the QAPJP/SAP.
I. Method Detection Limit (MDL) Study
a. The method detection limit (MDL) for each compound of interest must be established in
accordance with the specified method and the Code of Federal Regulations (40 CFR Part
136, App. B). A minimum of seven replicates must be analyzed for each matrix of
interest.
b. Surrogates and internal standards must be spiked into each MDL sample as specified in
the method. Internal standard area counts and retention times must meet method QC
acceptance criteria. Recoveries and % RSDs for surrogates and target compounds must
meet the criteria specified in the method. If the method does not specify recovery and/or
replicate %RSD criteria, then the %RSD for the seven replicates should be less than or
equal to 25% and the mean recovery for target compounds and surrogates should be
between 80-120%
c Samples must be analyzed on the same instrument under the same conditions (trap,
column, temperature program. amount of sample purged, etc.) as was used for the MDL
study.
VOA/SV-X-1 DRAFF 12/96
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PART i1-vo 4 tisv Sensitivity Check
d. The MDL study must be performed within one year prior to the start of the preparation
and/or analysis of the samples.
e. The MDL for each compound must be less than or equal o that compound’s method.
required quantitacion limit.
2. Laboratory Fortified Blank (LFB)
a. Verification of laboratory accuracy at the quantiration level requires the routine analysis
of an LFB spiked with target compounds at the quanticanon limit and, internal standard
and surrogate compounds spiked at the concentrations specified in the method. The stock
solution used for spiking the LFB must be prepared from a source other than the source
used for preparing the initial and continuing calibration standards.
b. One LFB containing all the target compounds at the quanhitacion limit must be analyzed
immediately prior to sample analysis but after instrument tuning and calibration.
Subsequently, an LFB must be analyzed every 12 hours. One LFB must be extracted with
each sample delivery group of seniivolacile samples, or whenever semivolatile samples
are extracted, whichever is more frequent.
c. Method QC acceptance criteria must be met for surrogates, internal standards and target
compounds. If the method does not specify recovery QC acceptance criteria for the LFB,
then the recovery for target compounds should be between 60-140%. Surrogate
compounds and internal standards for the LFB must meet validation criteria as per
Sections VI and VII of this document.
VOA/SV-X-2 DRAFr 12/96
-------
PART l1-VOA/5v Sensitivity Check
C. EVALUATION/ D. ACTION
C. EVALUATION
D. ACTION
Qualification of data should be based on an
All potential impacts on the sample data
combined evaluation of both the MDL study
resuhing from LFB and/or MDL study
and LFB results. To deternune appropriate
anomalies should be rioted in the Data
sample qualification, the MDL study should be
Validation Memorandum The validator should
evaluated first and then the LFB results.
also document and justify all technical decisions
made based on professional judgment in the
Data Validation Memorandum.
1.
Method Detection Limit (MDL) Study
1.
Method Detection Limit (MDL) Study
a. Verify that the MDL study was generat...i
a. If the required MDL study was not
in accordance with the method anc 40 CFR
performed at all or was not per-formed
Part 136 App. B. and that a mirumum of
according to the CFR criteria, then the
seven replicates for each matrix of interest
validator should evaluate the LFB data, if
were prepared and analyzed.
available, to deterrnme the action to be
taken. See Tables VOA/SV.X.l,
VOAJSV-X-2, and VOA/SV.X.3. If no
LFB data are available, then the validator
should use professional judgment to assess
the impact of analytical sensitivity on data
quality.
b. Verify that internal standard area counts
b. If internal stancard area counts andlor
and retention times meet method QC
retention times do not meet method QC
acceptance criteria,
acceptance criteria, then the validator
should follow the guidance provided in
Section VOAJSV-vJI
VOA/SV-X-3 DRAFT 12/96
-------
PART U-VOA/SV
Sensitivity Check
1. C. Compare all seven replicates of the MDL
study to verify that the %RSD for each
surrogate and target compound is less than
or equal to 20%.
d. Compare all seven replicates of the MDL
study to verify that the mean recovery for
each target and surrogate compound is
within 80-120%.
If the MDL target and surrogate compound
%RSD criteria are exceeded, then the
validacor should evaluate initial calibration
%RSDs to assess mstrument precision and
linearity. The validator should use
professional judgment to assess the impact
of laboratory precision on analytical
sensitivity and data quality.
d. If the mean percent recovery for a target or
surrogate compound is greater than 120%,
then the validazor should:
- Use professional judgment to estimate
(J) positive detects for that compound
in all samples associated with that
MDL study, taking into consideration
the LFB results.
- Accept the non-detects.
Ef the mean percent recovery for a target or
surrogate compound is less than 80% but
greater than or equal to 10%, then the
validator should:
- Use professional judgment to estimate
(3) positive detects for that compound
in all samples associated with that
MDL study, taking into consideration
the LFB results.
- Use professional judgment to estimate
(UJ) the non-detects for that compound
in all samples associated with that
MDL study, taking mto consideration
the LFB results.
If the mean percent recovery for a target or
surrogate compound is less than 10%, then
the validacor should estimate (J) positive
detects for that compound and reject (R)
the non-detects for that compound in all
samples associated with that MDL study
C. EVALUATIOt1 D. ACTION
1. c.
VOA/SV-X-4
DRAFF 12/96
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PART II-VOAJSV
Sensitivity Check
l. e. Check and recalculate the %RSDs and %
recoveries for at least three compounds per
MDL study. Verify that the recalculated
values agree within ± 10% of the reported
results.
f. Verify that the samples were analyzed on
the same insm.iments and under the same
conditions (trap, column, temperature
program, amount of sample purged, etc.) as
was used for the MDL study.
g. Compare the date of the MDL study to the
dates of all associated sample analyses to
verify that the MDL study was performed
within one year of the start of the first
sample prepared and/or analyzed in the
sample delivery group.
If any transcription and/or calculation
errors are detected, perform a more
comprehensive review to determine the
magnitude of the problem. If the problem
is extensive, the validator should have the
laboratory requanmace and resubmit all
corrected raw data and forms. If a
discrepancy remains unresolved, the
validacor must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
f. If the samples were not analyzed on the
same instruments or under the same
conditions as the MDL study, then the
validator should contact the laboratory to
obtain the correct MDL study. If an
acceptable MDL Study is unavailable, then
the validacor should evaluate the LFB data.
If no LFB data are available, then the
validator should use professional judgment
to assess the impact of analytical sensitivity
on data quality.
g. If the MDL study was not submitted or was
not performed within one year of the start
of preparation and/or analysis of the first
sample in the SDG, then the validacor
should contact the laboratory to obtain a
current MDL study. If an acceptable MDL
study is unavailable, then the validator
should evaluate the LFB data. If no LFB
data are available, then the valjdacor should
evaluate the instrument’s response to the
lowest standard of the initial calibration and
use professional judgment to assess the
impact of analytical sensitivity on data
quality
C. EVALUATION D. ACTION
I.e.
VOA/SV-X-5
DRAFT 12/96
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PART II-VOAJSV
Sensitivity Check
C. EVALUATION
D. ACTION
1. h. Verify that afl MDLs are less than or equal
to the method-required quanticadon limits.
If the LFB criteria are not met, then laboratory
performance related to method bias and
niethodlinstrument sensitivity is questionable.
2. Laboratory Fortified Blank (LFB)
* a. Check the standards preparation logs to
verify that the stock standard used to
prepare the LFB was from a source
independent from the initial and continuing
calibration standards.
b. Verify that an LFB was prepared and/or
analyzed at the correct frequency and that it
was spiked with the correct compounds at
their quantitation limits.
c. Verify that the reported recoveries for all
LFB spike compounds are within the
method QC acceptance criteria.
I. h. If the MDL study reveals that a target
compound has a detection limit greater than
the method-required quancitation limit, then
the validator should evaluate the LFB data.
If no LFB data are available, then the
validator should:
i. Elevate the quanutacion limic for that
target compound in all samples
associated with that MDL study to the
lowest concentration calibration
standard analyzed or to the laboratory-
reported MDL. whichever is higher.
ii. Estimate (J) positive detects which
were below the elevated quantitation
limit for that target compound in all
samples associated with that MDL
study.
2. Laboratory Fortified Blank (LFB)
a. If the LFB was not prepared from a source
independent from the initial and continuing
calibration standards, then the laboratory
performance related to method bias and
method/instrument sensitivity is
questionable. The validacor should review
other calibration verification checks, i.e.,
PES analyses to ensure calibration
accuracy. Professional judgment should be
used to qualify sample quantitacion limits.
b. If an LFB analysis was not performed or
the LFB was not analyzed for the correct
compounds at the proper frequency and
concentration, then the validator should use
professional jtdgment to assess the impact
of analytical sensitivity Ofl data quality
c. Sample data should be qualified based an
the number and type of compounds that
recover outside the method QC acceptance
criteria and based on the degree that
compound recoveries exceed the criteria.
VOA/SV-X-6
DRAFF 12/96
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PART II-VOA/SV Sensitivity Check
C. EVALUATION
D. ACTION
2. c. Continued from above. 2. c. I. If any of the LFB compound
recovenes are outside the method QC
acceptance criteria, then the LFB
results should be used to qualify
sample data for the specific compounds
that are included in the LFB solution.
The validator should use professional
judgment to qualify sample data for
non-LFB compounds, taking into
account the compound’s chemical
class, compound recovery efficiency,
and any analytical problems historically
associated with the compound or that
were encountered by the laboratory.
ii. If an LFB compound recovery is
greater than 140%, then the validator
should:
- Estimate (J) the affected compound
when detected in any sample
associated with that LFB to
indicate potential high bias.
- Accept the quantitauon limit of the
affected compound in any sample
associated with that LFB.
iii. If more than half of the LFB
compounci -ecoveries are greater than
140%, thea the validator should:
- Estimate (J) positive detects in
all samples associaed with that
LFB to indicate potential high
bias.
- Accept quantitation limits for
non-detects in all samples
associated with that LFB
iv. If an LFB compound recovery is less
than 60% but greater than or equal to
10%, then the validator should
- Estimate (J) the affected compound
when detected in any sample
associated with that LFB to
indicate potential low bias
- Estimate (Ui) the quantitauon limit
of the affected compound in any
sample associated with that LFB to
______ indicate potential low bias.
VOA/SV-X-7 DRAFT 12/96
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PART U-VOA/SV Sensitivity Check
C. EVALUATION D. ACTION
2. c. Continued from above. 2. c. v. If more than half of the LFB
compound recoveries are less than
60% but greater than or equal o 10%,
then the validator should
- Estimate (J) positive detects in
all samples associated with that
LFB to indicate potential low bias.
- Estimate (UJ) ji quanucation
limits for non-detects in all
samples associated with that LFB
to indicate potential low bias.
vi. If an LFB compound recovery is less
than 10%, then the vaiidator should:
- Estimate (J) the affected compound
when detected in any sample
assoc aced with that LFB to
indicate potential low bias.
- Reject (R) the quantitation limit of
the affected compound in any
samples associated with that LFB
to indicate that the data are
unusable due to the possibility of
false negatives.
vii. If more than half of the LFB
compound recoveries are less than
10%, then the validacor should:
• Estimate (J) j positive detects in
all samples associated with that
LFB to indicate potential low bias.
- Reject (R) the quantication litmcs
for all non-detects tn all samples
associated with that LFB to
indicate that the data are unusable
due to the possibility of false
______ negatives.
VOA/SV-X-8 DRAFT 12/96
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PART lI-VOA1SV
Sensitivity Check
C. EVALUATION
D. ACTION
2. c. Continued from above.
* d. Check and recalculate the % recovery for
at least one compound per LFB fraction.
Verify that the recalculated value agrees
within ± 10% of the reported result.
2. c. viii. If more than half of the LFB
compound recoveries are outside
the method QC acceptance limits
in one LFB, where some
recoveries are low and some
recoveries are high, then the
validacor should use professional
judgment to qualify or reject a
particular compound, class of
compounds or the endre fraction
for samples associated with that
LFB.
i x. Action on non-compliant surrogate
recoveries should follow the
guidance provided in Section
VOAJSV-VI. Professional
judgment should be used to
evaluate the impact that a non-
compliant LFB surrogate recovery
has on the sample data.
Action on non-compliant internal
standard areas should follow the
guidance provided in Section VII.
Professional judgment should be
used to evaluate the impact that
non-compliant LFB internal
standard areas have on the sample
data.
d. If any transcription and/or calculadon
errors are detected, perform a more
comprehensive review to determine the
magnitude of the problem. If the problem
is extensive, then the validaror should have
the laboratory requantitare and resubmit all
corrected raw data and forms. If a
discrepancy remains unresolved, the
validacor must use professional judgment o
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
ranonale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum .
* Note: The following subsections are applicable only to a Tier 111 data validation:
C.1.e, C.2.a. C.2.d
VOA/SV-X .9
DRAFT’ 12/96
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PART u-vo tisv Sensitivity Check
Table VOA/SV-X-l:
QUALIFICATION OF ORGANIC ANALYTES BASED ON MDL STUDY RESULTS
Sample Results
Mean % Recovery
%Rec < 10%
10% %Rec < 80%
80% %Rec 120% %R > 120%
Detects
I
Professional Jud menc
A Professional Judgmcnc
Non-Detects
a
Professional Judgment
A A
Sampl Results
c
%
ESO
I
>2S% I 25%
Detects
Profcssional iudgmenc
A
[ Non-detects
Professional Judgmenc [ A
* Taking into consideration LFB results.
Taking into considerazion initial calibration %RSDs.
Table VOA/SV-X-2:
QUALIFICATION OF ORGANIC ANALYTES BASED ON LFB* RECOVERIES WHERE:
ONE-HALF OF LFB COMPOUNDS OUTSIDE UPPER OR LOWER ACCEF ANCE LIMITS
Sample
Results
%Recovery
%Rec < 10%
10% %Rec <60%
60% %Rec 140%
%Rec> 140%
Detects
J
J
A
j
Non-detects
R
UJ
A
A
* LFB= Laboratory fortified blank spiked with several or all of the method target compounds at or below the
quantitation limit.
VOAISV-X-l0 DRAFT 12/96
-------
PART u-vo isv Sensitivity Check
Table VOA/SV-X-3:
QUALIFICAflON OF ORGANIC ANALYI ES BASED ON LFB* RECOVERIES WHERE:
> ONE-HALF OF LFB CO [ IPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE LIMITS**
Sample Results
%Recovery
%Rec < 10%
10% %Rec <60%
60% %Rec 140%
%Rec> 140%
Detects
J
J
A
J
All Non-detects
R
UI
A
A
* LFB = Laboratory fortified blank spiked with several or all of the method target compounds at or below the
quantitation limit.
** Professional judgment should be used when a combination of Low recoveries and high recoveries are obtained.
E. EXAMPLES
Example #1 : (Low LFB recoveries for several compounds)
Low concentration water samples were analyzed under CLP SOW OLCO2. 1 and, therefore, no
MDL study was required. LFB compounds, benzene, carbon tetrachioride, and trichioroethene
recovered below QC acceptance criteria but greater than 10%, (22%, 40%, and 38%,
respectively). The validator estimates (I) the positive benzene, carbon tetrachioride, and
trichioroethene detects in all the field samples associated with the LFB to indicate potential low
bias and estimates (Ui) the quantitation limits for the benzene, carbon tetrachioride, and
tnchloroethene non-detects in all the field samples associated with the LFB to indicate a decrease
in sensitivity and the possibility of false negatives. The validator reports the qualified results on
the Data Summary Table and notes this in the Data Validation Memorandum.
Example #2 : (High LFB recoveries for two compounds; Low internal stanaard area counts)
Low concentration water samples were analyzed under CLP SOW OLCO2. 1 and, therefore, no
MDL study was required. LFB compounds I ,2-dichloropropane and tetrachloroethene recovered
outside the upper QC acceptance criteria (160% and 200%, respectively). The IS area for
chlorobenzene-d5, in the LFB sample and in all field samples associated with the LFB, was
reported below the QC acceptance criteria but greater than 20% of the continuing calibration IS
response. Since all analytes associated with the IS chlorobenzene-d5 were esurnated (I or UI
indicating a potential high bias) previously in all affected samples due to the low IS area counts,
the validator notes the high LFB recoveries in the Data Validation Memorandum but takes no
additional action on the Data Summary Table.
Example #3 : (Low MDL recoveries for LFB compounds: Acceptable LFB results)
The analytical method used for sample analysis did not specify QC acceptance criteria for the
MDL study. The validator uses the default criteria for mean % recoveries (80-120%) and %RSDs
to evaluate the MDL data. The MDL study submitted by the laboratory did not meet the default
MDL recovery criteria for smyrene and vinyl chloride (55% and 32%, respectively) The validator
examines the LFB data subrnuted witn the field sample results and determines that all LFB method
QC icceptance criteria were met including sr rene and vinyl chloride. The validator accepts the
field sample data based on the acceptable LFB results and notes the low MDL recoveries in the
Data Validation Memorandum.
VOA/SV-X-11 DRAFT 12/96
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PART a-voA/sv Sensitivity Check
E. EXAMPLES
kaznple #4 : (High LFB recoveries for two compounds; High MDL %RSDs for two compouncis
The analytical method used for sample analysis did not specify QC acceptance criteria for the
MDL study. The validator uses the default criteria for mean % recoveries (80-120%) and %
RSDs to evaluate the MDL data. The MDL study submnted by the laboratory did not meet
default (25%) %RSD criteria for benzene and ethylbenzene (34% and 36%, respectively). The
validator reviews the initial calibration %RSDs and determines that benzene and ethylbenzene met
the initial calibration %RSD acceptance criteria. In addition, the analytical method used did not
specify QC acceptance criteria for the LFB. The validator uses the default recovery criteria of
60-14.0% to evaluate LFB results. The validacor examines the LFB submitted with the analytical
results and determines that benzene and ethylbenzene also exceeded the LFB % recovery criteria
of 140% (164% and 170%, respectively). Since the initial calibration %RSDs were acceptable,
the high MDL %RSDs were not utilized to qualify sample data. Based upon the LFB recoveries,
the validator uses professional judgment to estimate (1) the positive benzene and ethylbenzene
detects to indicate potential high bias for these two compounds and accept the quancitation limits
for benzene and ethylbenzene non-detects in all field samples associated with the LFB. The
validator reports the qualified results on the Data Summary Table and notes the sample
qualifications in the Data Validation Memorandum.
VOA/SV-X-12 DRAFT 12/96
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PART n-voAJsv PE Samples/Accuracy Check
XI. PERFORMANCE EVALUATION SAMPLES/ACCURACY ChECK
A. OBJECTIVE
Data for Performance Evaluation Samples (PESs) are generated to provide information on the overall
accuracy and bias of the analytical method and on laboratory performance. PESs are evaluated for false
negauves, false positives, and inaccurate target compound quanutauon. In general, the most serious
problem a PES can expose is the failure of the Laboratory to properly detect and identify a PES compound.
This failure is known as a false negative. False negatives significantly increase the ‘uncertainty’
surrounding any site decisions made concerning the ‘cleanliness” or contamrnauon present at a site. A
second problem revealed by PES analysis is the laboratory’s erroneous detection of target and non-target
compounds that were not spiked into the PES, otherwise known as false positives. False positives should
always be evaluated in conjunction with blank data to ascertain the probable source(s) of contamination.
Finally, the PES provides information on the magnitude and direction of quantitative bias for the entire
laboratory method, including sample preparation (extraction and cleanup) and analysis (chromatography
and calibration). Sample data that are biased high or low can potentially Impact site decisions, especially
when sample data have target compound concentrations at or near project action levels.
Ideally, a PES is comprised of the same matrix as the field samples being evaluated. However, for many
matrices (i.e., soil) PESs are not available. In these situations, a PES of another matnx (he., water) may
be analyzed with the field samples to assess laboratory performance on the ‘analysis” portion, even though
laboratory performance on the “sample preparation” portion cannot be assessed. The ‘altdator should use
professional judgment when evaluating samples of one matrix using PES data from another matrix.
B. CR FERLt
1. Zero Blind Performance Evaluation Samples
A Zero Blind PES is a quality control sample that is of a composition and concentration known
to the laboratory.
A Laboratory Control Sample (LCS) is a Zero Blind PES which is often used by the laboratory
as an internal quality control check of analytical accuracy and method bias.
An LCS containing several or all of the target compounds spiked at concentrations at or below
their quantitation limits is called a Laboratory Fortified Blank (LFB). Refer to Section X for
additional LFB guidance.
a. An LCS is required by some EPA methods and certain CLP SOWs. The frequenc”,
concentration, acceptance criteria and corrective actions for LCS analysis should be stated
in the method, Sampling and Anaiysis Plan (SAP) or the Quality Assurance Project Plan
(QAPjP) and should supoort the DQOs of the project. The LCS should be prepared in
the proper matrix for eacn parameter at the concentration level and frequency required
in the EPA-approved project SAP, QAPjP. audior method. The LCS must contain one
or more target compounds. The LCS must be prepared and analyzed concurrently with
field samples contained in the sample delivery group
VOAISV-XI-l DRAFT 12196
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PART II-VOA/SV PE Samples/Accuracy Check
b. The percent recoveries for LCS compounds must be within the method QC acceptance
criteria.
c. Surrogate compounds and internal standards for the LCS must meet validation crueria as
per Sections VI and VII of this document.
2. Single Blind Performance Evaluation Samples
A Single Blind PES is a quality control sample that is of a composition and concentration not
known to the labordtoty, but the sample is identified to the laboratory as a PES.
A Single Blind PES may be submitted with a sample delivery group to assess method bias,
laboratory performance and to evaluate data quality. A Single Blind PES may also be submitted
for analysis prior to sample shipment to prequaiify a laboratory for a specific matrix and/or
parameter.
a. The latest revision of the EPA Region I Performance Evaluation Program Guidance ,
requires that a Single Blind or Double Blind PES be sent with each sample delivery group
(20 samples or less) that is sent to a laboratory. A PES is required for each matrix,
parameter, and concentration level unless an EPA or non-EPA PES does not currently
exist for that particular matrix, parameter, or concentration level.
The PE Program applies to the Superfluid program including EPA Fund-lead and
PRP/ Federal Facility Oversight Projects. In addition, the FE Program applies to Fund-
lead projects performed by States under Cooperative Agreements and other Federal
Agencies under Interagency Agreements. The FE Program also applies to Non-Fund-
lead Superfund projects undertaken by potentially responsible parties. The FE Program
also applies to Non-Superfund Programs.
EPA-provided PE samples are available for certain categories of Superfund work as
specified in the latest revision of the EPA Region I Performance Evaluation Program
Guidance . The EPA Performance Evaluation Chemist provides the current list of EPA-
provided FE samples upon request. For those categones of Superfund work that do nor
have access to EPA-provided FE samples and for all Non-Superfluid program work
scientifically defensible FE samples should be obtained from commercial vendors.
b. Acceptance criteria for EPA PESs are statistically-derived by the Analytical Operations
Center under the QATS contract. Tabulated report forms for EPA PESs must be
submitted to the Region I OEME-QA Unit for scoring at the time of data validation, in
accordance with the latest revision of the EP t Reaion I Performance Evaluation Program
Guidance .
c. True values and QC acceptance criteria for all non-EPA PESs should be provided by the
manufacturer and these acceptance criteria must be fully documented and must be
scientifically defensible.
d. Surrogate compounds and internal standards for EPA and non-EPA Single Blind PE
samples must meet validation criteria as per Sections VI and VII of this document.
VOA/SV-X1-2 DRAFT 12/96
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PART II-VOA/SV PE Samples/Accuracy Check
3. Double Blind Performance Evaluation Samples
A Double Blind PES is a quality control sample that is of a composinon and concentration not
known to the laboratory and (he sample is ij identifiable as a PES nor is it idenufied to the
laboratory as a PES.
A Double Blino PES may be submitted with a sample delivery group, in lieu of a Single Blind
PES. to assess method bias, laboratory performance and to evaluate data quality.
a. The use of Double Blind PESs is dictated by the project DQOs and should be documented
in the EPA-approved SAP and/or QAPJP.
b. True values and acceptance criteria for Double Blind PESs must be fully documented and
must be scientifically defensible.
C. Surrogate compounds and internal standards for EPA and non-EPA Double Blind PE
samples must meet validation cnteria as per Sections VI and VU of this document.
C. EVALUATION! D. ACTION
C.
EVALUATION
D. ACTION
All potential impacts on the sample data resulting
from performance evaluation sample anomalies
should be noted in the Data Validation
Memorandum. The validator should also document
and justify all technical decisions made based on
professional judgment in the Data Validation
Memorandum.
1.
Zero Blind PES - LCS
1. Zero Blind PES - LCS
a. Verify that an appropriate LCS sample
a. If an appropriate LCS was not analyzed at
(correct parameter, concentration level,
the required frequency for the correct
target compounds and matrix) was prepared
parameters. concentration levels, tarset
and analyzed at the required frequency for
compounds or matrices, then the validator
each sample delivery group in accordance
should use professional judgment to
with the EPA approved project SAP,
determine if the sample data should be
QAPjP and/or method.
qualified or rejected.
b. Verify that the required LCS resuhs are
b. If the required LCS results were not
provided for each sample delivery group.
submitted for each sample delivery group,
then the validator should contact the
laboratory to obtain raw data and tabulated
results.
VOA/SV-X1.3 DRAFT 12/96
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PART ff-VOAISV PE Samples/Accuracy Check
C. EVALUATION D. ACTION
I. C. Verify that the reported recoveries for all 1. c. Sample data should be qualified based on
LCS spike compounds are within the the number and type of compounds that
method QC acceptance criteria, recover outside the method QC acceptance
criteria and based on the degree that
compound recoveries exceed the Criteria.
i. If any of the LCS compound
recoveries are outside the method QC
acceptance criteria, then the LCS
results should be used to qualify
sample data for the specific compounds
that are included in the LCS solution.
Professional judgment should be used
to qualify sample data for non-LCS
compounds, taking into account the
compound’s chemical class, compound
recovery efficiency, and any analytical
problems historically associated with
the compound or that were encountered
by the laboratory.
ii. If an LCS compound recovery is
greater than the upper limit of the
method QC acceptance criteria, then
the validator should:
- Estimate (J) the affected compound
when detected in any sample
associated with that LCS to
indicate potential high bias.
- Accept the quanticacion limit of the
affected compound in any sample
associated with that LCS.
iii. If more than half of the LCS
compound recoveries are greater than
the upper limit of the method QC
acceptance criteria, then the validator
should.
- Estimate (J) all positive detects in
all samples associated with that
LCS to indicate potential high
bias
• Accept fl quantitauon limits for
non-detects in all samples
associated with that LCS.
VOA/SV-XI-4 DRAFT 12/96
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PART ll-VOAJSV PE Samples/Accuracy Check
C. EVALUATION
D. ACTION
1. c. Continued from above. I. C. W. If an LCS compound recovery is less
than the lower limit of the method QC
acceptance criteria but greater than or
equal to 10%, then the validacor
should:
- Estimate (J) the affected compound
when detected in any sample
associated with that LCS to
indicate potential low bias.
- Estimate (Ui) the quantitation limit
of the affected compound in any
sample associated with that LCS to
indicate potential low bias.
v. If more than half of the LCS
compound recoveries are less than the
lower limit of the method QC
acceptance criteria but greater than or
equal to 10%, then the validator
should:
- Estimate (I) g positive detects in
all samples associated with that
LCS to indicate potential low bias.
- Estimate (UJ) all quantitanon
limnns for non-detects in all
samples associated with that LCS
to indicate potential low bias.
vi. If an LCS compound recovery is less
than 10%, then the validator should:
- Estimate (J) the affected compound
when detected in any sample
associated with that LCS to
indicate potential low bias.
• Reject (R) the quanutacion limit of
the affected compound in any
sample associated with that LCS to
indicate that the data are unusable
due zo the possibility of false
_______ negatives
VOA/SV-XI-5 DRAFT ’ 12/96
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PART rI-voAJsv PE Samples/Accuracy Check
C. EVALUATION
D. ACTION
1. c. Continued from above. 1 c. vii If more than half of the LCS
compound recoveries are less than
lOs, then the validator should:
- Estimate (I) fl positive
detects in all samples
associated with that LCS to
indicate potential low bias.
- Reject (R) the quantitation
limits for all non-detects in all
samples associated with that
LCS to indicate that the data
are unusable due to the
possibility of false negatives.
viii. If more than half of the LCS
compound recoveries are outside
the method QC acceptance limits
in one LCS, where some
recoveries are low and some
recoveries are high, then the
validator should use professional
judgment to qualify or reject a
particular compound, class of
compounds or the entire fraction
for samples associated with that
LCS.
ix. Based upon the number and type
of compounds misquancified and a
review of the project DQOs, the
validator should use professional
judgment to determine if the data
set for an entire fraction or
parameter is unusable and,
therefore, should be rejected.
Rejected data should be returned to
the laboratory and payment denied.
d. -Evaluate surrogate compounds and internal d. Action on non-compliant surrogate
standards for the LCS. recoveries and internal standard area counts
should follow the guidance provided in
Sections VI and VII, respectively
Professional judgment should be used to
evaluate the impact that non-compliant LCS
surrogate recoveries andJor internal
standard area counts have on the sample
data.
VOA/SV-XI-6 DRAFF 12/96
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PART u-voAJsv PE Samples/Accuracy Check
C. EVALUATION
D. ACTION
* 1. e. Check and recaiculate the percent recovery
for at least one compound per LCS
fraction. Verify that the recalculated value
agrees within ± 10% of the reported result.
1. e. If any transcription and/or calculation
errors are detected, perform a more
comprehensive review to determine the
magnitude of the problem. If the problem
is extensive, then the validator should have
the laboratory requanutace and resubmit all
correc:ed raw data and forms. If a
discrepancy remains unresolved, the
validator must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
2. Single Blind and Double Blind PESs
a. Verify that an appropriate Single Blind or
Double Blind PES (correct parameter,
concentration level, target compounds and
matrix) was analyzed at the required
frequency for each sample delivery group
in accordance with Region I PE policy
and/or the EPA approved SAP and/or
QAPJP.
b. Verify that Single Blind PES results are
provided for each sample delivery group in
accordance with Region I PE policy.
2. Single Blind Double Blind PESs
a. If a required Single Blind or Double Blind
PES was not analyzed at the required
frequency for the correct parameters,
concentranon levels, target compounds or
macrices, then the validator should use
professional judgment to determine if the
sample data should be qualified or rejected.
b. If the PES results were not subrmtted for
each sample delivery group, then the
validator should contact the laboratory to
obtain raw data and/or tabulated results. If
a PES was not submitted to the laboratory
by the sampler, then the validator should
contact the sampler to confirm the omission
of a PES and document that fact on the
worksheet and in the Data Validation
Memorandum.
VOA/SV-XI-7 DRAFT 12/96
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PART EI-VOA/SV
PE Samples/Accuracy Check
EPA PESs: If the PES was supplied and
scored by Region I OEME-QA, then the
Region I PES Score Report must be
evaluated to determine how many of the
analytes met or exceeded PES acceptance
criteria.
• Evaluate the “TCL MISSES” to assess the
potential for low bias and false negative
sample results.
S Evaluate the “TCL CONTAMINANTS ”
and “TIC CONTAMINANTS” in
conjunction with blank data to assess the
potential for high bias and false positive
sample results.
2. c. Region I EPA PESs
Note: PES results should no be qualified
based on QC sample data and should not be
reported on the Data Sumniaiy Table.
Rather, PES results should be discussed in
the Data Validation Memorandum or Tier I
Validation Cover Letter arid PES Score
Reports should be attached as supporting
documentation.
• Sample data should be qualified based on
the number and type of “TCL MISSES”
identified on the Region I PES Score
Report.
i. If a PES compound is not identified in
the PES, then the validator should:
- Estimate (J) the affected compound
when detected in any sample
associated with that PES to
indicate potential low bias.
• Reject (R) the quantitation limit of
the affected compound in any
sample associated with that PES to
indicate that the data are unusable
due to the possibility of false
negatives.
ii. Based upon the chemical class, the
number of compounds that were not
identified, and a review of the project
DQOs, the validator should use
professional judgment to determine if
the data set for an entire fraction or
parameter is unusable and, therefore,
should be rejected. Rejected data
should be remrned to the laboratory
and payment denied.
• Sample data should not be qualified based
on the number and type of TCL
CONTAiMINANTS and “TIC
CONTAMINANTS” identified on the
Region! PES Score Report
i. If a TCL or TIC contaminant is
detected in the PES and is also found
in a blank, then the validator should
evaluate and qualify sample data based
upon blank contamination in
accordance with Section V
ii If a TCL or TIC contaminant is
detected in the PES but is not present
in any blank, then that interference is
specific to the PES and does not
imnact samole data.
2. c.
C. EVALUATION
D. ACTION
VOAISV-X1-8
DRAFT 12/96
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PART II-VOA/SV PE Samples/Accuracy Check
C. EVALUATION
D. ACTION
2 C. Continued from above. 2. c Connnued from above.
S Evaluate the “TCL HITS” that were • Sample daca should be qualified based on
rnisquarnified to assess the potential for the number and type of misquantified
high and/or low bias in sample data. compounds (Action High/Action Low
“TCL HITS”) identified on the Region I
PES Score Report. Sample data should
not be qualified based on “Warning
Low/Warning High” scores for “TCL
HITS”.
i. If any of the PES compounds do not
meet PES acceptance criteria, then the
PES results should be used to qualify
sample data for the specific compounds
that are included in the PES sample.
Professional judgment should be used
to qualify sample data for non-PES
compounds taking into account the
compound’s chemical class, compound
recovery efficiency, and analytical
problems historically associated with
the compound or that were encountered
by the laboratory.
ii. If a PES compound is scored in the
“Action High” category, then the
validator should:
- Estimate (.1) the affected compound
when detected in any sample
associated with that PES to
indicate potential high bias.
- Accept the quantitation limit of the
affected compound in any sample
associated with that PES.
iii. If more than half of the PES
compounds are scored in the “Action
High” category, then the validator
should:
• Estimate (J) jj positive detects in
all samples associated with that
PES to indicate potential high bias
- Accept quantitauon limits for
non-detects in all samples
______ associated with that PES.
VOAJSV-XI-9 DRAFT 12/96
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PART ll-VOA/SV
PE Samples/Accuracy Check
C. EVALUATION
D. ACTION
2. c. Continued from above. 2. c. iv If a PES compound is scored in the
“Action Low” category, then the
validator should:
- Estimate (J) the affected compound
when detected in any sample
associated with that PES to
indicate potential low bias.
- Reject (R) the quanutation limit of
the affected compound in any
sample associated with that PES to
indicate that the data are unusable
due to the possibility of false
negatives.
v. If more than half of the PES
compounds are scored in the “Action
Low” category, then the validator
should:
- Estimate (J) j positive detects in
all samples associated with that
PES to indicate potential low bias.
- Reject (R) the quantitanon limits
for all non-detects in all samples
associated with that PES to
indicate that the data are unusable
due to the possibility of false
negatives.
vi. If more than half of the PES
compounds are scored in the “Action”
levels in one PES, where some
recoveries are low and some recoveries
are high, then the validator should use
professional judgment to qualify or
reject a particulai compound, class of
compounds or the entire fraction for
samples associated with that PES.
vii. Based upon the number and type of
compounds nusquanufied and a review
of the project DQOs, the validator
should use professional judgment to
determine if the data set for an entire
fraction or parameter is unusable and,
therefore, should be rejected. Rejected
data should be returned to the
laboratory ann payment denied.
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DRAFT’ 12/96
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PART fl-VOAJSV
PE Samples/Accuracy Check
C. EVALUATION
D. ACTION
2. c. Continued from above.
• Evaluate ‘T iC HITS’ and ‘TIC MiSSES”.
o Evaluate surrogate compounds and internal
standards for the EPA PES.
d. Non-EPA PESs
If the PES was obtained from a source
other than Region I OEME-QA, then the
validator should use the vendor’s criteria to
evaluate the PES results. Confirm that PES
acceptance criteria are fully documented
and scientifically defensible.
• Evaluate the “PES COMPOUND MISSES”
to assess the potential for low bias and false
negative sample results.
2. c. Continued from above.
• Sample data should be qualified based on
the number and type of “TIC HITS’ and
“TIC MISSES’ Identified on the Region I
PES Score Report.
i. If TIC identifications are required by
the method, then the validator should
use professional judgment to qualify
the sample data based upon entries in
the “TIC HITS’ and ‘TIC MISSES’
categories.
• Action on non-compliant surrogate
recoveries and internal standard area counts
should follow the guidance provided in
Sections VI and VII, respectively.
Professional judgment should be used to
evaluate the impact that non-compliant EPA
PES surrogate recoveries and/or internal
standard area counts have on the sample
data.
d. Non-EPA PESs
If the non-EPA PES acceptance criteria are
not fully documented and/or scientifically
defensible, then the validator should use
professional judgment to qualify or reject
the sample data.
• Sample data should be qualified based on
the number and type of “PES
COMPOUND MISSES” identified from the
vendor’s acceptance criteria.
i. If a PES compound is not ic ntifled in
the PES, then the validator should:
- Esurnate (J) the affected compound
when detected in any sample
associated with that PES to
indicate potential low bias.
- Reject (R) the quantitauon limit of
the affected compound in any
sample associated with that PES to
indicate that the data are unusable
due to the possibility of false
ne2atives,
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DRAFr 12196
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PART H-VOA/SV
PE Samples/Accuracy Check
C. EVALUATION D. ACTION
• Evaluate the PES COMPOUND
CONTAMINANTS” in conjunction with
blank data to assess the potential for high
bias and false positive sample results.
• Evaluate the “PES COMPOUND HITS”
that were misquantifled to assess the
potential for high and/or low bias in sample
results.
2. d. Continued from above.
ii. Based upon the chemical class, the
number of compounds that were not
identified, and a review of the project
DQOs, the validacor should use
professional judgment to determine if
the data set for an entire fraction or
parameter is unusable and, therefore,
should be rejected. Rejected data
should be returned to the laboratory
and payment denied.
• Sample data should not be qualified based
on the number and type of “PES
COMPOUND CONTAMINANTS”
identified from the vendor’s acceptance
criteria alone.
i. If a PES COMPOUND
CONTAMINANT is detected in the
PES and is also found in a blank, then
the validator should evaluate and
qualify sample data based upon blank
contamination in accordance with
Section V.
ii. If a PES COMPOUND
CONTAM NA14T is detected in the
PES but is not present in any blank,
then that interference is specific to the
PES and does not impact sample data.
• Sample data should be qualified based on
the number and type of zmsquantified “PES
COMPOUND HITS” identified from the
vendor’s acceptance criteria.
i. If any of the PES compounds do not
meet acceptance criteria, then the
validator should use the PES results to
qualify sample data for the specific
compounds that are included in the
PES sample. Professional judgment
should be used to qualify sample data
for non-PES compounds, taking into
account the compound’s chemical
class, compound recovery efficiency,
and analytical problems associated with
the compound either hisconcally or that
were encountered by the laboratory
2. d Continued from above.
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PART ll-VOA/SV
PE Samples/Accuracy Check
C. EVALUATION
D. ACTION
2. d. Continued from above. 2. d. Continued from above.
ii. If a PES compound recovery is outside
the upper limit of the vendor’s
documented acceptance limis (Note:
The validator should confirm that the
vendor’s acceptance limits are
calculated as plus and minus three
standard deviations from the mean,
similar to EPA-PES “Action Limits”.),
then the validacor should:
- Estimate (J) the affected compound
when detected in any sample
associated with that PES to
indicate potential high bias.
- Accept the quanutation limit of the
affected compound in any sample
associated with that PES.
iii. If more than half of the PES compound
recoveries are outside the upper limit
of the vendor’s documented acceptance
limits (See note above, Section 2.d.ii),
then the valjdator should:
• Estimate (1) positive detects in
all samples associated with that
PES to indicate potential high bias.
- Accept j quantitation limits for
non-detects in all samples
associated with that PES.
iv. If a PES compound recovery is outside
the lower limit of the vendor’s
documented acceptance limits (See note
above, Section 2.d.ii), then the
vajidacor should:
- Estimate (5) the affected compound
when detected in any sample
associated with that PES to
indicate potential low bias
Reject (R) the quantitation limit of
the affected compound in any
sample assoc aced with that PES
to indicate that the data are
unusable due to the possibility of
false ne auves
VOAISV-X1- 13
DRAFT 12/96
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PART u-voAisv PE Sam pies/Accuracy Check
C. EVALUATION
D. ACTION
2. d Continued from above. 2. d. Continued from above.
v. If more than half of the PES compound
recoveries are outside the lower limit
of the vendor’s documented acceptance
limits (See note above, Section 2.d.ii),
then the validator should:
- Estimate (J) ij positive detects in
all samples associated with that
PES to indicate potential low bias.
- Reject (R) the quantitation limits
for non-detects in all samples
associated with that PES to
indicate that the data are unusable
due to the possibility of false
negatives.
vi. If more than half of the PES compound
recoveries are outside the vendor’s
documented acceptance limits in one
PES (See note above, Section 2.d.ii),
where some recoveries are low and
some recoveries are high, then the
validacor should use professional
judgment to qualify or reject a
particular compound, class of
compounds or the entire fraction for
samples associated with that PES.
vii. Based upon the number and type of
compounds misquantified and a review
of the project DQOs, the validator
should use professional judgment to
determine if the data set for an entire
fraction or parameter is unusable and,
therefore, should be rejected. Rejec:ed
data should be returned to the
laboratory and payment denied.
• Evaluate surrogate compounds and internal • Action on non-compliant sur gace
standards for the non-EPA PES. recoveries and internal stana i area counts
should follow the guidance provided in
Sections VI and V I I, respectively
Professional judgment should be used to
evaluate the impact that non-compliant non-
EPA PES surrogate recoveries and/or
internal standard area counts have on the
samole data
VOA/SV-XI-14 DRAFf 12196
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PART EI-VOA/SV
PE Samples/Accuracy Check
2. e. Determine what percentage of PES analytes
were below or above PES acceptance
criteria.
* f. Check and recalculate the analytical
concentrations for at least one compound
per PES fraction. Verify that the
recalculated value agrees within ± 1O of
the reported result.
If more than half of the PES compounds
are high or low, then the valjdator should
check the raw data and/or contact the
laboratory to verify that the PE sample was
prepared according to the PE instructions
(if applicable). Check also that the
appropriate PE instructions (for that PE
concentration level) were sent to the
laboratory.
f. If any transcription and/or calculation
errors are detected, perform a more
comprehensive review to determine the
magnitude of the problem. If the problem
is extensive, then the validator should have
the laboratory requantitace and resubirat all
corrected raw data and forms. If a
discrepancy remains unresolved, the
validator must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
i. If corrected data reports affect the
original results reportea on the initial
EPA PES score report, then the
validator should resubmit the corrected
PES results to Region I OEME-QA for
a PES rescore. Sample data should be
reevaluated and requalified based on
the corrected PES data.
ii. If corrected data reports affect the
original results reported for the initial
non-EPA PES, then the validator
should reevaluate and requalifv sample
data based on the corrected PES data
Note:
The following subsections are applicable only to a Tier ifi data validation:
C.1.e, C.2.e, C.2.f
C. EVALUATION
D. ACTION
2. e.
VOA/SV-XI-15
DRAFF 12/96
-------
PART ll-VOAJSV PE Samples/Accuracy Check
Table VOAJSV-Xl- 1:
QUALIFICATION OF INDFVTDUAL ORGANIC ANALYTES BASED ON LCS RECOVERIES WHERE:
ONE-HALF OF LCS COMPOUNDS OUTSIDE UPPER OR LOWER ACCEFFANCE LIMITS
SanipleResults
% Recovery
%Rec < 10%J
10% %Rec IJL
Detects
J
I
A
j
Non-detects
R
UJ
A
A
LL - Lower Limit of method QC acceptance criteria
UL - Upper Limit of method QC acceptance criteria
Table V/SV-XI-2:
QUALIFICATION OF ORGANIC ANALYTES BASED ON LCS RECOVERIES WHERE:
> ONE-HALF OF LCS COMPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE LIM S*
Sample Results
%_Recovery
%Rec < 10%
10% %Rec UL
flDetects
J
J
A
j
Non-detects
R
UI
A
A
Professional judgment should be used when a combination of low recoveries and high recoveries are obtained.
LL - Lower Limit of method QC acceptance criteria
UL - Upper Limit of method QC acceptance criteria
VOA/SY-XI-16 DRAFT 12/96
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PART II-VOAJSV PE Samples/Accuracy Check
Table VOAJSV-XI-3:
QUALIFICATION OF ThJDIVIDUAL ORGANIC ANALYTES BASED ON PES RESULTS WHERE:
ONE-HALF OF PES coMPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE LIMITS
Sample Results
‘Single Blind
‘Double Blind
PES < Lower Limit
“Action Low”
•Single Blind
‘Double Blind
PES “Within Warning Limits’
“Warning HighfWarning Low”
‘Single Blind
‘Double Blind
PES > Upper Limit
“Action High”
Detects
J
A
j
Non-Detects
R
A
A
Table VOA/SV-XI-4:
Q JAL1FICATION OF ORGANIC ANALYTES BASED ON PES RESULTS WHERE:
> ONE-HALF OF PES COMPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE LIMITS ‘
Sample Results
•Single Blind
‘Double Blind
PES < Lower Limit
“Action Low”
•Single Blind
‘Double Blind
PES “Within Warning Limits”
“Warning High/Warning Low”
‘Single Blind
‘Double Blind
PES> Upper Limit
“Action High”
jDetects
S
A
j
jj Non-Detects
R
A
A
* Professional judgment should be used when a combination of low recoveries and high recoveries are obtained.
VOAISV-XI-17 DRAFF 12/96
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PART Ji-VOAJSV PE Sampl&Accuracy Check
E. EXAMPLES
Example #l (One LCS compound < lower limit; One LCS compound > upper PES acceptance limit)
A Laboratory Control Sample (LCS) containing 10 compounds spiked at three times the
quantitauon Iimi is found to have chlorobenzene with a % recovery of 150% and vinyl chloride
with a % recovery of 50%. The method QC acceptance criteria for LCS compound recoveries
are 60-140%. This amounts to less than one-half of the spike LCS compounds being outside the
LCS acceptance criteria. The validator estimates (I) positive detects for chlorobenzene and vinyl
chloride in all field samples associated with that LCS. The validator accepts the chlorobenzene
non-detects and estimates (UJ) the vinyl chloride non-detects in all field samples associated with
that LCS. The validator reports qualified data on the Data Summary Table and notes that the
chlorobenzene positive detects are biased high, the vinyl chloride positive detects are biased low
and the vinyl chloride non-detects contain possible false negatives in the Data Validation
Memorandum.
Example #2 (One Single Blind PES compound < lower PES acceptance limit)
A Single Blind Performance Evaluation Sample (PES) is found to have a chioroethane positive
result that scored below the lower PES acceptance limit. The validator determines that less than
one-half of the spike PES compounds are outside the PES acceptance criteria. Therefore, the
validator estimates (J) positive chioroethane detects and rejects (R) the quantitation limits for
chioroethane non-detects in all field samples associated with that PES. The validator reports
qualified data on the Data Summary Table and notes that the positive chloroethane detects are
biased low and chloroethane non-detects are rejected due to the possibility of false negatives in
the Data Validation Memorandum.
Exarnole #3 : (More than one-half of PES compounds greater than upper PES acceptance limits)
A Single Blind PES is found to have more than one-half of the spike volatile PES compounds with
% recoveries above the upper PES acceptance limits. The validacor estimates (J) positive
detects in all field samples associated with chat PES and accepts (A) all quantitanon limits for non-
detects in all field samples associated with that PES. The validator reports qualified data on the
Data Summary Table and notes the positive volatile results are biased high in the Data Validation
Memorandum.
Examole #4 : (More than one-half of PES compounds “Action High” or “Action Low )
A Single Blind PES is found to have more than one-half of the spike semivolatile PES compounds
with results that do not meet PES acceptance criteria. Some of the PES compounds are flagged
“Action Low” and some flagged “Action High” The site DQOs are to determine whether cleanuo
levels were achieved. The validawr determines that analytical error yields uncertainty in
quantitative accuracy which may adversely affect site decisions. Therefore, the validator uses
professional judgment to estimate (J) all positive detects in all field samples associated with that
PES and reject (R) all quantitation limits in all field samples associated with that PES The
validacor reports qualified data on the Data Summary Table and discusses the limited use of the
data in the Data Validation Memorandum.
VOA/SV-X1-lS DRAET 12/96
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PART u-voAjsv PE Samples/Accuracy Check
E. EXAMPLES
Example #5 : (One TCL MiSS”)
A Single Blind PES is found to have one “TCL MISS” for vinyl chloride which is a containinam
of concern at the site. The validacor estimates (J) all positive vinyl chloride detects and rejects
(R) all vinyl chloride quantitacion limits in all field samples associated with that PES. The
validator reports qualified data on the Data Summary Table and discusses this in the Data
Validation Memorandum.
Example #& (One “TCL Contaminant”, also in blank)
A Single Blind PES is found to have one “TCL Contaminant”, 1 ,2-dichloroethane, at 45 ppb. The
method blank contained 6 ppb of l,2-dichloroethane, resulting in a Blank Action Level of 30 ppb.
The validator uses the 1 ,2-dicbloroethane Blank Action Level to evaluate the sample data and
reports qualified data on the Data Summary Table. The validator suspects that the 1,2 -
dichloroethane false positive PES compound is a result of laboratoiy contamination and discusses
this in the Data Validation Memorandum. PES results are not reported on the Data Summary
Table.
Example #7 : (One “TCL Contaminant”, not in blank)
A Single Blind PES is found to have one “TCL Contaminant”, 2-chiorophenol, which is not
detected in any of the blanks but is detected in two samples. The validator determines that the
2-chiorophenol is an interference specific to the PES because it was not detected in any of the
method, instrument, or storage blanks. The validator uses professional judgment to accept the
positive 2-.chlorophenol detects in the field samples. The validator reports the data unqualified on
the Data Summary Table and discusses this in the Data Validation Memorandum.
VOA/SV-XJ-19 DRAFT 12/96
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PART H-VOA/SV Target Compound Identification
XII. TARGET COMPOUND IDENTIFICATION
A. OBJECTIVE
Qualitative criteria for compound identification have been established to minimize the number of erroneous
compound identif ications. An erroneous identification cart be either a false positive (reporting a compound
that is not present) or a false negative (not reporting a compound that is present).
The identification criteria can be applied more easily in detecting false positives than false negatives (non-
detects). More information is available for false positives due to the requirement for submittal of data
supporting positive identifications. False negatives represent an absence of data arid, therefore, are more
difficult to assess. However, false negatives can be revealed when a compound is identified and reported
to be a TIC when it should have been reported as a target compound.
B. CRITERIA
The Reajon 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region I Organic data. The CLP-Volatile/Se imvolatile iiethod QC
acceptance criteria listed in Appendices A and B should be used as the default criteria when none exist for
the Volatile/Semjvolatjle analytical method utilized and when similar QC parameters are required by the
non-CLP method and acceptance criteria have nor been met. Deviations, modifications or non-CLP
method-specific QC acceptance criteria may be used but must be explicitly defined in tabular format in the
site-specific EPA approved QAPJP/SAP or amendment to the QAPJP/SAP
1. The relative retentio: time (RRT) for the sample compound must be within ±0.06 RRT units of
the daily standard RRT.
2. Mass spectra for the sample compound and a current laboratory-generated standard (i.e., the mass
specirum from the associated daily calibration standard) must match according to the following
criteria:
a. All ions present in the standard mass spectrum at a relative intensity greater than 10
percent be present in the sample spectrum.
b. The relative intensities of these ions must agree within ± 20 percent between the
standard and sample spectra. (Example: For an ion with an abundance of 50 percent in
the standard spectrum, the corresponding sample ion abundance must be between 30
percent and 70 percent.)
C. Ions present at greater than 10 percent in the sarnole mass spectrum but not present in
the standard spectrum must be considered and accounted for
3. All major chromatograohic peaks (i.e., peaks present in the sample chromatograin at greater than
10 percent of the nearest internal standard) must be identified as either target compounds. TICs,
surrogate compounds, or internal standards
VOA/SV-XU-1 DRAFF 12/96
-------
1 u i H-VOAISV Target Compound Identification
C. EVALUATION! D. ACTION
j C. EVALUATION
}__D. ACTION
All potential impacts on the sample data resulting
from target compound identification anomalies
should be noted in the Data Validation
Memorandum. The validator should also document
and justify all technical decisions made based on
professional judgment in the Data Validation
Memorandum.
* 1.
Ch eck that the RRT of a reported compound is
1. a. If the RRT of a reported compound is
within ± 0.06 RRT units of the standard RRT.
outside of the retention time criteria, then
the validator should use professional
judgment to determine if mass spectral
identification criieria have been met and if
the compound has been correctly identified.
b. If the reported compound does not meet
mass spectral identification criteria and has
been incorrectly reported, then the vahdaior
should report the compound as a non-detect
and document the rationale for this decision
in the Data Validation Memorandum.
c. If instrument/analytical column
malfunctions have severely affected
retention times, making data suspect, then
the validator should use professional
judgment to reject (R) all associated sample
data.
VOAISV-XIJ-2 DRAVr 12/96
-------
PART ll-VOAJSV Target Compound Identification
EVALUATION
1__D. ACTION
compound spectra to the
2.
The application of qualitative criteria for
spectra and verify that the
GC/MS analysis of target compounds requires
criteria are tact,
professional judgment. It is left to the
validator’s discretion to obtain additional
information from the laboratory if it is deemed
necessary. If it is determined that incorrect
laboratory identifications were made, then the
validator should have the laboratory requantitate
and resubmit all corrected raw data and forms
If a discrepancy remains unresolved, the
validator must use professional judgment to
decide which identification is accurate. Under
these circumstances, the validacor may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the qualifiers
used should be documented in the Data
Validation Memorandum.
chrornatogram to verify that
3.
If a chromatographic peak is unaccounted for
interest are identified as
and is greater than 10% of the nearest internal
TICs, surrogate
standard, then the validator should have the
Standards.
laboratory requancitate and resubmit all
corrected raw data nd forms.
be aware of situations
4.
If cross-contamination has occurred, then the
samples preceding low
validator should use professional judgment to
or when VOA samples
determine whether or not a reported target
sparge unit) when
compound is native to the sample or an
possibility, and should
interferent from a previously analyzed sample.
to determine if
Additionally, the validator should use
has affected any
professional judgment to determine whether or
An instrument blank
not sample carryover has resulted in false
after samples which
negatives due to mass spectral identification
criteria (pertaining to ions present and
abundances) which cannot be met due to
interfering ions from cross contaminants.
Note: This section is applicable only to a Tier Ifl validation - If a validator suspects compound
misidentification while performing a Tier II validation, then the Site Manager must be contacted
to approve the necessary full or partial Tier 111 validation.
VOA/SV-Xfl-3 DRAFF 12/96
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PART a-voAJsv Target Compound Identification
E. EXAMPLES
Example #1 : (False negative-all major chromatographic peaks not identified)
The laboratory originally reported phenol as a TIC in the volatile fraction of soil sample SAAI2.
Phenol was reported as a non—detect in the semivolaule fraction. Upon review of the semivolatile
chromatogram for sample SAA I2, the validator notes that the laboratory failed to identify a peak
that eluted within the phenol retention time window. The laboratory was contacted and requested
to requantitate the false negative semivolatile phenol result and report phenol as a positive detect
in the sernivolatile fraction and deletes it from the VOA TIC list. The laboratory complied and
the validator reports phenol as a positive detect in the seinivolatile fraction on the Data Summary
Table.
Exarnple #2 : (False positive; False negative-mass spectral identification criteria not met)
In aqueous sample SAAO4, the validator notes that naphthalene and 2-chlorophenol have the same
retention time on the quantitation report. The sample mass spectrum contains the molecular ion
128 and the laboratory reported naphthalene as a positive detect. Review of the mass spectrum
shows a chlonne isotope ion at m/z 130 and fragmentation ions Consistent with 2-chlorophenol,
therefore, the validacor determines that 2-chiorophenol is a more accurate identification of this
peak. The laboratory was contacted and requested to requantitate the false positive naphthalene
and false negative 2-chlorophenol. The validacor reports 2-chlorophenol as a positive detect and
naphthalene as a non-detect on the Data Summary Table.
Example #3 : (False positive-sample compound RRT not within ±0.06 RRT units of the standard
compound RRT)
The laboratory origmally identified a peak as acetone and reported acetone as a positive detect in
sample SAA67. The mass spectrum contained low area counts for ion 58 and the validator
suspects a false positive. Upon review of the retention time data, the validacor discovers that the
RRT for the reported acetone peak was not within the standard ± 0.06 retention time window.
The validator uses professional judgment to determine that acetone was misidentified. This
unknown compound is less than 10 of the area of the nearest IS and, therefore, it is not reported
as a TIC. The validator reports acetone as a non-detect on the Data Summary Table and
documents this problem in the Data Validation Memorandum.
VOA/SV-Xfl-4 DRAFT 12/96
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PART iI-voAisv Compound Quantitation and
Reported Quantitation Limits
XI I I. COMPOUND QUANTITATION AND REPORTED QUANTITATION LIMITS
A. OBJECTIVE
The objective for the evaluation of compound quantitation and reported quantitation limits is to ensure that
reported quantitative results and quantitation limits are accurate. To this end, laboratory calculations from
raw data to the tinal reported concentrations are checked for accuracy.
B. CRITERIA
The Region I. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region I Organic data. The CLP-Volatile/Semivolacile method QC
acceptance criteria listed in Appendices A and B should be used as the default criteria when none exist for
the Volatile/Semivolatile analytical method utilized and when similar QC parameters are required by the
non-CLP method and acceptance criteria have not been specified. Deviations, modifications or rion-CLP
method-specific QC acceptance criteria may be used but must be explicitly defined in tabular format in the
site specific EPA approved QAPJP!SAP or amendment to the QAPJPISAP.
1. Reported quanutation limits must meet pioject-required DQOs.
2. a. Reported concentrations for positive detects and compound quanutation limits for non-
detects and adjustments of those concentrations/compound quantitation limits must be
calculated according to the appropriate method requirements.
b. Reported concentrations for positive detects and compound quantitation limits for non-
detects must be adjusted for percent solids, dilutions, concentrations and cleanup
procedures that are not accounted for in the method.
3. a. Target compound quantitation must be based on the internal standard (IS) specified in the
method.
b. Target compound quantitation must be based on the quantitation ion (rnlz) specified in
the method for both the IS and target compound.
c. Target compound quantitation must be calculated using the RRF from the appropriate
daily standard.
4. Target compound quanutation must be within the initial calibration range.
5. All soil/sedimentlsolid sample results must be adjusted for percent solids, and must have percent
solids greater than 30 percent.
Sediment samples are collected at CERCLA sites to establish whether or not the presence of
hazardous chemicals has impacted the resident organisms and their natural environmeru. The data
quality objectives for ecological risk assessmern generally require that the analytical method used
for sediment analysis achieve, at a minimum, the dry weight CLP SOW quantitation limits.
‘U.S. EPA Office of Water Reulations and Standards Industrial Technology Division -
Method 1620, p. 29, Section 14.16, Draft September 1989.
VOAISV-Xffl-1 DRAFT 12/96
-------
PART fl-v /Sv Compound Quantitation and
Reported Quantitation Limits
Most analytical methods that deal with soil-type matrices are applicable to both soils and sediments
with no difference in how those two matrices are prepared and analyzed. Since a definition for
soil and sediment matrices is not provided in the analytical methodology, Region [ has adopted
the detinition for soil samples used by the Office of Water Regulations and Standards Industrial
Technology Division (ITD). This definition states that soil samples are ‘soils, sediments, and
sludge samples containing more than 30% solids’.
High moisture sediments cannot be successfully analyzed by routine CLP analytical methods
Additional sampling arid analytical preparation steps, which are outside of the scope of a CL?
method, should be employed. For example, standing water may first be decanted, and then the
sample may be centrifuged or filtered to remove excess water (except in the case of samples to
be analyzed for volatile orgamcs). To achieve the dry weight quanutation limits, the laboratory
must perform a percent solids analysis prior to extraction and the initial volume of sample
extracted must be increased accordingly. This presumes that the samplers have collected sufficient
volume, above and beyond normal volume requirements, so that additional sample can be
extracted. As a last resort, the laboratory can decrease the final extract volume to a minimum of
0.5 milliliters.
Certain solid matrices, such as peat, are unusual in both their reactive chemistry as well as their
associated data quality objectives. Peat is a natural sink for organic compounds. It is composed
of both a solid spongy matrix (which tightly binds organic compounds) and the interstitial pore
water present therein.
Routine analytical methods underestimate the concentrations of organic compounds in peat
matrices because the typical organic preparation and extraction techniques do not breach the
matrix. In order for peat to be successfully analyzed, the matrix itself must be “sheared” into
small pieces to increase surface area so that the extraction solvent can interact to partition the
target organic compounds.
Sampling and analytical methodologies must be determined during project scoping processes and
must be based on the project data quality objectives. For more information, see Attachment A
of the Data Validation Manual.
VOAJSV-X1ll-2 DRAFT 12/96
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PART l1-VOA/SV Compound Quanhitation and
Reported Quantitation Limits
C. EVALUATION/ D. ACTION
C. EVALUATION
D. ACTION
1. Verify that the reported quantitacion limits meet
project-requited DQOs.
All potential impacts on the sample data
resulting from compound quanuiatzon anomalies
should be noted in the Data Validation
Memorandum. The validator should also
document and justify all technical decisions
made based on professional judgment in the
Data Validation Memorandum.
1. If reported quaflutatton limits do not meet the
project-required DQOs, then the validacor must
investigate and document the cause of the
deficiency and use professional judgment to
assess sample data.
*2. a. Recalculate, from the raw data, the
concentrations for at least one positive
detect and one sample quantitacion limit (for
a diluted sample or a soil sample) far each
fraction. in every field sample to verify that
laboratory reported sample results were
accurately calculated according to the
method.
2. a. If incorrect values, equations or factors
have been used to calculate sample results
andior sample quantitanon limits, then the
validator should have the laboratory
requantilate and resubmit all corrected raw
data and forms. If a discrepancy remains
unresolved, the validaor must use
professional judgment to decide which
value is accurate. Under these
circumstances, the validator may determine
that the sample data should be qualified or
rejected. A discussion of the rationale for
data qualification and the qualifiers used
should be documented in the Data
Validation Memorandum.
voA/sv-xm-3 DRAFI 12196
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PART ll-VOA/SV Compound Quantitation and
Reported Quantitation Limits
C. EVALUATION
D. ACTION
*2. b. Verify that the concentrations for positive
detects and sample quancitauon limits have
been adjusted to reflect sample dilutions,
concentrations, cleanup methods and dry
weight factors that are not accounted for in
the method.
2. b. If the concentrations for positive detects
and/or sample quantitation limits were not
correctly adjusted for sample dilutions,
concentrations, cleanup methods, or dry
weight factors, then the validator should
have the laboratory requancitate and
resubmit all corrected raw data and forms.
If a discrepancy remains unresolved, the
validator must use professional judgment to
decide which value is accurate. Under
these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
*3 Verify that the correct internal standard,
quantitation ion and standard RRF were used to
quantitate sample results for at least one positive
detect in each fraction in every field sample
.
3. If the laboratory utilized an incorrect IS,
quantitation ion, or RRF to quantitate a target
compound, then the validator should have the
laboratory requantitate and resubmit all
corrected raw data and forms. If a discrepancy
remainc unresolved, the validator must use
professional judgment to decide which value is
accurate. Under these circumstances, the
validator may determine that the data should be
qualified or rejected. A discussion of the
rationale for data qualification and the qualifiers
used should be documented in the Data
Validation Memorandum.
4. Verify that the concentrations for positive
detects are within the initial calibration range.
4. a. If the concentrations for positive detects
exceed the upper limit of the initial
calibration range and no dilutions were
reported, then the validator should estimate
(J) those positive detects that exceed the
initial Calibration range
b. If the concentrations for positive detects
fall below the lower limit of the initial
calibration range, then the validator should
estimate (I’) ‘hose positive detects.
VOA/SV-XIll-4 DRAFT 12/96
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PART rI-vovsv Compound Quantitation and
Reported Quantitation Limits
C.
EVALUATION
D.
ACTION
5.
Ascertain if any sod/sediment/solid sample
has
5.
a.
If a soil/sedirnentfsolid sample has greater
less than or equal to 30 percent solids,
than 30 percent solids, then the vaiidator
should accept all sample data
b.
If a soil/sediment/solid sample has percent
solids of greater than or equal to 10% but
less than or equal to 30%, then the
validator should:
• Estimate (J) positive detects.
• Reject (R) non-detects.
c.
If a soil/sediment/solid sample has less than
10 percent solids, then the validacor should
reject (R) positive and non-detect sample
results as unusable.
d.
The validator should include a discussion of
the sample matrices having low percent
solids in the Data Validation Memorandum.
The validator may need to contact the field
sampler to determine whether sampling
techniques were appropriate for the sample
matrix.
Note: The following subsections are applicable only to a Tier Ill data validation:
C.2.a, C.2.b, C.3
Table VOA/SV-X III - 1:
1UALIFICATION OF VOLXflLE/SEMIYOLAT1LE ORGANIC ANALYTES BASED ON
SAMPLE PERCENT SOLIDS
Sample Result
% Solids > 30%
10% % Solids 30%
% Solids < 10%
— Detects
A
J
R
Non-detects
A
R
R
VOA/SV-XBi-3 DRAFT 12/96
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PART I1-VOA/SV Compound Quazititaiion and
Reported Quantitation Limits
E. EXAMPLES
Example Mi : (10% % Solids 30%)
DQOs for the Oak Street site specify that soil samples be analyzed for low level PAHs and other
semivolatile compounds to assess human health risk posed by the site contanunacion. Semivolacile
soil sample SAA5S had 15% solids and positive detects for chrysene. naphthalene, and
benzo(a)pyrene. Due to the low percent solids, the chrysene, naphthalene. and benzo(a)pyrene
detects are estimated (J) and all semivolatile non-detects are rejected (R) as unusable because the
elevated sample quantitanon limits do not meet project DQOs. The “alidacor reports the qualified
data on the Data Summary Table and notes this problem in the Data Validanon Memorandum.
Example #2 : (% Solids ( 10%)
Volatile sediment sample SAA89 had 8% solids and positive detects for chiorobeazene, benzene,
and trichioroethene. As a result of the extremely low percent solids (< 10%), the validator
rejects (R) as unusable all positive detects and non-detects for this sample. The validator contacts
the field sampler to determine if sampling techniques were inappropriate for the sample matrix
resulting in high moisture content. The validator reports the qualified data on the Data Summary
Table and discusses the high moisture content of the sample and the inappropriateness of the
sampling and/or analytical methods in the Data Validation Memorandum.
VOA/SV-Xffl-6 DRAFTS 12/96
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PART [ I-VOi%JSV Tentatively Identified Compounds
XIV. TENTATIVELY mEN1WILD COMPOUNDS
A. OBJECTIVE
Chrornatographic peaks that are not target analytes, surrogate compounds, or internal standards are
potential tentatively identified compounds (TICs). TICs must be qualitatively identified by a mass spectral
librazy search, followed with interpretation by the laboratory’s mass spectral interpretation specialist for
potential compound identification. Laboratory-reported TICs are also assessed by the data validaor
B. CRITERIA
The Region I. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region I Organic data. The CLP-VolatileJSem .i voiatije method QC
acceptance criteria listed in Appendices A and B should be used as the default criteria when none exist for
the Volatile/Senijvolatfle analytical method utilized and when sirmiar QC parameters are required by the
non-CLP method and acceptance criteria have not been specified. Deviations, modifications or non-CLP
method-specific QC acceptance criteria may be used but must be explicitly defined in tabular format in the
site specific EPA approved QAPjPISAP or amendment to the QAPjP/SAP.
1. In accordance with the method, the laboratory must conduct mass spectral library searches for
each sample and blank to report the possible identity of a specified number of volatile and
senuvolatile chromatographic peaks which are not surrogate compounds, internal standards, or
target compounds, but which have an area count or peak height greater than 10 percent of the area
count or peak height of the nearest internal standard. All GCIMS library searched mass spectra
for every sample and blank must be examined by the laboratory for tentative compound
identification.
NOTE : The laboratory should not report, as a tentatively identified compound, any target
compound which is properly reported in another fraction. For example, late eluting
volatile target compounds should not be reported as semivolatile TICs.
2. TIC concentrations should be qualified by the laboratory as estimated (J). TIC concentrations
should be calculated by the laboratory assuming an RRF of 1.0 and using the closes: eluting IS
that is free of interferences.
3. Chromatograxns for blanks should not contain any TIC peaks.
4. Guidelines for making tentative identifications are as follows:
a. Major ions (greater than 10 percent relative intensity) in the reference spectrum should
be present itt the sample spectrum.
b The relative intensities of the major ions should agree within ± 20 percent between the
sample and reference spectra.
c. Molecular ions present in the reference spectrum should be present in the sample
spectrum.
VOAISV-XJV.I DRAFT 12/96
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PART II-VOA/SV Tentatively Identified Compounds
4. d. Ions present in the sample spectrum but not in the reference spectrum should be reviewed
for possible background contamination, interference, or coelunon of additional TIC or
target compound(s).
e. Since library searches often yield several Candidate compounds having closely matching
scores, all reasonable choices must be considered and the most reasonable Candidate
chosen.
f. When the above cricena are not met, but in the technical judgment of the validator or
mass spectral interpretation specialist the identification is correct, the validator may report
the identification.
g. If in the validator’s judgment the identification is uncertain or there are extenuating
factors affecting compound identifications, the TIC result may be reported as “unknown .
5. The following common laboratory artifacts/contaminants and their sources (e.g., aldol
condensation products, solvent preservatives, and reagent contaminants) should not be reported
as TICs.
Examples:
a. Common laboratory contaminants: CO 2 (m/z 44), siloxanes (m/z 73), diethyl ether,
hexane, certain freons (1,1 ,2-tricbloro- 1 ,2,2-trifluoroethane or fluoro-inchloromethane),
and phthalaces at levels less than 100 ug/L or 4000 ugfKg.
b. Solvent preservatives such as cyclohexene - a methylene chloride preservative Related
by-products include cyclohexanone, cyclohexenone, cyclohexanol, cyclohexenol,
chiorocyclohexene, and chiorocyclohexanol.
c. Aldol condensation reaction products include: 4-hydroxy-4-rnethyl-2-pentanone. 4-
methyl-2-pencen-2-one , and 5,5-dimethyl-2(5H)-furanone.
VOA/SV-XIV-2 DRAFF 12/96
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PART I1-VOA/SV Tentatively Identiried Compounds
C. EVALUATION/ D. ACTION
C. EVALUATION
D. ACTION
All potential impacts on the sample data
resulting from tentatively identified compound
anomalies should be noted in the Data
Validation Memorandum. The validator should
also document and justify all technical decisions
made based on professional judgment in the
Data Validation Memorandum.
* 1. a. Venfy that the laboratory has generated a 1. a. If the laboratory has neglected to generate a
library search for all required peaks in the library search for all required peaks, then
sample and blank chroinacograrns. the validator should have the laboratory
requanutate and resubmit all corrected raw
data and forms should be resubmitted. If a
discrepancy remains unresolved, the
validator must use professional judgment to
decide which identification is accurate.
Under these circumstances, the validator
may determine that the sample data should
be qualified or rejected. A discussion of
the rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
b. Venfy that reported TIC peaks were not b. If the laboratory performed a library search
surrogate compounds or internal standards. on a surrogate compound or internal
standard, the validator should not report
that compound as a TIC on the Tentatively
Idemified Compounds Table-Table III.
c. Verify that a target compound from another c. If the laboratory reported a target
organic fraction was not reported as a TIC. compound from another organic fraction as
a TIC, then the validator should check that
fraction to determine if the laboratory
correctly identified the target compound in
that organic fraction. If the laboratory did
not correctly identify the target compound
in that fraction, then the laboratory should
be contacted to requantitate the false
negative result, report that compound with
the proper fraction, and remove that
______ — compound from the TIC form .
VOA/SV-XIV-3 DRAFT’ 12/96
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PART II-VOA/SV Tentatively Identified Compounds
C. EVALUATION
D. ACTION
* 1. d. Verify that a target compound was not
missed by the target compound search
procedure and erroneously reported as a
TIC in the proper analytical fraction. The
valjdator should evaluate other sample
chromatograms and check library reference
retention times on quantirauon lists to
determine whether the false negative result
is an isolated occurrence or whether data
from the entire case may be affected.
1. d. If the laboratory reported a target
compound from the proper fraction as a
TEC, then the validaor should contact the
laboratory to requantitace the false negative
result, report that compound on the correct
form, and remove that compound from the
TIC form
‘2. Verify that all TICs are reported with estimated
(J) concentrations by the laboratory. Verify
that TIC concentrations were calculated
correctly, assuming a RRF of 1.0 and using the
closest eluting IS that is free of interferences,
2. Qualify all TIC concentrations as estimated (J)
if the laboratory has not already done so. If the
laboratory did not quanutate the TIC assuming
an RRF of 1.0 and using the appropriate IS,
then the validaror should have the laboratory
requantitate and resubmit all corrected raw data
and forms. If a discrepancy remains
unresolved, the validator must use professional
judgment to decide which value is accurate.
Under these circumstances, the validator may
determine that the sample data should be
qualified or rejected. A discussion of the
rationale for data qualification and the qualifiers
used should be documented in the Data
Validation Memorandum.
‘3. Venfy that the blanks do not contain any TIC
peaks. When a low level non-target compound
is detected in a sample, a thorough check of
blank chromatograms may be required. Look
for peaks which are less than 10% of the
area/height of the nearest, interference-free IS.
and which are present in the blank
chromacogram at a similar relative retention
time.
3. a. If any TIC is found in a sample at a
concentration greater than 10 times the
level detected in an associated blank, then
the TIC should be reported.
b. If any TIC is found in a sample at a
concentration less than or equal to 10 times
the level detected in an associated blank,
then the TIC should not be reported.
VOA/SV-XIV--4 DRAV 12/96
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PART EI-VOA/SV
Tentajively Identified Compounds
Examine all TIC mass spectra in every
sample and blank. Compare sample TIC
spectra with all library search spectra to
confii-rri that tile most reasonable candidate
was chosen according to the cnteria set
forth in Section XIV, B.4.
* b. Verify that TICs were reported as
unknowns if the TIC spectra presented do
not meet the criteria set forth in Section
XIV, B.4 and thus no reasonable choices
could be determined.
4. a. The validator must use professional
judgment to determine if the cruena in
Section XIV, B.4 were met and a
reasonable identification was made. If
there is more than one possible match, then
the result may be reported as “either
compound X or compound Y ”. If there is
a lack of isomer specificuv, the TIC result
may be changed to a non-specific isomer
result (e.g., l , 3 ,5-thmethyl benzene to
trimethyl benzene isomer) or to a
compound class (e.g., 2-methyl, 3-ethyl
benzene to substituted aromatic compound).
The validator may elect to quantitatively
report all similar isomers as the sum of the
individual isomers. For example, all
alkanes may be quantitatively summed and
reported as total hydrocarbons. The
validator must summarize any changes
made to the laboratory data and must
document the rationale used to justify those
changes in the Data Validation
Memorandum.
b. If it is determined that a tentative
identification of a non-TCL compound is
unacceptable, then the tentative
identification should be changed to
unknown or to an appropriate
identification.
c. Other case factors may influence TIC
judgments. If a sample TIC match is poor
but other samples have a TIC with a good
library match, similar relative retention
time, and the same ions, then identification
information may be inferred from the other
sample TIC results.
*4 a.
C. EVALUATION
D. ACTION
* Note:
*
5.
Review blank and sample TIC spectra to
ensure that common laboratory
artifacts/contaminants are not reported as
TICs. (See Section XIV, 3.5 for examples
5. If a common laboratory artifact andlor
contaminant is reported as a TIC in a blank or
sample, then the validator should not report the
TIC on Table III TICs.
of common laboratory
artifacts/contaminants.)
The following subsections are applicable only to a Tier m data validation:
C.1.a, C.1.d, C.2, C.3, C.4.a, C.4.b, C.5
VOA/SV-XIV-3
DRAfT 12196
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PART [ 1-VOA/SV Tentatively Identified Compounds
E. EXAMPLES
Example I : (Target analyte improperly reported as TIC in another fraction)
The laboratory originally reported I ,2-dichlorobenzene as a TIC in the volatile fraction of soil
sample SAAI2. 1,2-dichlorobenzerie, however, was reported as a nondetect in the semivotatile
fraction. Upon review of the semivolatile chromatogram for sample SAAI2, the validaor notes
that the laboratory failed to idenufy a peak that eluted within the l,2-dichlorobenzene retention
time window. The laboratory was contacted and requested to requantitate the false negative
sernivolatile 1,2-dichlorobenzene result and report I,2-dichlorobenzene as a positive detect in the
semivolacile fraction, as well as remove the result from the VOA TIC form. The laboratory
complied and the validacor reports 1 ,2-dichlorobenzene as a positive detect in the semivolacile
fraction on the Data Summary Table.
Examole #2 : (TIC not reported, lack of spectral confirmation)
Dichloronaphihalene is reported as a TIC in semivolatile sample SAA35. The reference
dichloronaphthalene mass spectrum has a molecular ion of 196 and a 198, m+2, ion, with a
relative intensity of 66.0%. The sample dichloronaphthalene mass spectrum has a molecular ion
of 196 but the 198 ion has a 10.0% relative intensity. Because the sample spectrum’s chlorine
isotope (m+2 ion) relative intensity is riot within ± 20.0% of the reference spectrum’s relative
intensity, the presence of dichloronaphthalene is not confirmed in the field sample. The validator
uses professional judgment to determine that dichloronaphthaiene is not present in the field sample,
changes the TIC designation to “unknown , and justifies this in the Data Validation Memorandum.
The validator does riot report that TIC on the Tentatively Identified Compound-Table III since
“unknownf are not included on that taule.
Examt”e #3 : (Unreported peak with relative intensity greater than 10% of the nearest IS)
The validator verifies that all peaks greater than 10% of the nearest IS for sample SAAO1 are
accounted for in the chromatogram and quanutation report for sample SAAOI. To do this, the
validator identifies target compound, internal standard, and surrogate peaks on the chromatogram
quancication report, and the Form I. The remaining peaks (greater than 10% of the nearest IS)
should be listed as TICs. The vaiidator notes that one peak (greater than 10% of the nearest IS)
is unaccounted for and contacts the laboratory to obtain sample and reference mass spectra and
to request revision of the Form I TIC. The laboratory complies and the validacor reports that TIC
on the “Tentatively Identified Compound-Table III” in the Data Validation Memorandum.
VOA/SV-XIY-6 DRAFI’ 12/96
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PART EI-VOAISV Semivolatile Cleanup
XV. SEMIVOLATILE CLEANUP
A. OBJECTIVE
Seinivolacile cleanup procedures are utilized to remove matrix interferences from sample extracts prior to
analysis. If not removed from the sample extracts, matrix interferences can inhibit accurate compound
identification and quantitation resulting in highly suspect data. Sernivolacile cleanup procedures are checked
by spiking the cleanup columns or cartridges with target compounds, and evaluating the recovery of
sermvolatiles through the cleanup procedure.
Several types of sernivolacile cleanup procedures exist, including but not limited to:
1. Gel Permeation Chromatography (GPC) - separates compounds based on molecular size and can
be used to remove high molecular weight incerferencs.
GPC is a size exclusion procedure that utilizes organic solvents and hydrophobic gels to separate
macromolecules. The packing gel is porous and is characterized by the exclusion range (range
of uniformity) of that pore size. The exclusion range must be greater than those of the molecules
to be separated.
General applications of GPC as a cleanup procedure for sernivolatile organic fractions include the
removal of lipids, polymers, copolymers, proteins, naturai resins and polymers, cellular
components, viruses, steroids and dispersed high molecular-weight compounds from the sample
extract.
Under CLP SOW OLMO3.2, the GPC column is packed with bead-like packing and connected to
a UV detector. After the GPC is calibrated and a blank analyzed, sample extracts are loaded into
sample loops and an automated sequence is started. The target compounds are eluted with
methylene chloride and collected during the pre-decermined retention times. The high molecular
weight interferences, those outside the exclusion range. elute earlier than the TCL semivolaule
compounds during the ‘dump’ phase, while the smaller interferents such as sulftr elute with a
later volume of solvent during the ‘wash’ phase.
2. Silica Gel Cleanup - separates incerferents of different polarity.
Silica gel is a regenerative adsorbent of amorphous silica with weakly acidic properties and is used
for separating compounds of differing chemical polarity. Silica gel can be used for the cleanup
of sample extracts containing polynuclear aromatic hydrocarbons (PAHs) arid derivacized phenolic
compounds.
The silica gel column is packed with the required amounts of adsorbent, topped with a water
adsorbent, and then loaded with a sample extract. The analytes are eluced with solvents of
increasing polarity, to achieve desired separation, leaving the interfering compounds on the
column.
Note’ The CLP SOW OLMO3.2 seimvolacile method uses only GPC cleanup
VOA/SV-XV-1 DRAFr 12/96
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PART II-VOA/SV Semivolatile Cleanup
B. CRITERIA
The Region I, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses
should be used to validate all Region 1 Organic data. The CLP-Volatile/Sernjvolatile method QC
acceptance criteria listed in Appendices A and B should be used as the default criteria when none exist for
the Volaule/Senuvolatile analytical method utilized and when similar QC parameters are required by the
non-CLP method and acceptance criteria have not been specified. Deviations, modifications or non-CLP
method-specific QC acceptance criteria may be used but must be explicitly defined in tabular format in the
site-specific EPA approved QAPjP/SAP or amendment to the QAP 1 P/SAP.
1. Gel Permeation Chromatography
a. Seinivolatile sample extracts, QC sample extracts, and method blank extracts must
undergo all cleanup procedures required by the method.
b. The GPC system must be calibrated initially in accordance with the method prior to the
analysis of field samples, QC samples or blanks to ensure acceptable solid phase
activation, peak shape, and resolution of target compounds and imerferents
c. i. GPC calibration must be checked on a continuing basis at the frequency
specified in the method.
ii. The method-required GPC calibration check solution must contain target and
surrogate compounds and interferents at the method-required concentrations and
must be analyzed according to the analytical method.
iii. Target compound recoveries must mee method QC acceptance criteria.
iv. Surrogate compound and internal standard area counts and/or retention times
must meet method QC acceptance criteria.
v. Peak shapes must be symmetrical and resolution must meet method QC
acceptance criteria.
-1. c. vi. Retention time shifts between GPC calibration checks must not exceed ±5%
between calibrations,
d. i. A GPC instrument blank spiked with surrogate compounds must be analyzed
after each GPC calibration and calibration check and prior in sample analysis
ii. Target compounds must not be present at greater than or equal to the
quanutation limit for any target compound in the GPC instrument blank
iii. Surrogate compound recoveries and internal standard area counts andfor
retention times (if added) in GPC instrument blanks must meet method QC
acceptance criteria after GPC cleanup. Note CLP SOW OLMO3 2 does not
require the addition of surrogate compounds or internal standards to the GPC
instrument blank.
VOA/SV-XV-2 DRAFT 12/96
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PART U-VOAJSV Semivolatile Cleanup
2 Silica Gel Cleanup
a. Seniivolatile sample extracts, QC sample extracts and method blank extracts must
undergo all cleanup procedures required by the method.
b. Each lot number of solid phase adsorbent must be checked in accordance with the method
prior to use to ensure acceptable solid phase activation, recovery of target analytes, and
elimination of interferents.
C. i. A Silica Gel Check solution must be prepared ith each cleanup batca and must
be analyzed prior to the Silica Gel column reagent blank. For each batch of
samples undergoing Silica Gel column cleanup, the column performance must
be checked with a Silica Gel Check solution to demonstrate that the compounds
of interest are being quantitatively recovered.
ii. The method-required Silica Gel Check solution must contain target and surrogate
compounds and incerferents at method-required concentrations and must be
prepared and analyzed according to the analytical method.
iii. Target compound recoveries must meet method QC acceptance criteria.
iv. Surrogate compound and internal standard area counts ana/or retention times
must meet method QC acceptance criteria.
d. i. A Silica Gel column reagent blank spiked with surrogate compounds must be
prepared with each cleanup batch. The Silica Gel column reagent blank must
be analyzed after the Silica Gel Check solution and prior to field samples.
ii. Target compounds must not be present at greater than or equal to the
quantitanon limit for any target compound in the Silica Gel column reagent
blank.
iii. Surrogate compound recoveries and internal standard area counts and/or
retention times (if added) in Silica Gel column reagent blanks must meet method
QC acceptance criteria after Silica Gel column cleanup
VOA/SV-XV .3 DRAFT 12196
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PART ll-VOA/SV
Semivolatile Cleanup
C. EVALUATION/ D. ACTION
C. EVALUATION
D. ACTION
1. Gel Permeation Chromatography (GPC)
a. Verify from result forms, if available, that
GPC cleanup was performed according to
the analytical method on all method-
required sample extracts, QC sample
extracts, and method blank extracts.
* b. Verify that the GPC system was calibrated
initially in accordance with the method
requirements and that peak shape and
resolution criteria were met.
* C. i. Confirm from the raw data that the
GPC calibration check was performed
at the method-required frequency.
* ii. Verify that a GPC calibration check
solution was analyzed in accordance
with the method and that the correct
target and surrogate compounds,
merferents and concentranons were
used.
All potential impacts on the sample data
resulting from sample cleanup anomalies should
be noted in the Data Validation Memorandum
The validator should also document and justify
all technical decisions made based on
professional judgment in the Data Validation
Memorandum.
1. Gel Permeation Chromatography (GPC)
a. If GPC was not performed according to the
analytical method on all method-required
extracts, then the raw data should be
reviewed for the presence of high
molecular weight contaminants and
professional judgment should be used to
qualify or reject sample data. The
validator should request sample cleanup and
reanalysis if GPC was required by the
method.
b. If the GPC system was not calibrated
initially in accordance with the method
(prior to the analysis of field samples, QC
samples or blanks) or fails to meet peak
shape and/or resolution criteria or the
initial calibration data are no available for
review, then the validator should evaluate
the last calibration check analyzed just
prior to sample analysis.
c. i. If GPC calibration checks have not
been performed at the method-required
frequency, then the quality of the GPC
operation may be suspect and the
validaror should use professional
judgment to qualify or reject sample
data.
ii. If a GPC calibration check solution
was not analyzed in accordance with
the method or the correct compounds
and/or concentrations were not used,
then the data quality may be adversely
affected. In these circumstances. the
validaror should use professional
judgment to qualify or reject sample
data.
VOA/SV-XV-4
DRAFT 12/96
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PART ll-VOA/SV
Semivolatile Cleanup
C. EVALUATION
D. ACTION
1. C iii. Check the reported data from the GPC
calibration check solution analyses to
verify that target compound recoveries
meet method QC acceptance criteria.
c. iii If GPC calibration check method QC
acceptance criteria are not met, then
the GPC calibration check solution
results should be used to qualify
sample data for specific compounds
included in the check solution.
Professional judgment should be used
to qualify or reject sample data for
non-check solution compounds, taking
into consideration the compound’s
chemical class. The vajjdator should
discuss the impact of unacceptable
recoveries on the sample data in terms
of high or low bias and note this in the
Data \‘alidation Memorandum.
If a GPC calibration check compound
recovety is greater than the upper limit
of the method QC acceDtance criteria,
then the validator should:
- Estimate (J) the affected compound
when detected in any sample
associated with that GPC
calibration check to indicate
potential high bias.
- Accept the quantitation limit of the
affected compound in any sample
associated with that GPC
calibration check.
If more than half of the GPC
calibration check compound recoveries
are greater than the upper limit of the
method QC acceptance criteria, then
the validacor should:
• Estimate (J) g j positive detects in
all samples associated with that
GPC c libration check to indicate
potential high bias
- Accept fl quantitacion limits for
non-detects in all samoles
associated with that CFPC
calibration check.
If a GPC calibration check comoound
recovery is less than the lower limit of
the method QC acceptance criteria but
greater than or equal to 10%, then the
validator should.
Estimate (J) the affected compound
when detected in any sample
associated with that GPC
calibration check to indicate
potential low bias
Estimate (UJ) the quantitat on brnit
ot the affected compound n any
samole associated with that GPC
calioration check to indicate
potentia ’ low bias
VOA/SV-XV-5
DRAFT 12/96
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PART ll-VOA/SV Semivolatile Cleanup
C. EVALUATION
D. ACTION
1. c. Continued from above. i. c. iii. Continued from above.
If more thazi half of the GPC
calibration check compound recoveries
are less than (he lower lim it of the
method QC acceptance criteria but
gre:iter than or equal to 10%, then the
validator should
- Estimate (J) jj positive detects in
all samples associated with that
GPC calibration check to indicate
potential low bias.
- Estimate (UJ) all quantitanon
limits for non- tects in all
samples associated with that GPC
calibration check to indicate
potential low bias.
If a GPC calibration check compound
recovery is less than 10%, then the
validator should:
- Estimate (J) the affected compound
when detected in any sample
associated with that GPC
calibration check to indicate
potential low bias.
- Reject (R) the quantitation limit of
the affected compound in any
samole associated with that DPC
calibration check to indicate that
the data are unusable due to the
possibility of false negatives
If more than half of the GPC
calibration check compound recoveries
are less than 10%, then the validacor
should:
S
- Estimate (J) j positive detects in
all samples associated with that
GPC calibration check to indicate
potential low bias.
- Reject (R) the quantitation limits
for non-detects in all samples
associated with that GPC
calibration check to indicate that
the data are unusable due to the
possibility of false negatives.
If more than half of the GPC
calibration check compound recoveries
are outside the method QC acceptance
limits in one GPC calibration check,
where some recoveries are low and
some recoveries are high, then the
vaiidator should use professional
judgment to qualify or reject a
particular compound, class of
compounds or the entire fraction for
samoles associated with that GPC
_______ calibration check
VOAJSV -XV-6 DRAFT’ 12/96
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PART ll-VOA/SV
Semivolatile Cleanup
C. EVALUATION
D. ACTION
i. C. iv. Verify that surrogate compound
recoveries and internal standard area
counts andIor retention times in the
GPC calibration check meet method
QC acceptance criterta.
* v. Review the raw GPC ,alibrntion check
data to verify that peaks are
symmethcal and resolution meets
method QC acceptance criteria for
target and surrogate compounds and
interferents in the GPC calibration
check solution.
* vi. Check the raw GPC calibration check
data to verify that retention times for
any compounds or incerferents in the
GPC calibration solution did not vary
more than ± 5% between calibrations.
* d. i.
Verify that a GPC instrument blank
was analyzed after each GPC
calibration and calibration check and
prior to sample analysis.
* ii. Verify that there are no target
compounds present at greater than or
eQual to the quantitation limit in the
GPC instrument blank.
* iii. Verify that surrogate compound
recoveries and internal standard area
counts and/or retention times (if added)
in the GPC instrument blank meet
method QC acceptance criteria.
1. c. iv. If surrogate compound recoveries
and/or internal standard area counts or
retention times in the GPC calibration
check do not meet method QC
acceptance criteria, then the validacor
should qualify the sample data in
accordance with Sections VI and VII
v. If the GPC calibration check method
QC acceptance criteria do not meet
peak shape and compound resolution,
then the raw sample data should be
examined for the presence of high
molecular-weight interzerences or the
loss of late eluun g target compounds
and professional judgment should be
used to qualify or reject sample data.
The validator should discuss the impact
of unacceptable peak shape and
resolution on the sample data in erms
of high or low bias andior the
possibility of false negatives and note
this in the Data Validation
Memorandum.
vi. Retention time shifts indicate
instrument performance problems that
require laboratory corrective actions.
If retention time shifts are excessive,
the GPC cleanup procedure may be the
cause of analyte losses and false
negatives, and the validator should
evaluate the sample data careñiilv and
document all deficiencies in the Data
Validation Memorandum.
d i. If a GPC instrument blank was not
analyzed at the correct frequency and
in the proper sequence, then the
validator must use professional
judgment in conjunction with the blank
guiaance provided in Section V to
qualify or reject sample data.
ii. If any target compounds are detected in
the GPC instrument blank at greater
than or equal to the quantitation limit,
then the quality of the GPC operation
is suspect. The validator must use
professional judgment in coniunctior
with the blank guidance provided in
Section V to qualify or reject sample
daa.
iii. If surrogate compound recoveries
andlor internal standard area counts or
retention times in the GPC instrument
blank do not meet method QC
acceptance criteria, then the vaiidacor
should qualify the sample data in
accordance with Sections V VI, and
V I I .
VOAJSV-XV-7
DRAFT’ 12/96
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PART II-VOAISV Semivolatile Cleanup
C. EVALUATION
D. ACTION
1. e. Compare the raw data to the reported
results, if available, and verify that no
calculation and/or transcription errors have
occurred. If result forms are not available,
then the validator must review the cleanup
logs to confirm that method required
cleanups were performed.
.
f. . eview MS/MSD. surrogate, and PES data
evaluate the efficiency of the GPC
cleanup. -
1. e. If the laboratory made any calculation
and/or transcnpuon errors, the validator
should have the laboratory requantitate and
resubmit all corrected raw data and forms.
If a discrepancy remains unresolved, the
validator must use professional judgment to
decide which value is most accurate.
Under these circumstances, the validator
may determine that the sample data should
be qualified or rejected. A discussion of
the rationale for data qualification and the
q ualifiers used should be documented in the
Data Validation Memorandum.
f. If any compound or compound class has
zero recovery indicating the possibility of
false negatives and/or recovers low
indicating a potential low bias, then the
validaror should discuss the possible false
negatives and/or potential low bias in the
Data Validation Memorandum and qualify
and/or reject sample results according to
the guidance provided in Sections VI, VIII
and XI.
2. Silica Gel Cleanup
a. Verify from result forms, if available, that
Silica Gel cleanup was performed according
to the analytical method on all method-
required sample extracts, QC sample
extracts, and method blank extracts.
b. Verify that each lot of Silica Gel used to
cleanup samples was checked prior to use
in accordance with method requirements.
,,
c. i. Verify from result forms, if available,
that a Silica Gel Check solution was
prepared with each batch of samples
undergoing Silica Gel cleanup and
analyzed prior to the Silica Gel column
reagent blank in accordance with the
analytical method.
2. Silica Gel Cleanup
a. If Silica Gel cleanup was not performed
according to the analytical method on all
method-required extracts, then the data
should be reviewed for the presence of
interferents and professional judgment
should be used to qualify or reject sample
data. The validator should request sample
cleanup and reanalysis if Silica Gel cleanup
was required by the method.
b. If each lot of Silica Gel was not checked,
then the solid phase may not be properly
activated potentially resulting in
unacceptable target compound recoveries,
the presence of interferents and possibly the
loss of target compounds (false negatives).
The validator should review the Silica Gel
Check solution data associated with each
batch of Silica Gel column cleanups to
ascertain if any target compounds should be
qualified or rejected using the guidance
provided in Section XV, D.2.c iii.
c. i. If the laboratory did not prepare and
analyze the Silica Gel check solution at
the correct frequency and sequence.
according to the method, then the
valicLator should use professional
judgment to qualify or reject sample
data
VOA/SV-XV-8 DRAFF 12/96
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PART ll-VOA/SV
Semivolatile Cleanup
C. EVALUATION
D. ACTION
*2. c. ii. Verify that a Silica Gel Check solution
was prepared and analyzed in
accordance with the method and that
the correct target and surrogate
compounds, incerferents and
concentrations were used.
iii. Check the reported data from the Silica
Gel Check solution analyses to verify
that target compound recoveries meet
method QC acceptance cntei-ia.
2. c. ii. If a Silica Gel Check solution was not
prepared and analyzed in accorciance
with the method or the correct
compounds and/or concentrations were
not used, then the data quality may be
adversely affected. In these
circumstances, the validator should use
professional judgment to qualify or
reject sample data.
iii. If Silica Gel cleanup method QC
acceptance criteria are not met, then
the Silica Gel Check solution results
should be used to qualify sample data
for specific compounds included in the
check solution. Professional judgment
should be used to qualify or reject
sample data for non-check solution
compounds, taking into consideration
the compound’s chemical class. The
validator should discuss the impact of
unacceptable recoveries on the sample
data in terms of high or low bias and
note this in the Data Validation
Memorandum.
If a Silica Gel Check solution
compound recovery is greater than the
upper limit of the method QC
acceptance criteria, then the validacor
should:
- Estimate (J) the affected compound
when detected in any sample
associated with that Silica Gel
Check solution to indicate potential
high bias.
- Accept the quantitarion lirnn of the
affected compound in any sample
associated with that Silica Gel
Check solution.
If more than half of the Silica Gel
Check solution compound recoveries
are greater than the upper limit of the
method QC acceptance criteria, then
the validator should:
- Estimate (J) j positive detects in
all samples associated with that
Silica Gel Check solution to
indicate potential high bias.
- Accept quancicacion limits for
non-detects in all samples
associated with that Silica Gel
Check solution.
VOA/SV-XV-9
DRAfl 12/96
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PART ll-VOA/SV Semivolatile Cleanup
C. EVALUATION
D. ACTION
2. c. Continued from above. 2. c. iii. Continued from above
If a Silica Gel Check solution
compound recovery is less than the
lower limit of the method QC
acceptance criteria but greater than or
equal to 10%, then the validawr
should:
- Estimate (J) the affected compound
when detected in any sample
associated with that Silica Gel
Check solution to indicate potential
low bias.
- Estimate (Ui) the quanucation limit
of the affected compound in any
sample associated with that Silica
Gel Check solution to indicate
potential low bias.
If more than half of the Silica Gel
Check solution compound recovenes
are less than the lower limit of the
method QC acceptance criteria but
greater than or equal to 10%, then the
validator should:
- Estimate (J) all positive detects in
all samples associated with that
Silica Gel Check solution to
indicate potential low bias.
- Estimate (UJ) j quantitation
limits for non-detects in all
samples associated with that Silica
Gel Check solution to indicate
potential low bias.
If a Silica Gel Check solution
compound recovery is less than 10%,
then the validator should:
- Estimate (5) the affected compound
when detected in any sample
associated with that Silica Gel
Check solution to indicate potential
low bias.
- Reject (R) the quantitauon limit of
the affected compound in any
sample associated with that Silica
Gel Check solution to indicate that
the data are unusable due to the
________ possibility of false ne2atives
VOA/SV-XV-1O DRAFT 12/96
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PART U-VOA1SV
Semivolatile Cleanup
* iv. Verify that surrogate compound
recoveries and internal standard area
counts andlor retention times in the
Silica Gel Check solution meet method
QC acceptance criteria.
* d. i. Verify that a Silica Gel column reagent
blank was prepared with each cleanup
batch and was analyzed after the Silica
Gel Check solution but prior to field
samples.
* jj Verify that there are no target
compounds present at greater than or
eaual to the quantitation limit in the
Silica Gel column reagent blank.
2. c. iii. Continued from above.
If more than half of the Silica Gel
Check solution compound recoveries
are less than 10%, then the validator
should:
• Estimate (J) jj positive detects in
all samples associated with that
Silica Gel Check solution to
indicate potential low bias.
- Reject (R) the quantitation limits
for jj non-detects in all samples
associated with that Silica Gel
Check solution to indicate that the
data are unusable due to the
poss biIity of false negatives.
If more than half of the Silica Gel
Check solution compound recoveries
are outside the method QC acceptance
limits in one Silica Gel Check solution,
where some recoveries are low and
some recoveries are high, then the
validator should use professional
judgment to qualify or reject a
particular compound, class of
compounds or the entire fraction for
samples associated with that Silica Gel
Check solution.
iv If surrogate compound recoveries
andior internal standard area counts or
retention times in the Silica Gel Check
solution do not meet method QC
acceptance criteria, then the validator
should qualify the sample data in
accordance with Sections VI and VII.
d. i. If a Silica Gel column reagent blank
was not prepared and analyzed at the
correct frequency and in the proper
sequence, then the validator must use
professional judgment in conjunction
with the blank guidance provided in
Section V to qualify or reject sample
data.
ii. If any target compounds are detected tn
the Silica Gel column reagent blank at
greater than or eaual to the quantitauon
limit, then the Silica Gel may be
contaminated. The validator shouid
evaluate the method blank data arid use
proiessional judgment in conjunction
with the blank guidance provided in
— Secucr V to aualifv or reJect data.
2. c. iii. Continued from above.
C. EVALUATION
D. ACTION
VOA/SV-XV-l I
DRAFT I2/9
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PART ll-VOAJSV
Semivolatile Cleanup
C. EVALUATION
D. ACTION
*2. d. iii. Verify that surrogate compound
recoveries and internal standard area
counts and/or retention times (if added)
in the Silica Gel column reagent blank
meet method QC acceptance criteria.
* e. Compare the raw data to the reported
results, if available, and verify that no
calculation andIor transcription errors have
occurred. If result forms are not available,
- : then the validator must review the cleanup
logs to confirm that method required
cleanups were performed.
f. Review MSIMSD, surrogate, and PES data
to evaluate the efficiency of the Silica Gel
cleanup.
2. d. iii. If surrogate compound recoveries
and/or internal standard area counts or
retention times in the Silica Gel
column reagent blank do not meet
method QC acceptance criteria, then
the validator should qualify the sample
data in accordance with Sections V.
Vt, and VII.
e. If the laboracoiy made any calculation
and/or transcription errors, the validacor
should have the laboratory requantitate and
resubmit all corrected raw data and forms.
If a discrepancy remains unresolved, the
validator must use professional judgment to
decide which value is most accurate.
Under these circumstances, the validator
may determine that the sample data should
be qualified or rejected. A discussion of
the rationale for data qualification and the
qualifiers used should be documented in the
Data Validation Memorandum.
f. If any compound or compound class has
zero recovery indicating the possibility of
false negatives and/or recovers low
indicating a potential low bias, then the
validator should discuss the possible false
negatives and/or potential low bias in the
Data Validation Memorandum and qualify
and/or reject sample results according to
the guidance provided Sections VI, VIII
and XI.
* Note: The following subsections are applicable only to a Tier III data validation:
C.1.b, C.1.c.i. C.1.c.ii, C.1.civ, C.1.c.v, C.1.vi, C.1.d.i, C.d.1.ii, C.1.d.iii, C.1.e, C.2.c.ii,
C.2.c.iv, C.2.d.i, C.2.d.ii, C.2.d.iii, C.2.e
VOA/SV-XV- 12
DRAFt’ 12/96
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PART II-VOA/SV Semivolatile Cleanup
Table SV.XV-l:
QUALIFICATION OF SEMIVOLATILE ANALYTES BASED ON
GPC CALIBRATION QUALITY CONTROL
] Criteria
Action
Peak
L__Resolution
As per method QC acceptance criteria.
Professional Judgment
Peak
Shape
Peak shapes must be symmetrical.
Professional Judgment
Retention
Time Shift
Retention time shifts between GPC calibration
checks must not exceed ± 5%.
Professional Judgment
GPC Instrument
Blank
Target analytes must be < QL and surrogate
compound recoveries and IS area counts andior
RTs (if added) must meet method QC acceptance
criteria. (Note: CL? SOW OLMO3.2 does not
require the addition of surrogate compounds to the
GPC instrument blank)
Refer o Sec:ion V for Blank
Actions
Table VOA/SV-XI -2:
QUALIFICATION OF SEMIVOLATILE ANALYTES BASED ON GPC CLEANUP qUALITY CONTROL
WHERE: ONE-HALF OF GPC CALIBRATION CHECK COMPOUNDS OUTSIDE UPPER OR
LOWER ACCEPTANCE LIMITS
Sample Results
%_Recovery
%Rec < 10% 10% %Rec UL
Detects
J
.r
A
Non-detects
-
R Ui
A
A
LL - Lower Limit of method QC acceptance criteria
UL - Upper Limit of method QC acceptance criteria
VOA/SV-XV-13 DRAFr 12/96
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PART !J-VOAISV Sernivolatile Cleanup
Table V/SV-XI-3.
QUALIFICATION OF SEMIVOLATILE ANALYTES BASED ON GPC CLEANUP OUALrFY CONTROL
W IERE: > ONE-HALF OF GPC CALIBRATION CHECK COMPOUNDS OUTSIDE UPPER OR
LOWER ACCEPTANCE LIMITS
Sam pie Results
%_Recovery
%Rec < 10% 10% %Rec UL
Detects
.1 J f
A
J
AilNon-detects
R UJ I
A
A
Note: Professional judgment should be used when a combination of low recoveries and high recoveries are
obtained.
LL - Lower Limit of method QC acceptance criteria
UL - Upper Linrn of method QC acceptance criteria
Table SV-XV-4:
QUALIFICATION OF SEMIVOLATILE ANALY ES BASED ON SILICA GEL
CLEANUP OUALITY CONTROL WHERE: £ ONE HALF OF SILICA GEL CHECK SOLUTION
COMPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE CRiTERIA
Sample Results
%_Recovery
%Rec < 10%_J
10% £ %Rec £ LL
1
j LL £ %Rec £ UL
%Rec > UL
Detects
J
J
A
J
Non4le tects
R
UJ
A
A
Silica Gel Column
Blank
Target analytes must be < QL and surrogate compound
recoveries and IS area counts and/or RTs (if added) must meet
method QC acceptance criteria.
Refer to Section
V for Blank
Actions
Noce Professional judgment should be used in applying the guidance above to qualify or reject sample data.
LL - Lower Limit of method QC acceptance criteria.
UL - Upper Limit of method QC acceptance critena.
VOA/SV-XV-14 DRAYr 12/96
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PART fl-VOA/SV Semivolatile Cleanup
Table V/SV-XI-5:
OUALIFICATION OF SEMIVOLATILE ANALYTES BASED ON SILICA GEL CLEANUP QUALiTY
C(Thfl I WHERE: > ONE-W TF OF T1’ GEL CHECK SOLUTION COMPOUNDS OUTSIDE
• — -— — .—-—.
•fl._Js _n_ — - - -
TJPPER OR LOWER ACCEPTANCE LI1 IITS
Sample Results
% Recovery
%Rec < 10%
10% %Rec < LL
LL %Rec UL
%Rec > UL
llDetects I
J
A
j
ii Non-detects
R
UJ
A
A
Note: Professional judgment should be used when a combination of low recoveries and high recoveries are
obtained.
LL - Lower Limit of method QC acceptance criteria
UL - Upper Limit of method QC acceptance criteria
E. EXAMPLES
Examoie ‘ : (Unacceptable GPC peak resolution and retention time shift)
The validator compares the raw GPC calibration data with CLP SOW OLMO3.2 criteria to verify that
the proper collection and dump cycles were utilized to ensure that all interferences were removed
without loss of target compounds. To do this, the validator reviews the peak shane, resolution, and
retention time shift data for the GPC calibration. The validacor notes that the calibration retention time
shift exceeded the ± 5% criteria. The validacor also notes that the baseline resolution between
perylene and sulfur is less than 90%. The validator uses professional judgment to estimate (J) the
positive detects and reject (R) the quanutation limits for non-detects for all samples associated with the
non-compliant GPC calibration. The validacor reports the qualified data on the Data Summary Table
and discusses the low bias and potential false negatives due to insufficient column resolution and
incorrect collect and dump cycles.
E ainole 2 : (Silica Gel Check % recovery > upper limit for one compound)
The validator exarmnes the raw Silica Gel cleanup data to verify that the percent recoveries from the
Silica Gel Check meet method-specific QC acceptance cnceria of 80-110%. The check solution
contains several PAHs at 3 times the method quancitation limit. The validator notes that one of the
check solution compounds, phenanthrene. was recovered at 150%. The validator uses professional
judgment to estimate (J) the positive phenanthrene detects and accepts (A) the quantitation limits for
phenanthrene non-detects on the Data Summary Table. The validator notes in the Data Validation
Memorandum that a high bias exists for phenanthrene and that positive results of phenanthrene may
actually be lower than the reported results.
VOAJSV-XV-15 DRAFT 12/96
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PART tI-VOAISV System Performance
XVI. SYSTEM PERFORMANCE
A. OBJECTIVE
The objective of assessing overall system performance is to determine if any methcd preparatory and/or
analytical procedures result in qualitative and/or quantitative system error or bias. All sample, QC sample,
and blank results are reviewed for accuracY, chromatography, precision, sensitivity, and contamination to
ascertain if there are any general trends in data quality.
B. CRITERIA
Since there are no specific criteria for system performance, professional judgment should be used to assess
the overall performance.
C. EVALUATION/ D. ACTION
C.
EVALUATION
D.
ACTION
9.
The results of Zero, Single and Double Blind
1.
The validator should refer to the previous
PESs, MDL study, LFB, calibration standaids,
sections for specific guidance on evaluating
MS/MSD, and surrogate spike compound
accuracy using PES, MDL study, LFB,
analyses may be used to assess the overall
calibration standard, MSIMSD and
system accuracy including purge and extraction
surrogate data. If the validator determines
efficiency and instrument response.
that analytical trends indicate a qualitative
and/or quantitative systematic bias, then the
a. Evaluate all PES and other relevant QC
validator should use professional judgment
data to determine if any analytical trends
to determine whether or not to qualify or
exist over the sample analysis period,
reject the sample data based on the extent
of the impact. The validator should discuss
b. The validator should ascertain from the
and justify all technical decisions in the
PES and other relevant QC data if there is
Data Validation Memorandum. The
a high or low quantitative bias for a
validator should differentiate between
pamcular compound or group of
sample matrix-related preparatory and
compounds.
analysis problems that are outside the
laboratory’s control and those preparatory
c. The validator should also ascertain from the
and analysis problems that are within the
PES and other relevant QC data if there is
laboratory’s control.
a oocential for false negatives and/or false
positives to be reported.
d. The validator should ascertain frca the
MS/MSD and surrogate spike compound
analyses if the sample matrix effects impact
compound recovery, thus indicating a
method bias outside the control of the
laboratory
VOAISV-XVI-l DRAFT 12/96
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PART tI-VOA/SV
System Performance
C. EVALUATION
D. ACTION
‘2. The results of the PES, LFB and calibration
standard analyses as well as field samples may
be used to assess the overall system
chromatography
* a Evaluate sample and QC sample
reconstructed ion chromatograms analyzed
on all columns to determine if the column
chromatography, peak shape, resolution,
and baseline drift has either deteriorated or
improved over the sample analysis period.
* b. The validacor should ascertain from the raw
J.aca if unacceptable chromatography may
contribute to a high or a low quantitative
bias for a particular compound or group of
compounds.
* c. The validator should also ascertain from the
raw data if unacceptable chromatography
may result in a potential for false negative
andlor false positive identifications.
* d. The validator should determine if
chromatography problems are a result of
the sample matrix or are unique to the
instrument. To that end, the validator
should review the data package narrative
for a discussion of possible matrix
problems that the laboracoiy may have
encountered.
* e. The validator should determine if
significant retention time shifts have
occurred between initial and continuing
calibration.
2. The validator should refer to the previous
sections for specific guidance on evaluating
compound identification and quantitation. If the
validator determines that chromaographic
trends indicate a qualitative and/or quantitative
systematic bias, then professional judgment
should be used to determine whether or not to
qualify or reject the sample data based on the
extent of the impact. The validator should
discuss and justify all technical decisions in the
Data Validation Memorandum. The validator
should especially note when chromatography
problems and column degradation are caused by
severe matrix interferences. The validator
should recommend additional cleanup
procedures and/or alternate analytical methods
for future site work.
VOA/SV-XVI-2
DRAFT 12/96
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PART fl-VOAJSV System Performance
C.
EVALUATION
-_D.
ACTION
3.
The results of the calibration standard, MDL
3.
The validator should refer to the previous
study, internal standard, surrogate spike
sections for specific guidance on evaluating
compound. MS/MSD, and field duplicate
laboratory and field precision and internal
analyses may be used to assess overall system
standard and surrogate compound analyses. If
precis ion.
the validator determines that an instrument
a. Compare the daily standard calibration area
produces erratic detector responses, then they
should use professional judgment to qualify or
counts to ascertain if the instrument
reject sample data. If MS/MSD RPDs indicate
generated consistent detector responses over
laboratory imprecision, then the validator
the sample analysis period,
should suspect laboratory technique and cake
into consideration the results of the field
*
b. Review the area counts of the internal
duplicate RPDs when using professional
standards and surrogate compounds for
judgment to qualify sample data. If field
each sample to ascertain if there is a change
duplicate RPDs indicate field imprecision
in detector response.
resulting from heterogeneous sample macrices
or field sampling error, then the validator
c. The validator should evaluate the MS/MSD
should use professional judgment to qualify
RPDs in conjunction with field duplicate
sample data based on the extent of impact. The
RPDs to identify any analytical trends,
validator should differentiate between lack of
ascertain if sample macrices were
precision due to instrument performance
homogeneous or heterogeneous, and
problems and that caused by matrix effects or
determine if sampling error may have
sampling error.
contributed to field imprecision.
VOA/SV-XVI-3 DRAFT 12/96
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PART ll-VOA/SV
System Performance
C. EVALUATION
D. ACTION
*4 The results of the LFB, PES, calibration and
internal standard analyses may be used to assess
the overall system sensitivity. (Note: VOA
surrogates may also be used because they are
equivalent to internal standards.)
a. Review all daily LFBs, low level
calibration standards, and PES data to
evaluate sensitivity for each instrument to
verify that no instrument has lost its ability
to accurately quanucare and identify
compounds at the quancicacion limit over the
sample analysis period, which could
i potentially result in false negatives and low
biased results.
* b. Check the area counts of the individual
sample, QC sample, calibration and blank
internal standards and calibration standards
to monitor instrument sensitivity changes.
* c. Review the sample chromatograms for
abrupt, discrete shifts in the
chromaographic baseline which may
indicate a change in the instrument’s
sensitivity or the zero setting. A baseline
“decline could indicate a decrease in
sensitivity in the instrument or an increase
in the instrument zero, possibly causing
target compounds, at or near the detection
limit, to truss detection (false negatives).
Additionally, a decline in the baseline may
result in incorrect peak integration and
subsequent inisquanutanon.
A sudden baseline shift could indicate
problems such as a change in the
instrument zero, a leak, degradation of the
column or the forniation of matrix
degradation products. The validator should
check for any abrupt shift in the zero
setting which may cause a false positive to
be reported. Additionally, a rise in the
baseline may result rn incorrect peak
integration and subsequent niisquanutation.
* d. The validator may determine that
instrument sensitivity is adequate but
sample matrix effects may preclude
obtaining the quanutanon limits required by
the project DQOs using the analytical
method employed.
4. The validator should refer to the previous
sections for specific guidance on evaluating
sensitivity, accuracy, compound identification,
and quanutacion. If the validator determines
that instrument sensitivity is unacceptable, then
the validator should use professional judgment
to qualify or reject the affected sample data.
The validator should discuss and justify all
technical decisions in the Data Validation
Memorandum. The validator should also note
if sample matrix interferences did not allow
quanucation limits to be achieved and should
recommend additional cleanup procedures
and/or alternate analytical methods for future
site work.
VOA/SV-XVI-4
DRAFT’ 12/96
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PART II-VOAI V System Performance
C.
EVALUATION
D.
ACTION
*5
The results of the PES and method. instrument,
5.
The validator should refer to the previous
cleanup, equipmentirmsace, trip, storage and
bottle blank analyses may be used to assess
overall system contamination,
sections for specific guidance on evaluating
blank contamination. If the validator
determines that there is a systematic blank error
introduced during sample collection or
a. Review all blank and sample results to
evaluate the possibility of sample
processing (extraction or analysis), then the
data should be qualified according to Section V
contamination introduced via either cross-
However, if the validator suspects intermittent
contamination from a previously run sample
or sporadic introduction of interferents during
or from general lab contamination,
analysis, then the validator should use
professional judgment to qualify or reject
b. Compare blank analysis on two different
sample data and document and justify all
instruments to determine if the
technical decisions in the Data Validation
contamination is instrument related or the
Memorandum.
interferents aze present in the blank from
sample processing activities.
c. Assess whether problematic blank results
are reproducible when replicate aliquots are
analyzed or aie sporadic interferences.
Sporadic interferences, such as methylene
chloride, acetone or phthalates, may
indicate that the incerferent is introduced
from the laboratory environment. The
validator should review sample
chromatograms for suspected outlier
interferents.
* Note: This section is only applicable to a Tier m data validation - If a validator suspects system
performance has degraded to the degree that data are affected and a Tier II validation has
been requested, then the validator should contact the Site Manager to approve the necessary
Tier III validation.
VOA/SV-XVI-5 DRAFT 12/96
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PART U-VOA/SV System Performance
E. EXAMPLES
Example #1 : (Abrupt decrease in baseline)
The validator notices a significant abrupt decrease in the baseline during the analysis of aqueous
sample SAP55. The validator examines the IS area counts and observes that a decrease in the area
counts for the last two internal standards has occurred. The valjdator notes that the VOA
surrogate compound areas for the last two surrogates also decreased. There were no PE samples
associated with these samples available for review. The validator uses professional judgment to
estimate (I) all positive detects associated with the two problematic internal standards and rejects
(R) all non-detects associated with the two problematic internal standards. The validator reports
the qualified data on the Data Summary Table. The validator notes the sensitivity loss of the
GC/MS instrument and justifies the decision to qualify sample data in the Data Validation
Memorandum.
Example #2 : (Peak broadening and tailing for volatile gases; PES quantitation low for I volatile gas)
The validator reexamines the Reconstructed Ion Chromatograms from packed column analysis and
notices peak broadening and tailing of the following volatile gases: vinyl chloride, chloromethane,
bromoethane, and chioroethane. The PE sample results were reviewed and found to have an
“Action Low” qualification for vinyl chloride which was the only volatile gas included in the PES.
The validator uses professional judgment to estimate (I) all positive volatile gas detects in all
samples associated with that PES, and to estimate (UI) the quantitation limits for all volatile gas
non-detects in all samples associated with thai PES. The validator reports the qualified data on
the Data Summary Table. The validator notes the GC/MS chromatography problem and justifies
the decision to qualify sample data in the Data Validation Memorandum.
VOA/SV-XVI-6 DRAFT 12/96
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PART Ii-Vo vsv Overall Assessment
XVII. OVERALL EVALUATION OF DATA
A. OBJECTIVE
The objective of the final evaluation of a data package is to identify the “analytical error” and any
“sampling error” associated with the data. The sum of the “analytical error” and the “sampling error”
equals the measurement error”. “Measurement error” will then be used by the end user in conjunction
with sampling vanabilicy (spatial variations in pollutant concentrations) to determine “total error” (total
uncertainty) associated with the data. Ultimately, the end data user will assess data usability in the context
of the pre-deterrnined Data Quality Objectives (DQOs) and resultant “total error” of the data.
B. CRITERIA
The Sampling and Analysis Plan (SAP) or Quality Assurance Project Plan (QAPJP) and DQO Summary
Form should specify the site specific DQOs and acceptable levels of uncertainty or “total error”.
C. EVALUATION/ D. ACTION
C. EVALUATION
D. ACTION
I. Obtain the SAP, QAPJP or DQO Summary
Form to review the DQOs for the sampling
event.
I. Synopsize in the first section of the Data
Validation Memorandum, Overall Evaluation of
Data, in bullet format, the appropriate project
DQOs for the data package.
2. Evaluate the appropriateness of the analytical
method chosen. For example, was the method
capable of achieving quantitation limits
sufficiently low to meet DQOs for risk
assessment? Was the method capable of
successfully analyzing each particular matrix
sampled?
2. If an inappropriate method was chosen for
sample analysis, then the validator should
discuss the method deficiencies and identify
more appropriate methods or modifications for
use in subsequent sampling rounds. The
validacor should include this discussion in the
Overall Evaluation of Data Section of the Data
Validation Memorandum.
3. Evaluate any analytical problems that were
identified,
3. Estimate and describe the “analytical error” that
contributes to the “measurement error’
associated with the data package in the Overall
Evaluation of Data Section of the Data
Validation Memorandum.
a. If “analytical error’ causes the data to be
unusable, then the validator should reject
the data and return it to the laboratory and
deny payment.
b If “analytical error” causes the data to be
of reduced worth to the Re2 ori, then the
Va! idacor should recommend that the
laboratory’s payment be reduced.
VOA/SV-XVII.l DRAFF 12/96
-------
PART II-VOAISV Overall Assessment
C. EVALUATION
D. ACTION
4. Evaluate any sampling issues chat were
identified.
Note: The validator is only responsible for
evaluating those “sampling errors” that
are identified during the routine data
validation process. Other “sampling
errors” may have occurred and they
should be assessed by the end user
prior to data use.
4. Estimate and describe the “sampling error” that
contributes to the “measurement error’
associated with the data package in the Overall
Evaluation of Data Section of the Data
Validation Memorandum. Examples of
“sampling error” for which the validator would
have information include highly contaminated
trip or equipment blanks as well as delayed
sample shipment that caused holding time
violations.
a. If “sampling error” severely impacts
potential data usability, then the validator
should note this in the Data Validation
Memorandum.
b. The end user should review the results of
the sampler’s field notes/trip report to
determine additional “sampling error”
issues with which to fully assess
“measurement error”.
5. Evaluate data quality in terms of “measurement
error” as a combination of “analytical error”
and ‘sampling error’.
5. Discuss data quality in terms of “measurement
error” as the sum of “analytical error” and
“sampling error”. All discussions should be
included in the Overall Evaluation of Data
Section of the Data Validation Memorandum.
6. Identify potential usability issues raised by an
unacceptable degree of “measurement error”.
6. If data usability is potentially compromised by a
high degree of “measurement error”, then the
validator should note this in the Overall
Evaluation of Data section of the Data
Validation Memorandum. If data quality
impacts the use of those data by the end user,
then the validator should detail in the Overall
Evaluation of Data Section of the Data
Validation Memorandum how data use will be
limited and for which end user, i.e., risk
assessor, hvdrogeologist, etc..
7. Sampling variability is not assessed during data
validation, and therefore, should be assessed by
the end user prior to data use.
7. The end user should review the results of the
Data Validation Memorandum in conjunction
with the sampler’s field notes/trip report to
assess the impact of sampling variability issues
on data usabiiitv.
VOA/SV-XVU-2 DRAFF 12/96
-------
APPENDICES
The following appendices were developed to assist the validator in volatile and semivolatile data validation The
appendices include method-specific Quality Control requirements for the following QC parameters: preservation
and technical holding times, GC/MS instrument performance check (tuning), initial and conunumg calibrations,
blanks, surrogate compounds, internal standards, matnx spike/matnx spike duplicates, field duplicates, sensitivity
check. PE samples/accuracy check, uirget compound identification, compound quantication and reported quantication
limits, tentatively identified compounds, semivolatile cleanup, system performance, and overall evaluation of data.
Appendices are included for the following methods:
Appendix A: CLP SOW OLMO3 2/Volatile Organic Analysis
Appendix B: CLP SOW OLMO3.2/Semivolatlle Organic Analysis
Appendix C: CLP SOW OLCO2. 1/Low Concentration Volatile Organic Analysis
Appendix D: CLP SOW OLCO2. 1/Low Concentration Semivolatile Organic Analysis
Additional appendices for other methods may be added as required.
Appendix E: VOA/SV Functional Guidelines Action Tables
-------
Appendix A
CLP SOW OLMO3.2/Volatile Organic Analysis
Method QC criteria, Equations, and Definitions
-------
OLMO3.2 1y0A
APPENDIX A
The following method QC criteria, equations, and definitions apply to data generated according to the USEPA CLP
Statement of Work for Organic Analysis, Multi-Media, Multi-Concentration, OLMO3.2, Exhibit D Yolatiles.
SECTION 1: PRESERVATION & TECHNICAL HOLDING TIME CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-1 -B for preservation and technical holding time data validation criteria.
SECTION II: GCIMS INSTRUMENT PERFORMANCE CHECK (TUNING) CR1TERj 1
Refer to the following method CC/MS instrumern performance (tuning) QC criteria for data validation:
The analysis of the instrument performance (tuning) check solution (50 ng BFB on column) must be performed at
the beginning of each 12-hour period during which samples or standards are analyzed. The tuning check,
bromofluorobenzene (BFB), for volatile analysis must meet the ion abundance criteria given below:
ION ABUNDANCE CRITERIA
50 8.0 - 40.0% of m/z 95
75 30.0 -66.0% ofrn/z 95
95 Base Peak, 100% Relative Abundance
96 5.0 - 9.0% of mlz 95 (see note)
173 Less than 2.0% ofrnlz 174
174 50.0 - 120.0% of rn/z 95
175 4 .0-9 0%ofmass ll4
176 93.0- 101.0% of m/z 174
177 5.0- 9.0% of mlz 176
Note : All ion abundances must be normalized to mlz 95, the nominal base peak, even though the ion
abundance of mlz 174 may be up to 120.0% that of m/z 95.
The mass spectrum of BFB must be acquired in the following manner. Three scans (the peak apex scan and the
scans immediately preceding and following the apex) are acquired and averaged. Background subtraction is required
ai d must be accomplished using a single scan no more than 20 scans pnor to the elution of BFB Part of the BFB
peak must not be background subtracted.
APPENDIX A - 1 DRAFF 12/96
-------
Appendix A OLMO3.2/VOA
SECTION m: [ NITIAL CALIBRATION CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
H, Section VOA/SV-HI-B for initial calibration data validauon criteria and the following method initial calibration
QC Criteria:
The iniual calibration standards must be analyzed upon contract award, whenever corrective action is taken which
may change or affect the ini::al calibration criteria or if the continuing calibration acceptance criteria have not been
met. Initial calibrations must be analyzed after the analysis of a compliant instrument performance check.
The initial calibration standards must include the target compounds listed in the Target Compound List (TCL) in
Section XIII of this Appendix, as well as the irnernal standards and the system monitoring compounds.
All initial calibration standards must be analyzed a x the following concentration levels: 10, 20, 50, 100, 200 ug/L
(unheated for aqueous and medium level soils/heated for low level soils).
Note: The CLP SOW OLMO3.2 minimum response factor method acceptance criterion differs from the
Region I Functional Guidelines initial and continuing calibration mimmwn response factor validation
criterion. If data quality objectives allow for greater variability of data, then an expanded minimum response
factor validation criterion should be documented in the EPA-approved site-specific QAPJP or amendment to
the QAPJP. If response factors less than 0.05 are allowed, then the validator should ensure that there is
sufficient QC data to support the use of low response factors in sample calculations.
RELATIVE RESPONSE FACTOR (RRfl - A measure of the relative mass spectral response of an analvie
compared to its’ internal standard. The RRF is calculated using the following equation:
A C
RRF=— -x---
cx
Where,
A, = Area of primary quantication ion response (EICP) for the compound to be measured
A,, = Area of primary quanmanon ion response (EICP) for the internal standard
C = Concentration of the internal standard
C ,- = Concentration of the compound to be measured
APPENDIX A -2 DRAFT 12/96
-------
Appendi c A OLMO3.2/VOA
AVERAGE (MEAN) RELATIVE RESPONSE FACTOR (RRF)- The average or mean RRF is determined by
the ana sis of five different standard concentrations and is used in calculating compound concentrations in samples.
The RRF is Calculated using the following equation:
= RRF
.L 1.
Where,
RRF = The individual RRFs for various concentration levels
n = The number of RRFs
PERCENT RELATIVE STANDAJW DEVIATION (%RSD) - The % RSD for each compound is a measure of
the linearity of the calibration curve. The % RSD is calculated usmg the following equation:
%RSD = Standard Deviation x 100
Mean
Where,
I n
Standard Deviation X 1
( r,—i )
—
x = Mean
a = total number of values
= each individual value used to calculate the mean
SECTION IV: CONTINUING CALIBRATION CRiTERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAISV -rv-B for continuing calibration data validation criteria and the following method continuing
calibration QC criteria;
The continumg calibration standard must be analyzed once every 12 hours, following the analysis of a compliant
instrument performance check and initial calibration, and prior to the analysis of field samples, QC samples and
blanks.
The continuing calibration standard must include the target compounds listed in the Target Compound List (TCL)
in Section XIII of this Appendix, as well as the internal standards and the system monitoring compounds.
Continuing calibration standards must be analyzed at a concentration level of 50 ug/L (unheated for aqueous and
medium level soils/heated for low level soils).
APPENDIX A - 3 rn rr 12196
-------
Appendix A OLMO3.2/VOA
Note: The CL? SOW OLMO3.2 minimum response factor method acceptance criterion differs from the
Region I Functional Guidelines initial and continuing calibration minimum response factor validation
criterion. If data quality objectives allow for greater variability of data, then an expanded minimum response
factor validation criterion should be documented in the EPA-approved site-specific QAPjP or amendment to
the QA.PjP. If response factors less than 0.05 are allowed, then the validator should ensure that there is
sufficient QC data to support the use of low response factors in sample calculations.
PERCENT DIFFERENCE (%D) - The % D is used to compare the iniual calibration RRF with the continuing
calibration RRF5O. The % Difference indicates both the direction and the magnitude of the comparison, i.e , the
% Difference may be either negative, positive or zero.
RRF -RRF
% Difference = C x 100
RRF
Where,
= Mean relative response factor from the most recent initial calibration meeting technical acceptance
criteria
RRF, = Relative response factor from continuing calibration standard
SECTION V: BLANK CRiTERIA
Refer to Region 1. EPA.NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAJS V-V-B for blank validation criteria and the following method QC criteria:
Method Required Blanks
1. Method Blank - A 5.0 niL aliquoc of reagent water or purified solid matrix approximate in weight or
volume to the samples that is carried through the entire analytical process to determine
the levels of contaminatiOn associated with the processing and analysis of samples. All
blanks are spiked with internal standards and surrogate compounds and blank analysis
must meet internal standard and surrogate compound criteria. The method blank must
be analyzed at least once luring every 12 hour time period on each GCIMS system used
for volatile analysis.
2. Storage Blank - Consists of two 41) ml VOA vials filled with reagent water prepared by the laboratory
when the first samples in an SDG are received. The vials are scored, under the same
conditions, with the field samples. After all of the samples in the SDG are analyzed, a
5.0 niL aliquoc of the storage blank is analyzed to determine whether contamination was
introduced during storage of the samples. All blanks are spiked with internal standards
and surrogate compounds and blank analysis must meet internal standard and surrogate
compound criteria. A minimum of one storage blank must be analyzed per SDG after
all samples for that SDG have been analyzed.
3. Instrument Blank - A 5.0 niL aliquot of reagent water that is carried through the entire analytical procedure
and is analyzed following highly contaminated samples containing target compounds that
exceed the iniual calibration range. The instrument blanks are used to determine if
contamination is introduced by a previous sample and the level associated with the
analytical instrument. All blanks are spiked with internal standards and surrogate
compounds and blank analysis must meet internal standard and surrogate compound
citena. An instrument blank must be analyzed after a sample that exceeds the
calibration range Until an instrument blank meets the technical acceptance criteria, the
system is considered contaminated.
APPENDIX A - 4 DRAFT 12/96
-------
Appendix A OLMO3.2/VOA
SECTION VI: SURROGATE COMPOUND CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAJSV-VI-B for surrogate compound data validation criteria and the following method surrogae
compound QC criteria:
The proper surrogate compounds must be quanu fled using correctly assigned internal standards and the correct
primary quanutation tons
10 uL. of a 25 ug/mL solution of surrogate compounds Toluene -d 3 , 4-Bromofluorobenzene, I ,2-Dichloroethane-d,
are added to 5 cnlJ5 g of sample, standard, QC sample, or blank for a final concentration of 50 ug/L or 50 uglkg.
10 uL of a 25 ug/mL solution of internal standards Chlorobenzene-d 5 and Bromochioromethane are added to 5 m.L/5
g of sample for a final concentration of SO ugJL or 50 ug/kg. 10 uL of a 25 ug/mL solution of surrogate
compounds Toluene-d 5 , 4 -Bromofluorobenzene, I ,2-Dichloroethane-dh are added to 5 niLs of reagent water
containing an aliquot of the methanol medium level soil/sediment extract.
Table Ano A.V1-l - CHARACTERISTIC IONS FOR SURROGATE COMPOUNDS
Surrogate
Characterictic Ions
Internal Standard
Primary Quantitation Ion
=__Secondary_Ion(s)
Toluene-d
98
70, 100
Chlorobenzene-d
4-Bromofluorobenzene
95
174, 176
Chlorobenzene-d 4
I ,2-Dicb1oroethane-d
65
102
Bromochloromethane
—
The surrogate % recovery is calculated using the following equation:
Surrogate Percent Recovery = x 100%
Q = Quanuiy of surrogate determined by analysts
Q = Quantity of surrogate added to samplelblank
Table Aoo A.Vl-2 - SURROGATE RECOVERY LIMITS
Method QC Criteria
Surrogate
Percent Recoierv Percent Recovery
(Water) (Soil/Sediment)
Toluene-d
88-110
84-138
Bromofluorobeazene
86-115
59-113
l.2-D ichloroetharte-d
76-114
70-12 1
APPENDIX A - 5 DRAFI’ 12196
-------
Appendix A OLMO3.2/VOA
If one or more sample surrogate recovery does not meet the acceptance criteria, the sample must be reanalyzed to
determine if the sample matrix is interfering with the surrogate recoveries. Reanalysis is not required if the sample
is a QC sample and both the matrix spike and matrix spike duplicate surrogate recoveries failed to meet the
acceptance criteria. If the sample was remalyzed and the surrogate recoverj’(ies) was acceptable in the reanalysis,
then only the reanalysis should have been submitted. However, if the reanalysis also recovers the surrogate(s)
outside of the ac:eptance limits, then both analyses should have been submitted.
SECTION V I I: INTERNAL STANDARDS CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-Vll-B for internal standard data validation criteria and the following method internal standard
QC criteria:
The correct internal standard must be used for sample compound quantitacion and the correct internal standard
prirnary;quantitation ion must be used for quantitation.
10 uL of a 25 ug/mL solution of internal standards Bromochloromethane, 1 ,4-Difluorobenzene, and Chlorobenzene-
d 5 are added to 5 rriLJ5 g of sample, standard, QC sample, or blank for a final concentration of 50 ug/L or 50
ug/kg.
Table App.A.Vll-l - VOLATILE INTERNAL STANDARDS WITH CORRESPONDING TARGET
COMPOUNDS AND SURROGATES ASSIGNED FOR GUANTITATION
IS IS IS
Bromochioromethane I , 4—Difluorobenzene Chlorobenzene—d S
Chloromethane 1,1, 1—Trichloroethane 2— 1-lexanor ie
Bromomethane Carbon Tecrachlonde 4—Methyl—2—Pentanone
Vinyl Chloride Bromodichloromethane Tetrachioroethene
Chloroethane 1 ,2—Dichloropropane 1,1 ,2,2—Tetrachloroethane
Methylene Chloride trans—1,3—Dichloropropene Toluene
Acetone Tnch loroethene Ch lorobenzene
Carbon Disulfide Dibromochioromethane Ethylbenzene
1, 1—Dicliforoethene 1,1 ,2—Trichloroethane Styrene
1, 1—Dichloroethane Benzene Xylene (total)
I ,2—Dichloroethene(tot.) cis—l ,3—Dichloropropene 4-Bromofluorobenzene (surr)
Chloroform Bromoform Toluene-d8 (surr)
1 ,2—Dichloroethane
2-Butanone
1 ,2-Dichloroethane-d4
(surr)
APPENDIX A -6 DRAFT 12/96
-------
Appendix A OLMO3.2/VOA
Table App.A.VH-2 - CHARACTERISTIC IONS FOR INTERNAL STANDARDS FOR VOLATILE
COMPOUNDS
Internal Standard
Characteristic Ions
Primary
Quantitatfon
Ion
Secondary Ion(s)
Bromochloromethane
128
49, 130, 51
1.4-Difluorobenzene
114
63, 88
Chlorobenzer ie-dS
117
82, 119
Internal standard area counts for each of the internal standards must be within the inclusive range of -50.0% and
+ 100.0% of the response of internal standards in the associated daily conunuing calibration standard.
The retention time of the internal standard must not vary by more than ± 30 seconds from the retention time of
the associated daily continuing calibration standard.
If one or more internal standard area count andlor retention time does not meet the acceptance criteria, then the
sample must be reanalyzed to determine if the sample matrix is interfering with the surrogate recoveries. Reanalysis
is not required if the sample is a QC sample and both the matrix spike and matrix spike duplicate failed to meet the
iixernal s:andard acceptance criteria. If the sample was reanalyzed and the internal standard area counts andlor
retention times were acceptable in the reanalysis, then only the reanalysis should have been submitted. However,
if the reanalysis also recovers the internal standard outside of the area count and/or retention nine acceptance
criteria, then both analyses should have been submitted.
SECTION VIII: MATRIX SPIKEIMATR [ X SPIKE DUPLICATE CRITERIA
Refer to Re on 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Parr
H, Section VOAJSV.Vffl -B for MS/MSD data validation criteria arid the following method MSIMSD QC cruet-ia:
The MS/MSD spike compounds listed below are spiked at 10 uL in a 25 ug/mL solution into the 5 rnL or 5 g
sample for a final concentration of 50 ug/L or 50 ugfkg.
A matrix spike and matrix spike duplicate must be performed for each group of samples of a similar matrix for each
SDG, or each matrix within an SDG or each group of samples of a similar concentration level (soils only) whichever
is most frequent. The following advisory matrix spike compound recoveries and RPDs are listed below:
APPENIMX A -7 DRAFT 12/96
-------
Appendix A OLMO3.2/VOA
Table App.A.Vffl-1 - MATRIX SPIKE RECOVERY AND RELATIVE PERCENT DIFFERENCE LIMITS
Compound
Method QC Criteria
Water
Soil/Sediment
% Recovery
RPD**
% Recovery
RPD
1,1-Dichloroethene
61-145
14
59-172
22
Trichloroethene
71-120
14
62-137
24
Benzene
76-127
11
66-142
21
Toluene
76-125
13
59-139
21
Ch lorobenzene
75-130
13
60-133
21
*The MSIMSD % recovery is calculated using the following equation:
Matrix Spike Recovery = SSR-SR x ioo
Where,
SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added
**The MS/MSD relative percent difference (RPD) is calculated using the following equation:
Relative Percent Difference = I M S MSDRI x 100
Where.
MSR = Matrix Spike Recovery
MSDR = Matrix Spike Duplicate Recovery
Note: The vertical bars in the formula indicate the absolute value of the difference, hence RPD is always positive.
SECTION IX: FIELD DUPLICATE CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
Ti, Section VOA/SV-IX-B for field duplicate data validation cruena.
APPENDIX A - S DRAFT’ 12/96
-------
Appendix A OLMO3.2/VOA
SECTION X: SENSITIVITY CHECK CRITERIA
Refer to Region L EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-X-B for sensitivity check data validation cruena.
SECTION X I: FE SAJ 4PLES - ACCURACY CHECK CRiTERIA
Refer to Re2ion 1. EPA-NE Data Validation Functional Guidelines for Evaluatinn Environmental Analyses , Part
[ I. Section VOA/SV-XI -B for accuracy check data validation cnteria.
SECTION XII: TARGET COMPOUND mEN1u T1CATION CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmentaj Analyses , Part
II. Section VOAJSV-XlI -B for target compound idenuficauon data validation criteria.
APPENDIX A - 9 DRAFF 12/96
-------
Appendix A
OLMO3 . 2/VOA
SECTION XIII: COMPOUNI) QUANTITATION A I) REPORTED QUANTITATION LIMITS CRITERIA
Refer to Region I. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part II, Section VOA/SV-XlII-B for compound
quaniitation and reported qiuanhitalion limit data validation criteria and the following method quantitation QC criteria:
Volatile target compounds nuist be quanticated using the internal standard method with the internal standards assigned in Appendix A, Section VII. The daily
RRF5O imist be used for sample quantutation. The sample target compounds must be quantified using the following primary quanctiatuon ions and must be
reported in the CRQLs listed below.
Table App A XIlI-l - TARGET COMPOUND LIST (TCL). PRIMARY QUANTITATION AND SECONDARY IONS. AND CONTRACT REOIJIREI)
O(JANTITATION LIMITS (CROI FOR OLMO3.I SOW VOLATILE ORGANIC COMPOUNDS
Quantitation Limits
Volatiles
CAS Number
74—87—3
74—83—9
75—01—4
75—00—3
75—09—2
6 7—64—1
75—15—0
75—35—4
75—34—3
540—59—0
67—66—3
107—06—2
78—93—3
71—55—6
56—23—5
7 5—2 7—4
78—87—5
I 0061—01—5
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
10 10 1200
52
96
64
66
49,51,86
58
78
61,98
65, 83, 85, 98. 100
61,99
85
64, 100, 98
57
99, 117, 119
119, 121
85
65, 114
Water
ug/L
Low
Soil
ug/Kg
Med.
Soil
ug/Kg
On
Column
(ng)
Characteristic Ions
Primary Secondary
Chi orornethane
Brornomethane
Vinyl Chloride
C l i 10 roe II ia ii e
Mechylene Chloride
Ace tone
Carbon Disiilfide
1, 1—Dichioroethene
I , 1—Dichioroethane
1, 2—Dichioroethene (total)
Chloroform
1, 2—Dichioroethane
2—Butanone
1, 1, 1—Trichloroethane
Carbon Tetrachioride
Brornodichloromethane
1, 2—Dichioropropane
cis—1, 3—Dichioropropene
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
50
94
62
64
84
43
76
96
63
96
83
62
43*
97
117
83
63
75
* - m/z 43 is used for quantitation of 2-Butanone, but mhz 72 must be present for positive identification.
APPENDIX A - 10
DRAFT 12/96
-------
Appciulix A
OLMO3.2/VOA
T L! ,’p.A XIII-, - T RcH T COMPOIJNI) LIST (TCL). PRIMARY QIJANTITATION AND SECONDARY IONS. AND CONTRACT REOUIRED
QIJANTITATION LIMITS (CROLs) FOR OLMO3.I SOW VOLATILE ORGANIC COMPOUNDS (CONT )
Quantitation Limits
Volatiles CAS l’ umber
95, 97, 132
208, 206
83,85,99,132,134
77
171, 175,250,252, 254 • 256
58, 100
58, 57, 100
129, 131,166
92
85,131,113,166
114
91
78, 103
91
Low
Med.
On
Characteristic
Ions
Water
Soil
Soil
Column
Primary
Secondary
ugfL
ug/Kg
ug/Kg
(ng)
Trichloroethene
79—01—6
10
]O
1200
(50)
130
Dibromochioromethane
124—48—1
10
10
1200
(50)
129
1,1,2—Trichioroethane
79—00—5
10
10
1200
(50)
97
Ben-zene
71—43—2
10
10
1200
(50)
78
trans—1,3—DichloroprOpefle
10061—02—6
10
10
1200
(50)
75
Bromoform
75—25—2
10
10
1200
(50)
173
4—Methyl—2--pentanone
108—10—1
10
10
1200
(50)
43
2—Ilexanone
591—78—6
10
10
1200
(50)
43
Tetrachioroethefle
127—18—4
10
10
1200
(50)
164
Toluene
108—88—3
10
10
1200
(50)
91
1,1 ,2,2—Tetrachioroethan
79—34—5
10
10
1200
(50)
83
Chlorobenzene
108—90—7
10
10
1200
(50)
112
Ethy lbenzene
100-41—4
10
10
1200
(50)
106
Styrerie
100—42—5
10
10
1200
(SO)
104
Xylenes (Total)
1330—20—7
10
10
1200
(50)
106
APPENDIX A - II
DRAFT 12/96
-------
Appendix A OLMO3.2/VOA
SAMPLE CONCENTRATION - The amount of analyte present in a sample is calculated using the RRF5O of the
conunwng calibration standard in the following equations.
Sample conceturanon for water:
— ( Ar) (IS) (.Df )
ug/L - (Arn) (RRF) (V 0 )
Sample concentration for low level soil/sediment:
(Ar) (IS)
ug/Kg (Dry weight basis) = (A 5 ) (RRF) (W 3 ) (D)
Sample concenu-atiori for medium level soil/sediment:
( Ar) (IS) (Vs) (1000) (Dt )
ug/Kg (Dry weight basis) = (A ) (RRF) (Va) (We) (D)
Where,
A 0 = Area of the primary quantitation ion response (EICP) for the compound to be measured
A = Area of the primary quantitanon ion response (EICP) for the specific internal standard
IS = Amount of internal standard added in nanograms (ng)
RRF = Relative Response Factor from the (Ambient temperature purge for water and medium level
soil/sediment and heated purge for low level soillsediment) calibration standard
V 0 = Volume of water purged in milliliters (niL)
Df = Dilution Factor - The dilution factor for analysis of water samples for volanles by this method is
defined as the ratio of the number of milliliters (niL) of water purged (i.e., V 0 above) to the
number of niL of the original water sample used for purging. If no dilution is performed , Df= 1
The dilution factor for analysis of soil/sediment samples for volatiles by the medium level method
is defined as follows:
uL most conc extract used to make dilution + uL clean solvent
uL most conc. extract used to make dilution
W = We ghc of the sample added to the purge tube in grams (g)
D = 100 - % Moisture
100
V 1 = Total volume of the methanol extract in milliliters (niL)
V 2 = Volume of aliquot of the methanol extract in rnicrolicers (uL) added to reagent water for purging
W 2 = Weight of soil/sediment extracted in grams (g)
APPENDIX A- 12 DRAFt 12/96
-------
Appendix A OLMO3.2/yOA
CRQL CALCULATIONS
Water:
( V )
Adjusted CRQL = Contract CRQL x x (Df)
0’
Where,
V 0 and Df are defined in the sample concencracton equation above
V 0 = Contract sample volume (5 mL)
Soil/Sediment-Low:
Adjusted CRQL = Contract CRQL x (( XL
Where,
W 1 and D are defined in the sample concentration equation above
W 0 = Contract sample weight (5 g)
SocI/SedjmenL Med:
Adjusted RQL = Contract RQL x (h’) (tI ) (vi) (Di )
(W 3 ) (Va) (Va) (D)
Where,
V 1 . Df, WI, Va, and D are defined in the sample concentration equation above
W 1 = Contract sample weight (4 g)
V , = Contract soil aliquot volume from soil methanol extract (100 uL)
V , = Contract soil methanol extract volume (10,000 uL)
APPENDEX A - 13 DRAFT 12196
-------
Appendix A OLMO3.2/VOA
SECTION XIV: TENTATIVELY H)ENTIFIED COMPOUND CRITERIA
Refer (0 Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA1SV-XIV-B for tentatively identified compound (TIC) data validation criteria and the following
method TIC QC criteria:
The validacor is required to report up to 30 TICs in the Data Validation Memorandum.
TENTATIVELY IDENTWIED COr’v [ POUN1) CONCENTRATION - The estimated concentration for non-target
compounds tentatively identified shall be determined by the internal standard method using the following equations:
Sample concentration for water:
IL - ( Ar) (IS) (Df )
ug — (A 5 ) (RRF) (V 0 )
Sample concentration for low level soil/sediment:
(AX) (IS)
ug/Kg = (A 15 ) (RRF) (W 5 ) (D)
Sample concentration for medium level soil/sediment:
( As) (IS) (Vs) (1000) (Dif )
ug/Kg = (A 5 ) (RRF) (Va) (We) (D)
Where,
= Area of the primary quaiititation ion response (EICP) for the non-target compound to be measured
A = Area of the primary quancitation ion response (EICP) for the specific internal standard
IS = Amount of internal standard added in nanograms (ng)
RRF = Reiative Response Factor assumed to be I
V 0 = Volume of water purged in milliliters (mL)
Df = Dilution Factor - The dilution factor for analysis of water samples for volanles by this method is
defined as the ratio of the number of milliliters (mL) of water purged (i.e., V 0 above) to the
number of mL of the original water sample used for purging. If no dilution is performed, Df= 1
The dilution factor for analysis of soil/sediment samples for volatiles by the medium level method
is defined as follows
uL most conc. extract used to make dilution + uL clean solvent
uL most conc extract used to make dilution
W 3 = Weight of sample added to the purge tube in grams (g)
D = 100 - % Moisture
100
= Total volume of the methanol extract in milliliters (mL)
V 3 = Volume of aliauoc of the methanol extract in microliters (uL added to reagent water for purging
W 0 = Weight of soil/sediment extracted in grams (g)
APPENDIX A - 14 DRAFT 12/96
-------
Appendix A OLMO3.2/VOA
SECTION XV: SEMIVOLATILE CLEANUP CRITERIA
Nat applicable to volatile analysis.
SECTION XVI: SYSTEM PERFORMANCE CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-XVI-B for system performance data validation cnceria.
SECTION XVH: OVERALL ASSESSMENT CRITERIA
Refer to Region 1. EPA-NE Dac Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-XVII-B for overall assessment data validation criteria.
APPENDIX A - 15 DRAFF 12/96
-------
Appendix B
CLP SOW OLMO3.2/Semivolatile Organic Analysis
Method QC criteria, Equations, and Definitions
-------
OLMO3 .2 ISV
APPENDIX B
The following method QC criteria, equations. and defin -itions apply to data generated according to the USEPA CLP
Statement of Work for Organic Analysis, Multi-Media, Multi-Concentration, OLMO3.2, Exhibit D
Semivolatiles.
SECTION I: PRESERVATION & TECHNICAL HOLDING TIME CRITERIA
Refer to Renion I, EPA-NE Data Validation Functional Guidelines for Evaluating Environnierual Analyses , Part
II, Section VOA/SV-I-B for preservation and technical holding time data validation criteria.
SECTION II: GCIMS INSTRUMENT PERFORMANCE CHECK (FUNING) CRITERIA
Refer to the following method GCIMS instrument performance (tuning) QC criteria for data validation:
The analysis of the instrument performance (tuning) check solution (50 ng DFTPP on column) must be performed
at the beginning of each 12-hour period during which samples or standards are analyzed. The tuning check,
decafluorotriphenyiphosphine (DFTPP), for semivolatile analysis must meet the ion abundance cnteria given below:
rnL 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 (see note)
199 5.0- 9.0% ofmlz 198
275 10.0 - 30.0% of m/z 198
365 Greater than 0.75% of rn/i 198
441 Present, but less than mlz 443
442 40.0- 110.0% of mlz 198
443 15.0 - 24.0% of mlz 442
NoteS All ion abundances must be normalized to m/z 198, the nominal base peak, even though the ion
abundances of m/z 442 may be up to 110% that of m/z 198.
The mass spectrum of DFT?P must be acquired in the following manner. Three scans (the peak apex scan and the
scans immediately preceding and following the apex) are acquired and averaged. Background subtraction is
required, anc nust be accompiished using a single scan no more than 20 scans prior to the elunon of DFTPP Part
of the DFTPP peak must not be background subtracted.
APPENDL B . I DRAFF 12/96
-------
Appendix B OLM O3.2/SV
SECTION m: INITIAL CALIBRA11ON CRITERIA
Refer o Region I, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAJSV-IH-B for initial calibration data validation criteria and the following method initial calibrauon
QC criteria:
The initial calibration standards must be analyzed upon contract award, whenever corrective action is taken which
may change or affect the initial calibration criteria or if the conunuing acceptance criteria have not been met. Initial
calibrations must be analyzed after the analysis of a compliant instrument performance check.
The initial calibration standards must include the target compounds listed in the Target Compound List (TCL) in
Section XI [ I of this Appendix, as well as the internal standards and the system monitoring compounds.
2 uL of the initial calibration standard must be injected and all initial calibration compounds and system monitoring
compounds must be analyzed at the following concentration levels; 10, 20, 40, 60, 80 ngluL. However, the
following eight compounds only require a four point calibration and are injected at conceturacion levels of 50, 80,
120, and 160 ngfuL: 2,4-dinirrophenol, 2,4,5-trichlorophenol, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 4-
nicrophenol, 4,6-dinitro-2-methytphenol, and penrachlorophenol since detection at less than 50 ng per injection is
difficult.
Note: The CLP SOW OLMO3.2 minimum response factor method acceptance criterion differs from the
Region I Functional Guidelines initial and continuing calibration minimum response factor validation
criterion. If data quality objectives allow for greater variability of data, then an e .’ panded minimum response
factor validation criterion should be documented in the EPA-approved site-specific QAPJP or amendment to
the QAPJP. If response factors less than 0.05 are allowed, then the validator should ensure that there is
sufficient QC data to support the use of low response factors in sample calculations.
RELATIVE RESPONSE FACTOR (RRF) - A measure of the relative mass spectral response of an analyte
compared to its’ internal standard. The RRF is calculated using the following equation:
A C.
RRF = —f- x —
A 15 C
Where,
= Area of primary quantitatlon ion response (EICP) for the compound to be measured
A 5 = Area of primary quantitauon ion response (EICP) for the internal standard
C,, = Amount of the internal standard injected (ng)
C, = Amount of the compound to be measured injected (ng)
APPENDIX B - 2 DRAFT 12/96
-------
Appendix B OLMO3.2/SV
AVERAGE (MEAN) RELATIVE RESPONSE FACTOR (RRF) - The average or mean RRF is determined by
the analysis of five different standard concentrations and is used in calculating a compound concentration in samples.
The RRF is calculated using the following equation:
— RRF
RRF=>
n
Where,
RRF = The individual RRFs for various concentration levels
n = The number of RRFs
PERCENT R.ELAT1VE STANDARD DEVIATION (%RSD) - The % RSD for each compound is a measure of
the linearity of the calibration curve. The % RSD is calculated using the following equation: -
%RSD = Standard Deviation
Mean
Where,
H ( x.- ) 2
Standard Deviation = (
x = Mean
a = total number of values
x, = each individual value used to calculate the mean
SECTION 1Y: CONTINUING CALIBRATION CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
I I, Section VOAJSV.IV -B for continuing calibration data validation criteria and the following ±ethod continuing
calibration QC criteria:
The continuing calibration standard must be analyzed once every 12 hours, foilowing the analysis of a compliant
instrument performance check and initial calibration, and prior to the analysis of field samples, QC samples and
blanks
The continuing calibration standard must include the target compounds listed in the Target Compound List (TCL)
in Section XIII of this Appendix, as well as the internal standards and the system monitonng compounds.
Continuing calibrations must be analyzed at a concentration level of 50 ng/2 uL except for the following eight
compounds which are analyzed at a concentration level of 100 ngI2 uL. 2.4-dinitrophenol, 2,4,5-trichiorophenol,
2 -nitroaniljne. 3-nitroamljne, 4-nitroamline, 4-nitrophenol, 4 ,6-dinitro-2-methylphenol andpenachlorophenol since
detection at less than 50 ng per injection is difficult.
4PPENIMX B -3 DRAFT 12/96
-------
Appendix B OLMO3.2/SV
Note: The CLP SOW OLMO3.2 minimum response factor method acceptance criterion differs from the
Region I Functional Guidelines initial and continuing calibration minimum response factor validation
criterion. If data quality objectives allow for greater variability of data, then an expanded minimum response
factor validation criterion should be documented in the EPA-approved site-specific QAPJP or amendment to
the QAPjP. if response factors less than 0.05 are allowed, then the validator should ensure that there is
sufficient QC data to support the use of low response factors in sample calculations.
PERCENT DIFFERENCE (%D) - The % D is used tO compare the ini(ial calibration RRF with the continuing
calibration RRFSO. The % Difference indicates both the direction and the magniwde of the comparison, 1 e, the
% Difference may be either negative, positive or zero.
RRF - RRF
% Difference = c 100
RRF 1
Where,
RRF = Mean relative response factor from the most recent initial calibration meeting technical acceptance
criteria
RRFC = Relative response factor from continuing calibration standard
SECTION V: BLANK CRiTERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
I I, Section VOA/SV-V.B for blank data validation criteria and the following method QC criteria:
Method Required Blank
Method Blank. A volume of reagent water or purified solid matrix approximate in weight or volume to the
samples which is carried through the entire analytical process to determine the levels of
contamination associated with the processing and analysis of the samples. All blanks are spiked
with internal standards and surrogate compounds and blank analysis must meet internal standard
and surrogate compound criteria. Method blank extraction and analysis must be performed once
per each SDG, or each 20 samples in an SDG, or whenever samples are extracted by the same
procedure, whichever is most frequent, and analyzed on each GC/MS system used w analyze
associated samples.
SECTION ‘11: SURROGATE COMPOUND CRITERIA
Refer to Reeion I, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-VI-B for surrogate compound data validation criteria and the following method surrogate
compound QC criteria:
The proper surrogate compounds must be quantified using correctly assigned internal standards and the correct
primary quanutacion ions.
APPENDIX B . 4 DRAFI’ 12/96
-------
Appendix B OLMO3.2/SV
Surrogate compounds Nitrobenzene4, 2-Fluorobiphenyl, Terphenyl-d 14 , and 1.2-Dichlorobenzene-d 4 (advisory) are
added to all samples, standards, QC samples, and blanks at a concentration of 100 ug/mL and surrogate compounds
Phenol-d , 2-FluorophenoL 2,4,6-Tribromophenol. and 2-Chiorophenoki, (advisory) are added to all samples,
standards, QC samples, and blanks at a concentration of 150 ug/rnL.
Table App.B.V1-1 - CHARACTERISTIC IONS FOR SURROGATE COMPOUNDS
Surrogate
Characteristic Ions
Internal Standard
Primary
Quantitation Ion
Secondary Ion(s)
Nitrobenzene-d,
82
128, 54
Naphthalene-4 3
2-Fluorobiphenyl
172
171
Acenaphthene -d. 0
Terphenyl-d 4
244
-
122, 212
Chrysene-d 1 .
Phenol4
99
—
42, 71
1.4-Dichlorccenzene-d ,
2-Fluorophenol
112
64
1,4-Dichlorobenzene4
2,4,6-Tribromophenol
330
332, 141
Phenanthrene -d, 0
2-Ch lorophenol-d 4
(Recovery limits advisory)
1 ,2-Dichlorobenzene-d 4
(Recovery limits advisory)
132
152
—
68, 134
115, 150
1 , -Dichlorobenzene-d ,
1 ,4-Dichlorobenzene-d ,
The % surrogate recovery is calculated using the following equation:
Surrogate Percent Recovery = x 100%
= Quantity of surrogate determined by analysis
= Quantity of surrogate added to sample/blank
APPENDDC B - 5 DRAFF 12196
-------
Appendix B OLMO3.2/SV
Table App.B VI-2 - SURROGATE RECOVERY LIMITS
Surrogate
Method_QC_Criteria
Percent Recovery
(Water)
Percent Recovery
(Soil/Sediment)
Nttrobenzene4 (B/N)
35-114
23-120
2-Fluorobiphenyl (B/N)
43-116
30-115
Terphenyl-d 14 (B/N)
33-141
18-137
Phenol-d (Acid)
10-110
24-1 13
2-Fluorophenol (Acid)
21-110
25-121
2,4,6-Tribromophenol (Acid)
10-123
19-122
2-Chlorophenol-d 4 (Acid)
33-110
(advisory)
20-130
(advisory)
1 ,2-Dichlorobenzene-d 4 (BIN)
16-110
(advisory)
20-130
(advisory)
If two or more acid or base neutral surrogate compounds fail to meet their recovery acceptance criteria, the
laboratory should check calculations, sample preparation logs, the surrogate compound spiking solutions, and the
instrument operation. If sample surrogate recoveries do not meet the acceptance criteria, as a result of the above
mentioned problems or other unknown problems, the sample should be re-extracted and reanalyzed to determine
if the sample matrix is interfering with the surrogate recoveries. Re-extraction and reanalysis are not required if
the sample is a QC sample and both the matrix spike and matrix spike duplicate surrogate recoveries failed to meet
the acceptance criteria. Reanalysis is required if the failed surrogate recoveries are the result of instrument
malfunction. If the sample was re-extracted and reanalyzed and the surrogate recoveries were acceptable in the
reanalysis, then only the reanalysis should have been submitted. However, if the re-extracted/reanalyzed sample
also recovers the surrogates outside of the acceptance limits, then both analyses should have been submitted.
APPENDIX B -6 DRAFr 12/96
-------
Appci I orr Io3.2I
SECTION \‘II: INTERNAL STANDARDS CRITERIA
Refcr to gion I. PPA-NE Data Validation_Functional Guidelines for Evaluating Environmental AnaI , Part I I, Section VOA/SV-VJl-fl for internal standard
data valulalu)!I crilerij and the following method internal standard QC criteria:
The correct internal standard and the correct internal standard primary quantitalion ion must be used for sample compound quanlitation.
The internal standard compounds listed below are added into all samples, standards, QC samples, and blanks at a concentraimon of 40 ng/2 uL.
Table App B VU-I - SEMIVOLATILE INTERNAL STANDARDS WITh CORRESPONDING TARGET COMPOUNDS AND SURROGATES
ASSIGNED FOR QUANTITATION
IS IS IS IS IS IS
I ,4 — Dichlorobenzene—d4 Naphthaleiic—d8 Acenaphthene—d 10 Phenanflirene-.—d 10 Chrysene—d 12 Perylene—1 12
Phenol Nitrohenzene I lexachiorocyclo— 4 ,6—Dinitro——2— Pyrene Di—n---octy l-
I)is(2—Ch loroclhyl) Isophorone pentadiene methylphenol Bmitylbenzyl- phihalate
ether 2—Nitrophenol 2,4,6—Trichioro— N—niiroso-di— phthalate Benzo(b)fluor—
2—C ltlorophenol 2,4—Dimethyl— phenol phenylamine 3 ,3’—Dichloro— anthene
I ,3—Dichlorohcniciie phenol 2,4,5—Trich loro— 4—Bromophenyl benzidine Benzo(k)fluior—
I ,4—Dich lorobenzciic hus(2—Ch loro-—-- phenol plienoletlier Benzo(a)— anthene
I ,2—D lchlorohenLene ethoxy)meihanc 2—Chloronaphihalene 1-lexachloro ---— anihracene Benzo(a)pyrene
2—Mei hiy lphenol 2,i —Dichloro— 2—Nitroanil me benzene bis(2—ethyl- Indeno(l ,2,3—cd)-
2,2’ -oxybis- phenol Dimeihylphihalate Pentachloro— hexyl)phtha late pyrene
(I -Chioropropane) I ,2 .4—Trichloro— Acenaplim Itylene phenol Chrysene Dibenz(a,h)-
‘l—t IeIhyIphienoI bcnzcne 3—Nitroaniline Phenanthrene Terphenyl—d 14 anthracene
N—Nitrosn—Di— n— Naphthalcne Acenaphthene Carbazole (snrr) I3enzo(g,h,i)-
propylamiiie 4—Chloroanil me 2,4—Dinitrophenol Anthracene perylene
I lcxach loroethane I kxachloro— 4—Nitrophenol Di—n—butyl-
2— 11 mini ophc noI himiad mene I)ihenzofiiran ph ihalate
(simm i) 4—Chi loro—3— 2,4—Dinitrotohimene Fluoranthene
F hienol—d S (surr) meihyiphenol 2,6—Dinitrotolmiene 2,4 ,6-Trmbromno-
2—Cliloro 1 ,licnol-d4 2—Meilmylnaphi— Dicihylphihalate phenol (surr)
(siui I ) t Ii .i lene ‘I—Cl m loroplienyl
I ,2- I)tchilorobcnzcnc-d-l Nitrobenzene—d5 phenyletlier
(siirr) (siirr) Pluorene
4—Nitroaniline
2—Pluorobiphenyl
(surr)
(s,mrr) = surrogate conipolmn(l
APPENDIX II -‘ DRAVF 12/96
-------
Appendix B OLMO3.2/SV
Table App B Vll-2 - CHARACTERISTIC IONS FOR INTERNAL STANDARDS FOR SEMIVOLATILE
COMPOUNDS
Internal Standard
Characteristic Ions
Primary Quantitation Ion
J Secondary Ion
1,4-Dichlorobenzene-d 1
152
115
Naphthalene-d
136
68
Acenaphthene-d 10
164
162, 160
Phenanthrene-d 10
188
94, 80
Chrysene-d 12
240
120, 236
Perylene-d 1 ,
264
260, 265
Internal standard area counts for each of the internal standards must be within the inclusive range of -50 0% and
+ 100.0% of the response of internal standards in the associated daily continuing calibration standard.
The retention time of the internal standard must not vary by more than ± 30 seconds from the retenuon time of
the associated daily continuing calibration standard
If one or more internal standard area count and/or retention time does not meet the acceptance criteria, then the
samp’e must be reanalyzed to determine if the sample matrix is interfering with the surrogate recoveries. Reanalysis
is not required if the sample is a QC sample and both the matrix spike and matrix spike duplicate failed w meet the
internal standard acceptance crneria. If the sample was reanalyzed and the internal standard area counts and/or
retention times were acceptable in the reanalysis, then only the reanalysis should have been submitted. However,
if the reanalysis also recovers the internal standard outside of the area count and)or retention time acceptance
criteria, then both analyses should have been submitted.
APPENDIX B - 8 DRAFT 12/96
-------
Appendix B
OLMO3 .2/S V
SECTION VIII: MATRIX SPIKE! MATRIX SPIKE DUPLICATE CRITERIA
Refer to Region I. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-VIII-B for MSIMSD data validation criteria and the following method MS/MSD QC criteria:
A matrix spike and matrix spike duplicate must be extracted and analyzed for each group of samples of a similar
matrix for each SDG, or each matrix within an SDG or each group of samples of a similar concerurauon level.
The following advisory matrix spike compound recoveries and RPDs are listed below:
MS/MSD base neutral compounds l,4-dichlorobenzene, N-riuroso-di-ri-propylarmne, l,2,4-trichlorobenzene,
acenaphthene, 2,4-dinitrotoluene, and pyrene are spiked at a concentration of 100 uglmL and MSIMSD acid
compounds phenol, 2-clilorophenol, 4-chloro-3-methylpheriol, 4-nitrophenol, and pentachiorophenol are spiked at
a concentration of 150 ug/mL.
Table Ann V1H-1 - MATRIX SP1K1 D AVERY AND RELAT1V P D MT DFFFPRF ’JrP LIMITS
• •,_,_._,. ——
APPENDIX B - 9
DRAFT 12/96
-------
Appendix B OLMO3.2/SV
*The MS/MSD % recovery is calculated using the following equation:
Matrix Spike Recovery = SS SR x 100
Where,
SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added
•*The MS/MSD relative percent difference (RPD) is calculated using the followmg equation:
Relative Percent Difference = 1 I M S; MSDRJ X 100
Where,
MSR = Matrix Spike Recovery
MSDR = Matnx Spike Duplicate Recovery
Note: The vertical bars in the formula indicate the absolute value of the difference, hence the RPD is always
positive.
SECTION I:X: FIELD DUPLICATE CRiTERIA
Refer to Reeion 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II. Section YOAJSV-LX-B for field duplicate data validation criteria.
SECTION X: SENSITIViTY CHECK CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-X-B for sensitivity check data validation criteria.
SECTION Xi: PE SAMPLES - ACCURACY CHECK CRITERIA
Refer to Re ior. I EPA-NE Data Validation Functional Guideiines for Evaluaun Environmental Analyses , Part
II, Section VOA/SV-X1-B for accuracy check data validation criteria
SECTION XII: T ..U GET COMPOUND IDENTIFICATION CRITERIA
Refer to Region 1 EPA- 4E Data Validation Functional Guidelines for Evaluaun2 Environmental Analyses , Part
II. Section VOA,SV-XII-B for target compound identification data validation criteria.
APPENDIX B - 10 DRAFF 12/96
-------
A PPCI
OLM O3.2/S
SECTION XIII: COMPOUND QI TANTITATION AND REPORTED QUANTITATION LIMITS CRITERIA
Refer to Region I. FF!a Y 1idaiion Functional Guidelines for Evaluating Environm lal Part II, Section VOA/SV-XIII-B for compound
qiianhiiai lon anti reported qiiaflhiLailofl limit data validation criteria and the following method quantitation QC criteria:
Semivolatule target compounds must he qtiantitated using the internal standard method with the internal standards assigned in Appendix B, Section VII. The
daily RRF5O must he used for sample quantutation. The sample target compounds must be quantitied using the following primary quanulacion ions and must
be reported to the CRQLs listed below:
Table A j XIII-l - TARGET COMPOUND LIST (TCL). CONTRACT REQUIRED QUANTITATION LIMITS (CROLs), PRIMARY
OIJANTITATION IONS. AND SECONDARY IONS FOR OLMO3. I SOW SEMIVOLATILE ORGANIC COMPOUNDS
Quantitation Limits
Low Med
Water Soil Soil
ug/L ug/Kg ug/Kg
Characteristic Ions
Primary Secondary
Phenol
bis (2—Chioroethyl) ether
2—Chi orophenol
1, 3—Dichlorobenzene
1, 4—Dichlorobenzene
1 2—Dichlorobenzene
2—Methyiphenol
2 • 2 -oxybis
(1-Chioropropane) U
4—Methyl phenol
N—tjitroso—di—n-
propylamine
Ilexachioroethane
Ni trobenzene
I sopho rone
2—Nitrophenol
2, 4—1)1 methyl phenol
bis (2—Chioroethoxy)
methane
2, 4—DicilloropheflOl
1, 2, 4—Trichlorobenzene
Naphthalene
4—Chi oroaniline
ilexachi orobutadi ene
108—60—1
106—44—5
if Previously known by the name bis(2-Chloroisopropyl) ether
45
108
77,79
107
Semivolatiles
CAS Number
Column
(ng)
108—95—2
111—44—4
95—57—8
541—73—1
106—46—7
95—50—1
95—48—7
10
10
10
10
10
10
10
330
330
330
330
330
330
330
10000
10000
10000
10000
10000
10000
10000
(20)
(20)
(20)
(20)
(20)
(20)
(20)
94
93
128
146
146
146
108
65,66
63,95
64,130
148,113
148,113
148,113
107
10
10
330
330
10000
10000
(20)
(20)
621—64—7
67—72—1
98—95—3
78—59—1
88—75—5
105—67—9
10
10
10
10
10
10
330
330
330
330
330
330
10000
]0000
10000
10000
10000
10000
(20)
(20)
(20)
(20)
(20)
(20)
70
117
77
82
139
107
42,101,130
201,199
123,65
95,138
65,109
121,122
111—91—1
120—83—2
120—82—1
91—20—3
106—47—8
87—68—3
10
10
10
10
10
10
330
330
330
330
330
330
10000
10000
10000
10000
10000
10000
(20)
(20)
(20)
(20)
(20)
(20)
93
162
180
128
127
225
95,123
164,98
182,145
129,127
129
223,227
APPENDIX B - II
DRAFT 12196
-------
Appendix II
OLMO3.2/SV
Lth! n B.X!!I-I - TARGET COMPOUND LIST (TCL), CONTRACT REOUIRED OLJANTITATI0N LIMITS (CROLs) PRIMARY
QUANTITATION IONS. AND SECONDARY IONS FOR OLMO3.I SOW SEMIVOLATILE ORGANIC COMPOUNDS (CONT
Qiiantitation Limits
Low
Med
Semivolatiles
CAS Number
ug/L
ug/Kg
Characteristic
ug/Kg (ng) Primary
Ions
Secondary
4—Chloro—3—methylpheno l
59—50—7
10
330
10000 (20)
2—Methylnaphthalene
91—57—6
10
330
107
10000 (20)
144,142
llexachiorocyclopentadierie
77—47—4
10
330
142
10000
141
2,4,6—Trichiorophenol
88—06—.
10
330
237
10000 (20)
235,272
2,4,5—Trichloro heno1
95—95—4
25
830
196
25000
198,200
2—Chloronaphthalene
91—58—7
10
330
196
10000 (20)
198,200
2—Nitroaniline
88—74—4
25
830
162
25000
164,127
Dirnethylphthalate
131—11—3
10
330
65
10000 (20)
92,138
Acenaphthylene
208—96—8
10
330
163
10000 (20)
194,164
2,6—Dinitrotoluene
606—20—2
10
330
152
10000 (20)
151,153
3—Nitroaniline
99—09—2
25
830
165
25000 (50)
89, 121
Acenaphthene
83—32—9
10
330
138
10000 (20)
108,92
2,4—Dinitrophenol
51—28—5
25
830
153
25000 (50)
152,154
4—Nitrophenol
100—02—7
25
830
184
25000 (so)
63,154
Dibenzof iran
132—64—9
10
330
109
10000
139,65
2,4—Dinitrotoluene
121—14—2
10
330
10000
(20) 168
(20)
139
Diethy lphtha late
84—66—2
10
330
10000
(20)
165
63,182
4—Chiorophenyl—plienylether
7005—72—3
10
330
10000
149
177,150
Fluorene
86—73—7
10
330
10000
(20)
(20)
204
206,141
4—Nitroaniline
100—01—6
25
830
25000
(50)
166
165,167
4 ,6—Dinitro—2—methy]phenol
534—52—1
25
830
25000
(50)
138
92,108
N—nltroso-di-phenylamine
86—30—6
10
330
10000
(20)
198
182,77
4— romophenyl—phenylether
101—55—3
10
330
10000
(20)
169
168,167
Ilexach lorobenzene
118—74—1
10
330
10000
(20)
248
250,141
Pentachiorophenol
87—86—5
25
830
25000
(50)
284
142,149
Phenanthrene
85—01—8
10
330
10000
266
264,268
Anthracent
120—12—7
10
330
10000
(20)
(20)
178
179,176
Carbazole
86-74-8
10
330
10000
178
179,176
Di—n—buty lphtha late
84—74—2
10
330
10000
(20)
167
166,139
Fluoranthene
206—44—0
10
330
10000
149
150,104
Pyrene
129—00—0
10
330
10000
(20)
202
101,100
Buty lbenzy lphthalate
85—68—7
10
330
10000
202
101,100
APPENDIX B - 12
DRAFT 12/96
-------
Appendix B
OLM O3.2/SV
I th! p fl.XIII-l - TA ET COMP0t NI) LIST ( TCL . CONTRACT REOIJIREI) OIJANTITATION L1M!T JCROIs). PRIMARY
OIJANTITATION IONS. AND SECONDARY IONS FOR OLMO3.I SOW SEMIVOLATILE ORGANIC COMPOUNDS (CONT )
Quantitalion Limits
Characteristic Ions
Primary Secondary
Semivolatiles
3, 3’ —Dichlorobenzidlne
Benzo (a) anthracene
Chrysene
bis(2- LLhylhexyl)phthalate
Di—n—octy1phtha1aN
Benzo (b) tluoranthene
Benzo (k) fluoranthene
Benzo (a) pyrene
Indeno(1, 2, 3—cd)pyrene
Dibenz (a h) anthracene
enzo (g, h, i) perylene
CAS Wumber
91—94—1
56—55—3
2 18—01—9
117—81—7
117—84—0
20 5—99—2
207—08—9
50—32—8
193—3 9—5
53—70—3
191 —24—2
Law
Water Soil
ug/L ug/Kg
10 330
10 ‘330
10 330
10 330
10 330
10 330
10 330
10 330
10 330
10 330
10 330
Med
Soil
ug/Kg
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
Column
(ng)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
252
228
228
149
149
252
252
252
276
278
276
254,126
229, 226
226, 229
167,279
253,125
253,125
253,125
138,227
139,279
138, 277
APPENDIX B - 13
DRAfl’ 12/96
-------
Appendix B OLMO3.2/SV
SA1 {PLE CONCENTRATION - the amount of analyte present in a sample is calculated using RRFSO of the
continuing calibration standard in the following equations:
Sample concentration for water:
- ( A. ) (IS) (Vs) (Df) (GPC )
ug/L - (A 2 ) (RRF) (V 1 ) (V 0 )
Sample concentration for low and medium level soil/sedimeru:
( AX) (IS) (Va) (Do (GPC )
ug/Kg (Dry weight basis) = (A) (RRF) (V 1 ) (We) (D)
Where,
A = Area of the primary quantitanon ion response (EICP) for the compound to be measured
A = Area of the primary quantication ion response (EICP) for the specific internal standard
IS = Amount of internal standard added in nanograxns (ng)
RRF = Relative Response Factor from the most recent continuing calibration standard
Df = Dilution Factor - The dilution factor for analysis of water and soil/sediment samples for
seniivolatiles by this method is defined as follows:
uL most conc. extract used to make dilution + uL clean solvent
uL most conc. extract used to make dilution
If no dilution is performed, Df 1.
W = Weight of sample extracted in grams (g)
D = 100 - % Moisture
100
V 1 = Volume of the concentrated extract in microliters (uL)
V 0 = Volume of water extracted in milliliters (mL)
V, = Volume of extract injected in microliters (uL)
GPC = GPC factor (If no GPC is performed, GPC = 1; if GPC is performed, then GPC = 2.0)
CRQL CALCULATIONS
Water:
( V) (V) (V) (DO )
Adjusted C’RQL = Contract RQL x v 0 ) (v )(v )
Where,
V 1 , V 0 , V, and Df are defined in the sample concentration equation above
V = Contract sample volume (1000 niL)
V , = Contract injection volume (2 uL)
V = Contract concentrated extract volume (1000 uL if GPC is not performed, 500 uL if GPC was
performed).
APPENDIX B -14 DRAfl’ 12/96
-------
Appendix B OLMO3.2/SV
CRQL CALCULATIONS
Soil/Sediment:
Adjusted CROL = Contract CRQL x
Where,
V,, Df, W , V, and D are delined in the sample concentrauon equation above
W = Contract sample weight (30 g for low level and 1 g for medium level soil/sediment samples).
V 7 = Contract injection volume (2 uL)
V = Contract concentrated extract volume (1000 uL if GPC is riot performed, 500 uL if GPC was
performed).
SECTION XIV: TENTATiVELY IDENIikthD COMPOUND CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAISV-XIV.B for tentatively identified compound (TIC) data validation criteria and the following
method TIC QC criteria:
The validator is required to report up to 30 TICs in the Data Validation Memorandum.
TENTATiVELY mENrii,jj D COMPOUND CONCENTRATION - the estimated concentration for non-target
compounds tentatively identified shall be determined by the internal standard method using the following equations:
Sample concentration for water:
- ( Ar) (IS) (Vs) (Df) (GPC )
ug/L - (A 5 ) (RRF) (Vi) (V 0 )
Sample concentration for low and medium level soil/iediment:
— ( Ax) (IS) (t/ ) (Df) (GPC )
ug/Kg - (A ) (RRF) (Vi) (W 5 ) (D)
Where,
= Area of the characteristic ion (EICP) for the non-target compound to be measured
A, 3 = Area of the characteristic ion (EICP) for the specific internal standard
IS = Amount of internal standard added in nanograms (rig)
RRF = Relative Response Factor is assumed to be I
Df = Dilution Factor - The dilution factor for analysis of water and soil/sediment samples for
sernivolatiles by this method is defined as follows:
uL most conc extract used to make dilution + uL clean solvent
uL most conc. extract used to make dilution
If no dilution is performed, Df = 1.
W , = Weight of sample extracted in grams (g)
D = 100 - % Moisture
100
V 1 = Volume of the concentrated extract in microliters (uL)
V 0 = Volume of water extracted in milliliters (niL)
V = Volume of extract injected in microliters (uL)
GPC = GPC factor (If no GPC is performed, GPC = 1; if GPC is performed, then GPC = 2.0)
-------
Appendix B OLMO3.2/SV
SECTION XV: SEMIVOLATILE CLEANUP CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
H, Section VOA/SV-XV-B for semivolaule data validation criiena and the following method semivolatile cleanup
QC criteria:
GPC
[ nina! GPC calibration consists of analyzing the GPC calibration solution to establish the correct “Collect” and
“Dump” time periods and a GPC blank to ensure that the system is free of contaminants.
1. The GPC Calibration Solution contains the following analytes in methylene chloride at the
specified concentrations:
corn oil - 25.0 mg/mL perylene - 0.02 mg/mL
bis-(2-ethylhexyl)phthalate - 0.5 mglmL sulfur (optional) - 0.08 mg/mL
methoxychlor - 0.2 mg/niL
2. The GPC blank consists of methylene chloride.
The GPC must be recalibrated every 7 days with the GPC Calibration Solution followed by a methylene chloride
GPC blank.
Table App.B XV!-l - INITIAL AND CONTINUING GPC CALIBRATION CRITERIA
Peak
Resolution
Corn Oil and phthalate peaks must exhibit > 85% resolution.
Phthalate and methoxychlor peaks must exhibit > 85% resolution.
Methoxychior and perylene peaks must exhibit > 85% resolution.
Perylene and sulfur peaks (if sulfur was added) must not be saturated
and must exhibit >90% baseline resolution.
Peak Shape
Peaks must be observed and should be symmetrical for all compounds
in the calibration solution.
Retention
Time
The retention times must not vary more than ± 5.0% between
calibrations.
Blanks
A GPC blank must be analyzed after each initial GPC calibration.
Target analytes cannot be present at greater than the CRQL for any
target analyte except phthalate esters, which must be < 5x CRQL.
SECTION XVI: SYSTEM PERFORMANCE CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Eva1uatin Environmental Analyses , Part
H, Section VOAISV-XVI-B for system performance data validation criteria.
SECTION XVII: OVERALL ASSESSMENT CRITERIA
Refer to Region I EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-XVII-B for overall assessment data validation criteria.
APPENDIX B -16 DRAFT 12/96
-------
Appendix C
CLP SOW OLCO2. 1/Low Concentration Volatile Organic Analysis
Method QC criteria, Equations, and Definitions
-------
OLCO2. 1/VOA
APPENDIX C
The following method QC criter:a. equations, and definitions apply to data generated according to the USEPA CLP
Statement of Work for Organic Analysis, Low Concentration Water, OLCO2.I, Exhibit D Volatiles.
Note: MSIMSD are not applicable. MS/MSDs are riot required for work under this SOW.
Capillary GC columns are mandatory. Packed columns cannot be used.
SECTION I: PRESERVATION & TECHNICAL HOLDING TIME CRITERIA
Refer to Region I, EPA-NE Data Validation Functional Guidelines for Evaluating Environiner.tal Analyses , Part
II, Section VOAISV4 -B for preservation and technical holding time data validation cnceria.
SECTION II: GC!MS INSTRUMENT PERFORMANCE ChECK (TUNING) CRITERIA
Refer to the following method GC/MS instrument performance (tuning) QC criteria for data validation:
The analysis of the instrument performance (tuning) check solution (50 ng BFB on column) must be performed at
the beginning of each 12-hour period during which samples or standards are analyzed. The tuning check,
bromofluorobe ene (BFB), for volatile analysis must meet the ion abundance criteria given below
ION ABUNDANCE CRITERIA
50 8.0 -40.0% of rn/z 95
75 30.0-66.0% of mlz 95
95 Base Peak, 100% Relative Abundance
96 5.0 - 9.0% of m/z 95 (see note)
173 Less than 2.0% of tn/z 174
174 50.0 - 120.0% of mlz 95
175 4.0 - 9.0% of mass 174
176 93.0- 101.0% of m/z 174
177 5.0 - 9.0% of m/z 176
Note All ion abundances must be normalized to m/z 95, the nominal base peak, even though the ion
abundance of mlz 174 may be up to 120% that of m/z 95
The mass spectrum of BFB must be acquired in the following manner. Three scans (the peak apex scan and the
scans immediately preceding and following the apex) are acquired and averaged. Background subtraction is
required, and must be accomplished using a single scan no more than 20 scans prior to the elution of BFB. Part
of the BFB peak must not be background subtracted.
APPENDIX C - I DRAFT 12/96
-------
Appendix C OLCO2.1/VOA
SECTION ff1: II 4TTIAL CALIBRATION CRiTERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAJSV-III-B for initial calibration data validauon criteria and the following method initial calibration
QC criteria:
The initial calibration standards must be analyzed upon contract award, whenever corrective action is taken which
may change or affect the initial calibration criteria or if the continuing calibration acceptance criteria have not been
met. Initial calibrations must be analyzed after the analysis of a compliant instrument performance check.
The initial calibration standards must include the target compounds listed in the Target Compound List (TCL) in
Section XIII of this Appendix, as well as the internal standards and the system monitoring compound.
All imtial calibration standards must be analyzed at the following concentration levels; 1.0, 2.0, 5 0, 10, and 25
ug/L except for the ketones which are analyzed at 5.0, 10, 25, 50, and 125 ugiL.
RELATIVE RESPONSE FACTOR (RRF) - A measure of the relative mass spectral response of an analyte
compared to its internal standard. The RRF is calculated using the following equation:
A C
RRF= — -x--
A 13
Where,
= Area of primary quantitation ion response (EICP) for the compound to be measured
A = Area of primary quantitation ion response (EICP) for the internal standard
C = Concentration of the internal standard
C, = Concentration of the compound to be measured
AVERAGE (MEAN) RELATIVE RESPONSE FACTOR (RRF) - The average or mean RRF is deternuned by
the analysis of five different standard concentrations and is used in calculating a compound concentration in
samples. The RRF is calculated using the following equation:
— RRF
RRF=E I
I 1
Where,
RRF = The individual RRFs for various concentration levels
ii = The number of RRFs
APPENDLX C - 2 DRAFF 12/96
-------
Appendix C OLCO2.1/VOA
PERCENT RELATIVE STANDARD DEVIATION (%RSD) - The % RSD for each compound is a measure of
the linearity of the calibration curve. The % RSD is calculated using the following equation:
%RSD = Standard Deviation 100
l4ean
Where,
H ( x— ) 2
Standard Deviat1.on = I
N (n—i)
x = Mean
a = total number of values
x, = each individual value used to calculate the mean
SECTION IV: CONTINUU1G CALIBRATION CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
11, Section VOAJSV-IV-B for continuing calibration data validation criteria and the following method continuing
calibration QC criteria:
The continuing calibration standard must be analyzed once every 12 hours, following the analysis of a compliant
instrument performance check and initial calibration, and prior to the analysis of field samples, QC samples and
blanks.
The continuing calibration standard must include the target compounds listed in the Target Compound List (TCL)
in Section XIfl of this Appendix, as well as the internal standards and the system monitoring compound.
Continuing calibrations must be analyzed at a finai concentration of 5 ugIL for non-ketone compounds and at a final
Concentration 25 ug/L for the ketones.
Note: The low concentration method % Difference for continuing calibration differs fIom the Region I
Functional Guidelines ontinning calibration % Difference criteria (± 25.0 %). The low concentration method
requires that the continuing calibration % Difference for most target compounds and surrogates be less than
or equal to ± 30.0%. The following compounds do not have a minimum % D requirement but must meet
a minimum RRF criterion of 0.010: carbon dlsululde, chloroethane, chioromethane, cis-1,2-djchjoroethene,
trans-L,2-dichloroethene, 1,2-dlchloropropane, and methylene chloride. Furthermore, OLCO2.1 does not
specify R.RF or % D criteria for the following compounds: acetone, 2-butanone, 1,2-dibromo-3-
chloropropane, 2-hexanone, 4..methyl-2-pentanone, and 1,2,4-trichlorobenzene. (Ifdacaqualitv objectives allow
for greater variability of data, then expanded %D and minimum response factor criteria should be documented in
the EPA-approved site-specific QAPJP or amendment to the QAPJP. If response factors less than 0.05 are allowed,
then the validator should ensure that there is sufficient QC daia w support the use of low RFs in sample calcuiacions
APPENDDC C - 3 DRAFT 12/96
-------
Appendix C OLCO2. 1/VOA
PERCENT D [ FFER.ENCE (%D) - The % D is used to compare the initial calibration mean RRF with the
continuing calibration RRF5. The % Difference indicates both the direction and the magnitude of the comparison,
i.e., the % Difference may be either negative, positive or zero.
RRF -RRF
% Difference = C x 100
RRF 1
Where,
RRF = Mean relative response factor from the most recent initial calibration meeting technical
acceptance criteria
RRFC = Relative response factor from continuing calibration standard
SECTIQ 1 V: BLANK CRITERIA
Refer to Re jon I, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAJSV-V-B for blank data validation criteria and the following method QC criteria.
Method Reauired Blanks
1. Method Blank - A 25.0 mL aliquot of reagent water that is carried through the entire analytical process
to determine the levels of Contamination associated with the processing and analysis of
samples. All blanks are spiked with internal standards and surrogate compounds and
blank analysis must meet internal standard and surrogate compound criteria. The method
blank must be analyzed at least once during every 12 hour time period on each GC/MS
system used for volatile analysis.
2. Storage Blank - Consists of two 40 niL VOA vials filled with reagent water prepared by the laboratory
when the first samples in the SDG are received. The vials are stored, under the same
conditions, with the field samples. After all the samples in the SDG are analyzed, a 25.0
rnL aliquot of the storage blank is analyzed to determine whether contamination was
introduced during storage of the samples. All blanks are spiked with internal standards
and surrogate compounds and blank analysis must meet internal standard and surrogate
compound cnteria. A mirumum of one storage blank must be analyzed per SDG after
all samples for that SDG have been analyzed.
3. Instrument Blank - A 25.0 m l aliquot of reagent water that is carried through the entire analytical procedure
and is analyzed following highly contaminated samples contaimng target compounds that
exceed the initial calibration range. The instrument blanks are used to determine if
contamination is introduced from a previous sample and the level associated with the
analytical instrument. All blanks are spiked with internal standards and surrogate
compounds and blank analysis must meet internal standard and surrogate compound
criteria. Instrument blanks are analyzed after a sample/dilution which contains a target
compound at a concentration greater than 25 ug/L (ketones 125 ug’L) or a non-target
compound at a concentration greater than 100 ug/L or saturated ions from a compound
(excluding peaks in the solvent front)
APPENDIX C -4 DRAFT 12/96
-------
Appendix c OLCO2.1/VOA
SECTION VI: SURROGATE COMPOUND CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-VI-B for surrogate compound data validation criteria and the following method surrogate
compound QC cn(erla:
The proper surrogate compounds must be quanntied using the correctly assigned internal stanoards and the correct
primary quantnation ions
The surrogate compound, 4-Bromofluoroberizene, is added to all samples, standards, QC samples, and blanks for
a final concentration of 5 ug/L.
Table Apo.D VT-i - CHARACTERISTIC IONS FOR SURROGATE COMPOUNDS
Surrogate
Characteristic Ions
Primary Quantitatfon Ion Secondary_Ion(s) Internal_Standard
4 -Bromofluorobenzene
174 95, 176 1 ,4-Difluorobe iuene
The surrogate % recovery is calculated using the following equation:
Surrogate Percent Recovery = x 100%
Qd = Quantity of surrogate determined by analysis
Q 1 = Quantity of surrogate added to samplefblank
Table Apo D,VI-2 - SURROGATE RECOVERY LIMITS
Surrogate
Method QC Criteria
—
Percent Recovery
(Water)
4-Bromofluorobenzene
80-120
Sample reanalysis is required for samples that do nct meet the surrogate recovery acceptance criteria.
APPENDIX C -5 DRAFT 12/96
-------
Appendix C OLCO2.1/VOA
SECTION V I I: INTERNAL STANDARDS CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-VH-B for internal standard data validation criteria and the following method internal standard
QC criteria.
The correct internal standard must be used for sample compound quantitauon and the correct internal standard
primary quancitauon ion must be used for quantitation.
The internal standards Bromochioromethane, I ,4-Difluorobenzene. and Chlorobenzene-d are added to all samples,
standards, QC samples, and blanks for a final concentration of 5.0 ugfL.
Table App.D VlI-L - LOW CONCENTRATION VOLATILE INTERNAL STANDARDS WITH
COR1 ESPONDFNG TARGET COMPOUNDS AND SURROGATES ASSIGNED FOR QUANTITATTON
IS IS IS
I . 4-Difluorobenzene Chlorobenzened I . 4-Dichlorobenzene-d 4
Acetone Benzene Bromoform
Bromochioromethane Bromodichioromethane I ,2-Dibromo-3-chloropropane
Bromomethane Carbon tetrachioride I ,2-Dtchlorobenzene
2-Butanone Chlorobenzene 1 ,3-Dichlorobenzene
Carbon disulfide Dibromochioromethane I ,4-Dichlorobenzene
Chloroethane 1 ,2-Dtbromoethane I ,2.4-Trichlorobenzene
Chloroform I ,2-Dichloropropane
Chioromethane cis-i,3-Dichloropropene
1,1 -Dichloroethane trans-I ,3-Dichloropropene
I ,2-Dichloroethane Ethylbenzene
I, l-Dichloroethene 2-Hexanone
cis- 1,2-Dichloroetherie 4-Methyl-2-pentanone
trans-i ,2-Dichloroethene Styrene
Methylene chloride 1,1 ,2,2-Tetrachtoroethane
Vinyl chloride Tetrach loroethene
Toluerie
I, I, 1-Trichioroethane
4-Bromofluorobenzene I, I ,2-Trichloroethane
(surr) Trich loroetherie
Xylenes (total)
APPENDIX C - 6 DRAFF 12/96
-------
Appendix C 01C02. 1/VOA
Table Ann D VI1.2 - CUARACTFRISTIC IONS FOR INTERNAl. STANDARDS FOR LOW
CONCENTRATION VOLATILE COMPOUNDS
Internal Standard
Characteristic Ions
Primary Quantitation Ion
Secondary Ion(s)
I,4-Dtfluorobenzene
114
63. 83
1 ,4-Dichjorobenzene-d4
152
115, 50
Chlorobenzene-d5
117
82, 119
Internal standard area counts for each of the internal standards must be within the inclusive range of ± 40% of the
response of irnernal standards in the associated daily continuing calibration standard.
The retention time of the internal standard must not vary by more than ± 20 seconds from the retention time of
the associated daily continuing calibration standard.
Sample reanalysis is required for samples that do not meet the internal standard acceptance criteria.
SECTION VIII: MATRIX SPIKE/MATRIX SPIKE DUPLICATE CRITERIA
The Low Concentraüon method does not require MS/MSD analysis therefore, no method-specific criteria are
available for MSIMSD. Refer to Region 1, EPA-NE Data Validation Functional Guideiines for Evaluating
Environmental Analyses , Part II, Section VOAJSV-VIII-B for MSIMSD validation criteria if MS/MSD analyses are
performed.
SECTION LX: FIELD DUPLICATE CRiTERIA
Refer to Region I, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
fl. Section VOA/SV-IX-B for field duplicate data validation criteria.
SECTION X: SENSITiVITY CHECK CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluatin2 Environmental Analyses , Part
H, Section VOA/SV-X -B for sensitivity check data validation criteria.
APPENDIX C -7
DRAFI’ 12/96
-------
Appendix C OLCO2.1/VOA
SECTION Xi; PE SAMPLES - ACCURACY CHECK CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
11, Section VOA/SV-XI-8 for accuracy check data validation criteria and the following method accuracy check QC
criteria:
The LCS is a method-required internal laboratory quality control sample that must be prepared, analyzed and
reported once per SDG. It must be prepared arid analyzed concurrently with the samples in the SDG using the same
instrumentation as the samples.
Compound
Final Concentration
ug/L
Method Required
QC % Recovery Limits
Vinyl chloride
5.0
60 - 140
1,2- Dichtoroethane
5.0
60 - 140
Carbon tetrachloride
5.0
60 - 140
1,2-Dichloropropane
5.0
60 - 140
Tnchloroethene
5.0
60 - 140
1,I.2-Tnchloroethane
5.0
60 - 140
Benzene
5.0
60 - 140
cis-1,3-Dicbloropropene
5.0
60 - 140
Bromoform
5.0
60 - 140
Tetrachioroethene
5.0
60 - 140
1,2-Dibromoethane
5.0
60 - 140
1,4-Dtchlorobenzene
5.0
60 - 140
SECTION XII: TARGET COMPOUND IDENTLFICATION CRITERIA
Refer to Region 1, EPA-NE Data Validation Functionr Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-XH-B for target compound identification data validation criteria.
APPENDLX C - S DRAFT 12/96
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Appendix C OLCO2.1/VOA
SECTION Xffl: COt vEPOUND QUANTITATION AND REPORTED QUANTITATION LIMITS CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part II, Section VOA/SV.
XllI-B for compound quantitatiori and reported quantitation limit data validation criteria and the following method quanucation QC criteria:
Volatile target compounds must be quantitaced using the internal standard method with the internal sundards
assigned in Appendix A, Section VII. The daily RRF5 must be used for sample quantuanon. The sample target
compounds must be quantified using the following primary quarititanon ions and must be reported to the CRQLs listed below
Table App.D XHI-l - TARGET COMPOUND LEST (TCL), PRIMARY QUANTITATION AND SECONDARY IONS. AND
CONTRACT REQUIRED QUANTITATEON LIMITS (CRQLs’ FOR OLCO2.O SOW VOLATILE ORGANIC COMPOUNDS
Quantitatjon Limits
Low On Characteristic loris
Water Column Primary Secondary
Volatiles CAS Number ug/L (ng) -
Chiorornethane 74—87—3 1 (25) 50 52
Bromochioroniethane 74-97-5 3. (25) 128 49,130
1,2-Dibromoechane 106-93-4 1 (25) 107 109,188
Bromomethane 74—83—9 1 (25) 94 96
Vinyl Chloride 75—01—4 1 (25) 62 64
Chioroethane 75—00—3 1 (25) 64 66
Methylene Chloride 75—09—2 2 (50) 84 86,49
Acetone 67—64—1 5 (125) 43 S e
Carbon Disulfjde 75—15—0 1 (25) 76 78
1,1—Dichioroethene 75—35—4 1 (25) 96 61,63
1,1—Dichioroethane 75—34—3 1 (25) 63 65,83
iS -1,2—DiChloroethene 156—59—2 1 (25) 96 61,98
crans-1,2-Djchloroethene 156-60-5 1 (25) 96 61,98
Chloroform 67—66—3 1 (25) 83 85
l, 2 —:..ichloroethane 107—06—2 1 (25) 62 98
2—Bucanone 78—93—3 5 (125) 43 72*
l,l,1—Trjch loroethane 71—55—6 3. (25) 97 99,61
Carbon Tetrachlorjde 56—23—5 1 (25) 117 119
Bromod3.chloromet e 75—27—4 1 (25) 83 85,127
l , 2 —Dichloroprocane 78—87—5 1 (25) 63 112
cis—l,3—Djch lorapropene 10061—01—5 1 (25) 75 77
Trichiorcethene 79—01—6 1 (25) 95 130,132
Dthrcmoch lorometh a ne 124—48—1 1 (25) 129 127
1, :,2—Trlchloroethane 79—00—5 1 (25) 97 83,85,99,132,134
Benzene 71—43—2 1 (25) 78 --
trans—l,3—Dich1oropr p 10061—02—6 1 (25) 75 77
Brornoforrn 75—25—2 1 (25) 173 175,254
4—Methyl—2—pentanone 108—10—1 5 (125) 43 58,100
2—Hexanone 591—78—6 5 (125) 43 58,57,100
Tetrachioroetherie 127—18—4 1 (25) 166 168,129
Toluerie 108—88—3 1 (25) 91 92
l,l, 2 , 2 —Tetrachloroethane 79—34—5 1 (25) 83 131,85
l 2 ,4-Trlchlorobenze r ie 120-82-1 1 (25) 120 182,145
1,2-Dichloroberizerie 95-50-1 1 (25) 146 111,148
l ,3-D ichlorobenzene 541-73-1 1 (25) 146 111,148
l,4-Dlchloroberizene 106-46-7 1 (25) 146 :11,148
Ch lorobenzene 108—90—7 1 (25 112 77,114
Ethv lberizene 100—41—4 1 (25, 91 106
Styrerie 100—42—5 1 (25) 104 78
Xvlenes (Total) 1330—20—7 1 (25) 106 91
l.. 2 -Dlbromo-3-chloroprcpane 96-12-8 1 (25) 75 155,157
- m/z 43 is used fcr auant:tat on of 2-Butar.one, but m/z 72 must be present for posit ve
ident:f cation.
APPENDIX C - 9 DRAFT 12/96
-------
Appendix C OLCO2.1/VOA
SAMIPLE CONCENTRATION - The amount of analyte present in a sample is calculated using the RRF5 of the
continuing calibration standard in the following equation:
Sample concentration for water:
(Ar) (IS) (Df)
ug/L = (A ) (RRF) (v 0 )
Where,
A, = Area of the primary quancicacion ion response (EICP) for the compound to be measured
A = Area of the primary quancication ion response (EICP) for the specific internal standard
IS = Amount of internal standard added in nanograms (ng)
RRF = The Relative Response Factor from the most recent continuing calibration standard
V 0 = Total volume of water purged in milliliters (niL)
Df = Dilution Factor - The dilution factor for analysis of water samples for volatiles by this method is
defined as the ratio of the number of milliliters (mL) of water purged (i.e., V 0 above) to the
number of niL of the original water sample used for purging. If no dilution is performed, Df= 1.
CRQL CALCULATIONS
Water.
( V )
Adjusted CRQL = Contract CRQL x (V) x (Df)
Where,
V 0 and Df are defined in the sample concentration equation above
V, = Contract sample volume (5 to 25 mL)
APPENDLX C - 10 DRAFF 12/96
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Appendix C OLCO2.1/VOA
SECTION XIV: TENTATIVELY IDENTL1 ThD COMPOUND CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAJSV-XIV-B for tentatively identified compound (TIC) data validation criteria and the following
method TIC QC criteria:
The validator is required to report up to 30 TICs in the Data Validation Memorandum.
TENTATIVELY IDEN1wthD COMPOUND CONCENTRATION - the estimated concentration for non-target
compounds tentatively identified shall be deternuned by the internal standard method using the following equations:
Sample concentration for water:
IL — ( Ar) (IS) (Df )
ug - (A 1 ) (RRF) (V 0 )
Where,
A, = Area of the primary quantitaLion ion response (EICP) for the non-target compound to be measured
A, = Area of the primary quantitation ion response (EICP) for the specific internal standard
IS = Amount of internal standard added in nanograms (ng)
RRF = Relative Response Factor assumed to be I
V 0 = Total volume of water purged in milliliters (mL)
Df = Dilution Factor - The dilution factor for analysis of water samples for volatiles by this method is
defined as the ratio of the number of milliliters (mL) of water purged (i.e. V, above) to the
number of mL of the original water sample used for purging If no dilution is performed, Df= 1.
SECTION XV: SEMIVOLATILE CLEANUP CRITERIA
Not applicable to low concentration volatile analysis.
SECTION XVI: SYSTEM PERFORMANCE CRiTERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAISV-Xvj-B for system performance data validation criteria.
SECTION XVII: OVERALL ASSESSMENT CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAJSV-XVlI.S for overall assessment data validation criteria.
APPENDIX C - 11 DRAFT 12/96
-------
Appendix D
CLP SOW OLCO2. 1/Low Concentration Semivolatile Organic Analysis
Method QC criteria, Equations, and Definitions
-------
OLCO2. l/SV
APPENDIX D
The following method QC criteria, equations, and definitions apply to data generated according to the USEPA CLP
Statement of Work for Organic Analysis, Low Concentration Water, OLCO2.1, E’chibit 0 Sexnivolatjles.
Note: MS/MSD are not applicable. MS/MSDs are not required for work under this SOW.
Capillary GC columns are mandatory. Packed columns cannot be used.
SECTION I: PRESERVATION & TECHNICAL HOLDING TIME CRrrERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-1-B for preservation and technical holding tune data validation criteria.
SECTION II: GC/MS INSTRUMENT PERFORMANCE CHECK (TUNING) CRITERIA
Refer to the following method GCIMS instrument performance (tuning) QC criteria for data validation:
The analysis of the instrument performance (tuning) check solution (50 ng DFTPP on column) must be performed
at the beginning of each 12-hour period during which samples or standards are analyzed. The tuning check,
decafluorotriphenyiphosphine (DFTPP), for sernivolatile analysis must meet the ion abundance criteria given below:
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 rnlz 198
197 Less than 1.0% of mfz 198
198 Base Peak, 100% Relative Abundance (see note)
199 5.0 -9.0% ofm/z 198
275 10.0 - 30.0% of mlz 198
365 Greater than 0.75% of m/z 198
441 Present, brz less than mhz 443
442 40.0- 110.0% of mhz 198
443 15.0 -24.0% of mIz 442
Note : All ion abundances must be normalized to rnlz 198, the nominal base peak, even though the ton abundances
of m/z 442 may be up to 110% that of mlz 198
The mass spectrum of DFTPP must be acquired in the following manner. Three scans (the peak apex scan and the
scans immediately preceding and following the apex) are acquired and averaged. Backgrounu subtraction is required
aria must be accomplished using a single scan no more than 20 scans pnor to the eluuon of DFTPP Part of the
DFTPP peak must not be background subtracted
APPENDIX D - I DRAFT 12/96
-------
Appendix D OLCO2.l/SV
SECTION III: INITIAL CALIBRATION CIUTERIA
Refer to Region I EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
U, Section VOA/SV-III-B for initial calibration data validation criteria and the following method initial calibration
QC criteria:
The initial calibration standards must be analyzed upon contract award, whenever corrective action is taken which
may change or affect the initial calibration criteria or if the continuing calibration acceptance criteria have not been
met. Initial calibrations must be analyzed after the analysis of a compliant instrument performance check.
The initial calibration standards must include the target compounds listed in the Target Compound List (TCL) in
Section X III of this Appendix, as well as the internal standards and the system monitoring compounds.
1 uL volume of the initial calibration standard must be injected and all initial calibration standards must be analyzed
at the following concentration levels; 5.0, 10, 20, 50, and 80 ng/uL except for eight target compounds and one
surrogate compound. Compounds 2,4-dinitrophenol, 2,4,5-trichiorophenol, 2-nitroaniljne, 3-nirroaniline, 4-
miroaniline, 4-nitrophenol, 4-6-dinitro-2-methylphenol, pentacblorophenol, and 2 ,4,6-tribromophenol(surr) must
be analyzed at 20, 50, 80, 10, and 120 ngluL.
RELATIVE RESPONSE FACTOR (R RF) - A measure of the relative mass spectral response of an analyte
compared to its internal standard. The RRF is calculated using the following equation:
A C.
RRF=— -x--
C,
Where,
A, = Area of primary quantitation ion response (EICP) for the compound to be measured
= Area of primary quantitation ion response (EICP) for the internal standard
C,, = Concentration of the internal standard
C. = Concentration of the compound to be measured
AVERAGE (MEAN) RELATIVE RESPONSE FACTOR (RRF) - The average or mean RRF is determined by
the analysis of five different standard concentrations and is used in calculating a compound concentration in samples.
The RRF is calculated using the following equation:
— ‘ RRF
RRF=
1 1
Where,
RRF = The individual RRFs for various concentration levels
n = The number of RRFs
APPENDIX D -2 DRAFI’ 12/96
-------
Appendix D OLCO2.1/SV
PERCENT RELATIVE STAI’4DARJ) DEVIATION (%RSD) - The % RSD for each compound is a measure of
the linearity of the calibration curve. The % RSD is calculated using the following equation.
%RSD = Standard Deviation 100
L’4ean
Where,
( x
Standard Deviation = 1
N (n— i)
x=Mean
n = total number of values
= each individual value used to calculate the mean
SECTION IV: CONTThWII’4G CALIBRATION CRiTERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses . Part
I I , Section VOAJSV-IVB for continuing calibration data validation criteria and the following method continuing
calibration QC criteria:
The continuing calibrat:on standard must be analyzed once evezy 12 hours, following the analysis of a compliant
instrument performance check and initial calibration, and prior to the anrlysis of field samples, QC samples and
blanks.
The continuing calibration standard must include the target compounds listed in the Target Compound List (TCL)
in Section XIII of this Appendix, as well as the internal standards and the system monitoring compounds.
Continuing calibration standards must be analyzed at a final concentration of 20 ug/L for the majority of the
compounds and 80 ugIL for the eight compounds specified in the initial calibration section.
Note: The Low Concentration method % Difference QC criteria for continuing calibration differs somewhat
from the Region I Functional Guidelines continuing calibratic % Difference criteria. The Low Concentration
method requires that the continuing calibration % Differ :e be less than or equal to ±30.0% for two
compounds, 2-nitrophenol and 2,4,-dimethvlpheno l; whereas ae Fnnctional Guidelines requires qualification
of all data associated with a continuing calibration with % Difference greater than ± 25.0%. Refer to CLP
SOW OLCO2.l for those compounds that do not have % D requirements. If data quality objectives allow for
greater variability of data, then expanded % D validation criteria should be documented in the site-specific QAPjP
or amendment to the QAPJP.
APPENDIX D - 3 DRAFT 12!96
-------
Appendix D OLCO2.1/SV
PERCENT DIFFERENCE (%D) - The % D is used to compare the initial calibrauon mean RRF with the
continuing calibration RRF. The % Difference indicates both the direction and the magnitude of the comparison,
i.e., the % Difference may be either negative, positive or zero.
RRF -RRF
% Difference = ____ x 100
RRF 1
Where,
RRFI = Mean relative response factor from the most recent initial calibration meeting technical
- acceptance criteria
RRFc = Relative response factor from continuing calibration standard
SECTION V: BLANK CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAISV-V-B for blank data validation criteria and the followmg method QC criteria:
Method Required Blank
Method Blank - A volume of reagent water approximate in volume to the samples which is carried through the
entire analytical process to determine the levels of contamination associated with the processing
and analysis of the samples. All blanks are spiked with internal standard and surrogate
compounds and blank analysis must meet internal standard and surrogate compound criteria. A
method blanc must be extracted at least once for every SDG, for each 20 samples in an SDG, and
whenever samples are extracted. Each method blank must be analyzed on each GCIMS used to
analyzed the samples prepared with the method blank.
SECTION VI: SURROGATE COMPOUND CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAISV-Vl-B for surrogate compound data validation criteria and the following method surrogate
compound QC criteria:
Surrogate compounds must be quantified using the correctly assigned internal standards and the correct primary
quantication ions.
Surrogate compounds Nitrobenzene4, 2-Fluorobiphenyl, Terphenvl-d 14 , Phenol-d 5 , and 2-Fluorophenol are added
to all samples, standards, QC samples, and blanks at a concentration of 40 ug/mL and surrogate compound 2,4,6-
Tnbromophenol is added to all samples, standards. QC samples, and blanks at a concentration of 120 u2’mL.
APPENDIX D -4 DRAFT’ 12/96
-------
Appendix D OLCO2.1/SV
Table App.E.VI-1 - CHARACTERISTIC IONS FOR SURROGATE COMPOUNDS
Characteristic Ions
mary Quanti tion Ion Seconda Ion(s Inte aI S ndard
Surrogate —
Nitrobenzene4 82
128, 54
Naphthalene -d 3
2-Fluorobiphenvl 172
171
Acenaphchene.d 10
244
122, 212
Chxysene-d,,
99
42, 71
l,4-Djchlorobenzene -d 4
112
64
1 , 4 -Dichlorobenzene-d 1
330
332, 141
Phenanthrene -d 10
The surrogate % recovery is calculated using the following equation:
Surrogate Percent Recovery = - x 100%
= Quantity of surrogate determined by analysis
Q. = Quantity of surrogate added to sample/blank
Table Apy.E.V1-2 - SURROGATE RECOVERY LIMITS
Surrogate
Method QC Criteria
Percent Recovery
(Water)
Nitrobenzene-d
-
40-110
2-Fluorobiphenyl
30-110
Terphenvl-d 14
20-140
Phenol4
15-115
2-Fluorophenol
15-110
2,4,6-Tribromophenol
15-130 I
If the surrogate acceptance cntena are not met, the laboratory should check calcu1at ons, surrogate standard
solutions, and instrument performance. If the failed criteria are the result of instrument malfunction, only sample
reanalysis is required to meet surrogate acceptance criteria. Sample re-exiractionlreanalysis is required for samples
that do not meet the surrogate recovery acceptance cnteria, as a result of the incorrect surrogate standard solutions
or any other unknown problem.
APPEND D - DRAFF 12/96
-------
Appendix 1) OLCO2.1/SV
SECTION VII: INTERNAL STANDARDS CRITERIA
Refer to Region I. EPA-NE Data Validation Fi ciioi al GnideIi jor Evat t i 1 g Environmental Analyses , ‘Part H, Section VOA/SV-V1J-fl for internal standard
data validation criteria and the following iuetliotl internal standaiti QC criteria
The correct inti rnal standard must be used for sample compound quantification and the correct internal standard primary qnañtitation ion must be used for
quanittat ion
The internal standard compounds listed below are injected into all samples, standards, QC samples, and blanks at a concentration of 20 ng/uL.
App E.Vll-l - LOW CONCENTRATION SEMIVOLATILE INTERNAL STANDARDS WITh CORRESPONDING TARGET COMPOUNDS AND
SURROGATES ASSIGNED FOR OtJANTITATION
is IS IS IS IS IS
I ,4 — flichlorobenzene-—-il4 Naphthalene—dR Acenaphthene—d 10 Phenanthrene—d 10 Chrysene—d 12 Pervlene—d 12
Phenol Nitrobenzene Hexachlorocyclo— 4,6—Dinitro—--2— Pyrene Di—n-—--octy l-
bis(2—Cliloroethyl) Isophorone pentadiene methyiphenol Butylbenzy l- phthalate
ether 2—Nitrophenol 2,4,6—Trichloro—— N—nitroso-di— phthalate Benzo(b)fluor—
2—Ch loropheno l 2,4—Dirnethyl— phenol phenylamine 3,3’—Dtchloro— anthene
2-Meihy lplienol phenol 2,4,5—Trichloro—— 4—Broinophenyl benzidine Benzo(k)fluor—
2 ,2’-oxybis- bis(2—Chloro— phenol phenolether Benzo(a)— anthene
(l-Chloropropane) ethoxy)methane 2—Chloronaphthalene Ilexachloro— anthracene Benzo(a)pyrene
4—Met liylplìeno l 2,4—Dicliloro— 2—Nitroaniline benzene bis(2—ethyl- lndeno( I ,2,3—cd)-
N-Nttroso-Di-n- phenol Dimethylphthalate Pentachioro— hexyl)phthalate pyrene
propylamine Naphtha lene Acenaphihylene phenol Chrysene Dibenz(a,h)-
Ilexachloroethane 4-Chloroaniline 3—Nitroaniline Plienanthrene Terphenyl—d 14 anthracene
2-F ltiorophenol hlexach loro— Acenaphihene Anthracene (surr) Benzo(g,h,i)-
(surr) biitadiene 2,4—Dinitrophenol Di-n-btityl- perylene
Phenol-d5 4—Chloro—--3— 4—Nitrophenol phtha late
(surr) methylphenol Dibenzofuran Fitioranthene
2-Methyl naph- 2,4—Dinitrotolnene 2,4 ,6-Tribromo-
thalene 2 ,6—Dinitrotoluene phenol (surr)
Niirohcnzene-d5 Diethylphtltalate
(surr) •1—Chlorophenyl-
phenylether
Fltiorene
4—Nitroaniline
2—l l norobiphenyl
(sun)
(sun) = stunt ogate conupouuntl
APPENDIX D - 6 DRAFT 12/96
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Appendix D OLCO2.l/SV
Table App.E VII-2 - CHARACTERISTIC IONS FOR INTERNAL STANDARDS FOR LOW
CONCENTRATION SEMI VOLATILE COMPOUNDS
Internal Standard
Characteristic Ions I
Primary
Quantitation
Ion
Secondary Ion(s)
L,4-Dich lorobenzene-d 4
152
115
Naphthalene-d
136
68
Acenaphthene-d 10
164
162, 160
Phenanthrene-d 10
188
94, 80
Chrysene-d 1 ,
240
120, 236
Perylene-d 11
264
260, 265
Internal standard area counts for each of the internal standards must be within the inclusive range of - 50% and +
100% of the response of internal standards in the associated daily continuing calibration standard.
The retention time of the internal standard must not vary by more than ± 20 seconds from the retention time of
the associated daily continuing calibration standard.
If the internal standard acceptance criteria are not met, the laboratory should check calculations, internal standard
solutions, and instrument performance. If the failed criteria are the result of instrument malfunction, only sample
reanalysis is required to meet surrogate acceptance criteria. Sample reanalysis is required for samples that do not
meet the internal standard acceptance criteria, as a result of the incorrect internal standard solutions or any other
unknown problem.
SECTION VIII: MATRIX SPIKEIMATRIX SPIKE DUPLICATE CRITERIA
The Low Concentration method does not require MSTMSD analysis therefore, no method-specific criteria are
available for MS/MSD. Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating
Environmental Analyses , Part II, Section VOAISV-VIll-B for MS/MSD validation criteria, if:MS/MsD analyses
are perfo—ncd.
SECTION LX: FIELD DUPLICATE CRiTERIA
Refer to ReQion 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Secuon VOA/SV-IX-B for field duplicate data validation criteria.
SECTION X: SENS1TWITY CHECK CRITERIA
Refer to Reaton I Ep4 4 Data Validation Functional Guidelines for E’iaiuatine Environmental Analyses , Part
II. Section VOA/SV-X-B for sensitivity check data validation criteria
APPENDIX D -7 DRAFT 12/96
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Appendi c D OLCO2.1/SV
SECTION XI: PE SAMPLES - ACCURACY CHECK CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II. Section VOAISV-XI-B for accuracy check data validation criteria.
The LCS is a method required internal laboratory quality control sample that must be prepared, analyzed and
reported once per SDG. It must be prepared and analyzed concurrently with the samples in the SDG using the same
instrumentation as the samples.
Compound
Final Concentration
ug/L
Method Required QC %
Recovery Limits
Phenol
40.0
40 - 120
2-Chlorophenol
40.0
50 - 110
4-Chloroaniline
40.0
10 - 120
2 ,4,6-Trichlorophenol
40.0
40 120
bis(2-Chloroethvl)ether
20.0
50 - 110
N-Nitroso-di-n-propvlamine
20 0
30 - 110
Hexachloroethane
20.0
20 - 110
Isophorone
20.0
50 - 110
Naphthalene
20.0
30 - 110
2,4-Duiitroco [ uene
20.0
30 - 120
Dtethylphthalate
20.0
50 - 120
N-Nicrosodiphenvlamine
20.0
30 110
Hexach lorobenzene
20.0
40 - 120
Benzo(a)pyrene
20.0
50 - 120
SECTION X LI: TARGET COMPOUND WENTLJ ICATION CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II. Section VOA/SV-XI1-B for target compound identification data validation criteria.
APPENDIX D -8 DRAFF 12/96
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Appendix D OLCO2.1/SV
SECTION XIII: COMPOUND QUANTITATION AND REPORTED QUANTITATION LIMIT CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOA/SV-XIII-B for compound quantitation and reported quanutacion limit data validation criteria and
the following method quantitation QC criteria:
Sernivolatile target compounds must be quantitated using the internal standard method With (he inte—ial standards
assigned in Appendix E, Section VII. The daily RRF2O must be used for sample quanwanon. The sample target
compounds must be quantified using the following pnmary quanutnuon tons and must be reported o the CRQLs
listed below:
App E.XIfl-1 - TARGET COMPOUND LIST (TCL’L CONTRACT REQUIRED OUANTITATION LIMITS
( CROL& , PRIMARY OUANTITATEON IONS. AND SECONDARY IONS FOR OLCO2.0 SOW
SEMIVOLATILE ORGANIC COMPOUNDS
Quantitation Limits
Water Characteristic Ions
Setnivolatiles CAS Number ug/L Primaiy Secondary
Phenol 108—95—2 5 94 65, 66
bis(2—Chloroethyl) ether 111 1 4 5 93 63. 95
2—Chiorophenol 95—57--.-8 5 128 64, 130
2—Methylphenol 9548.7 5 108 107
2,2’-oxybts
(1-Ch loropropane)# 108—60——i 5 45 77, 79
4—Methylphenol l06 -11 5 5 108 107
N—Nitroso.--dj—n-
propylanune 621—64—--7 5 70 42, 101, 130
Hexachloroethane 67—72—1 5 117 201, 199
Nitrobenzene 98—95—3 5 77 123, 65
Isophorone 78—59——i 5 82 95, 138
2—Nitrophenol 88—75—5 5 139 65, 109
2 ,4—Dimethylpheno l 105—67—9 5 107 121, 122
bis(2—Chloroethoxy)
methane 111—91—1 5 93 95, 123
2 . 4 —Dich lorophenol 120—83—2 5 162 164. 98
Naphihalene 91—20——3 5 128 129, 1 7
4—Chioroaniline 106—47----S 5 127 129
Hexacbjorobutadjene 87—68—3 5 225 223, 227
4 —Chloro——3—methylphenol 59—50——7 5 107 144, 142
2 —Methylnaphthalene 9157—6 5 142 141
Hexachlorocyc lopentadiene 77__47—4 5 237 235, 272
2 ,4,6—Trichlorophenol 88—06—2 5 196 198, 200
2 ,4 ,5—Trich!oropheno l 95 —95-. - --4 20 196 198, 200
2—Chloronaphmalene 91—58—7 5 162 164, 127
2—Njcroamline 88—74---4 20 65 92, 138
Dtmethy lphthalare 131—11—3 5 163 194, 164
Acenaohthylene 208—96-—S 5 [ 52 151, 153
2 ,6—Dinjtroio luene 6 06—20——2 5 165 89. 121
3—Nicroaniline 99—09—2 20 138 108, 92
Ac naphthene 83—32—9 S 153 152, 154
2,4—Dinicrophenol 51—28—5 20 184 63, 154
# Previously known by the name bis(2-Chloroisopropyl) ether
APPENDIX D - 9 DRAFT 12/96
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Appendix D OLCO2.1/SV
APP.EX1II-I - TARGET COMPOUND LEST (TCL). CONTRACT REQUIRED OUANTITATION LIMETS
( CRQLs). PREMARY OUANTITATr0N IONS. AND SECONDARY IONS FOR OLCO2. SOW
SEMIVOLATILE ORGANIC COMPOUNDS (CONT )
Quantatation Limits
Water Characteristic Ions
Semivolatiles CAS Number ug/L Pnmazy Secondary
4—Nitrophenol 100—02—7 20 109 139, 65
Dibenzoftiran 132—64-—9 5 168 139
2,4—Din itrocoluene 121—14—2 5 165 63, 182
Diethy lphthaiace 84—66—2 5 149 177, 150
4—Chloropheny l—pheny lether 7005—72—3 5 204 206, 141
Fluorerie ._73......7 5 166 165, 167
4—Nitroaniline I00—O1--- 6 20 138 92, 108
4 ,6—Dinitro-—2—methylpbeno l 534—52—1 20 198 [ 82, 77
N—nitrosodiphenyiamine 86—30—--6 5 [ 69 168, 167
4—Broniophenyl—phenylether 101—55—3 5 248 250, 141
Hexach lorobenzene 118—74—1 5 284 142. 249
PencachiorophencE 87—86—5 20 266 264, 268
Phetianthrene 85—01—8 5 178 179, 176
Anthracene 120—12—7 5 178 179, 176
D i—n——bucy lphtha late 84—74-—2 5 149 150, 104
Fluoranthene 206—44—0 5 202 101, 100
Pyrerie 129—00——0 5 202 101, 100
Buty lbeazy lphthalate 85—68——7 5 [ 49 91, 206
3 ,3’—Dich lorobenzidine 91—94-—I 5 252 254, 126
Benzo(a)anthracene 56—553 5 228 229, 226
Chrysene 218—01—9 5 228 226, 229
bts(2—Ethythe yI)phthaIate 117—81—7 5 149 167, 279
Di—n-—octy lphtha late 1 17—84—-0 5 149 —
Benzo(b)fluoranthene 205—99—2 5 252 253, 125
BenzoØc)f luoran thene 207—08—9 5 252 253, 125
Ber zo(a)pyrene 50—32----8 5 252 253, 125
Indeno(1,2,3—cd)pyre ne 193—39—5 5 276 138, 227
Dibenz(a,h)anthracene 53—70—3 5 278 139, 279
Benzo(g,h,i)perylene 191—24—--2 5 276 138, 277
APPENDIX D - 10 DRAFT 12196
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Appendix D OLCO2.l/SV
SAMPLE CONCENTRATION - The amount of analyce present in a sample is calculated using the RRF2O of the
continuing calibration standard in the following equation:
Sample concentration for water:
(A. ) (IS) (Va) (Df)
ug/L 7A. (RRF) (V 0 ) (V 2 )
Where,
= Area of the primary quantitation ion response (EICP) for the compound to be measured
= Area of the primary quantitation ion response (EICP) for the specific internal standard
IS = Amount of internal standard added in nanograms (ng)
RRF = The Relative Response Factor from the most recent continuing calibration standard
Df = Dilution Factor - The dilution factor for analysis of water samples for senuvolanles by this method
is defined as follows:
uL most conc. extract used to make dilution + uL clean solvent
uL most conc. extract used to make dilution
If no dilution is performed, Df = 1.
V 1 = Volume of the concentrated final extract in microliters (uL)
V 0 = Volume of water extracted in milliliters (mL)
V = Volume of extract injected in microlicers (uL)
CRQL CALCULATIONS
Water:
Adjusted CRQL = Contract CROL x
Where,
V , V , V 1 and Df are defined in the sample concentration equation above
V, 1 = Contract sample volume (1000 niL)
V, = Contract injection volume (1 uL)
= Contract concentrated extract volume (1000 uL)
APPENDIX D - 11 DRAFT 12/96
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Appendix D OLCO2.1/SV
SECTION XIV: TENTATIVELY IDENTWIED COMPOUND CRITERIA
Refer to Region 1, EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Analyses , Part
II, Section VOAJSV-XIV-B for tentatively identified compound (TIC) data validation criteria and the following
method TIC QC criteria:
The validaor is required to report up to 30 TICs in the Data Validation Memorandum.
TENTATIVELY IDENTII ’ LED COMPOUND CONCENTRATION - the estimated concentration for non-target
compounds tentatively identified shall be determined by the internal standard method using the following equations:
Sample concentration for water:
- ( Ar) (IS) (Va) (Df )
ug/L - (A. ) (RRF) (V 0 ) (Vi)
Where,
= Area of the primary quantitation ion response (EICP) for the non-target compound to be measured
= Area of the primary quantitation ion response (EICP) for the specific internal standard
IS = Amount of internal standard added in nanograms (ng)
RRF = Relative Response Factor of I (one) is assumed
Df = Dilution Factor - The dilution factor for analysis of water samples for semivolatiles by this method
is defined as follows:
uL most conc. extract used to make dilution + uL clean solvent
uL most conc. extract used to make dilution
If no dilution is performed, Df = 1.1
V , = Volume of the concentrated final extract in microliters (uL)
V 0 = Volume of water extracted in milliliters (mL)
V = Volume of extract injected in nücroliters (uL)
SECTION XV: SEMIVOLATILE CLEANUP CRITERIA
Not applicable to low concentration semivolatile analysis.
SECTION XVI: SYSTEM PERFORMANCE CRITERIA
Refer to Region 1. EPA-NE Data Validation Functional Guidelines for Evaluating Environmental Part
H, Section VOAJSV-XVI-B for system performance data validation criteria.
SECTION XVII: OVERALL ASSESSMENT
Refer to Reeion I EPA-NE Data Validation Functional Guidelines for Evaluatina Environmental Analyses , Part
II, Section VOA/SV-XVII-B for overall assessment data validation criteria.
APPENDIX D - 12 DRAFT 12/96
-------
Appendix E
VOA/SV Functional Guidelines Action Tables
Note: This appendix is a compilation of the data validation actions that appear in tabular format
in Part U - VOLATILE! SErvUVOLATILE Data Validation Functional Guidelines. Other actions
that are presented in tabular format are not contained in this appendix and the validator must
refer to Part LI to obtain the complete set of actions.
-------
VOA/SV ACTION TABLES
APPEN1MX E
Table VOA/SV-j- 1:
Q!JALIFICATION OF VOLATILE ANALYTES BASED ON
PRESERVATION & TECHNICAL HOLDING TIMES
PRESERVATION
]____________
TECHNICAL H
OLDING TIMES
Mamx
Rcfrte &
Ltgli t
Protected
ACId
Preserved
7
Days
7 < MT 14
Days
14 < fiT 3
Days
> 28 Days
.
AQ
No
Yes or No
I - detects
R-non-dctects
i - detects
R-non-detccts
I - detects
R-non-Iietec ts
I - detects
AQ
Yes
Yc
A
A
I - detects
UI-non-detects
R-non-detects
I - detects
Aromatics
R-non-dececzs
I - detects
I
AQ
Yes
No
A
R-non-deteccs
-
R-non-detecrs
I
Non-aromatics
Non-aromatics
- detects
R-non-detects
A - detects
I
A-non-detects
- detects
Ui-non-detects
S/S
No
N/A
I- detects
R-non-detects
I - detects
R-non-dcteccs
—
I - detects
R-non-detects
I - detects
S/S
Yes
N/A
A
A
I - detects
R-non-detecis
UJ-non-iteteccs
I - detects
R-non-detec s
-___________________ —
Table VOAJSv-I -2:
QUALIFICATION OF SEMIVOLATTLE ANALYTES BASED ON
PRESERVATION & TECHNICAL HOLDING T1M
PRESFRVATION J
•
TECHNICAL HOLDING TIMES
Matrix
ReIng. & Light
Protected
Extracted
and/or
Extracted
and/or
If Extraction HT > 28 days
Analyzed
Within H.T.
Analyzed
Outside H.T
and/or
Analytical HT > 60 days
—
I detects
J - detects
AQ and S/S
Yes
A
UI - non-detects
R - non-detects
AQ and S/S
No
J - detects
J - detects
I - detects
UJ - non-detects
UI - non-detects
R - non-detects
NOte: AQ = Aqueous, S/S = Soil/Sediment
For other matrices, the validator should estimate (J) positive detects and use professional judgment
to qualify or reject non-detects when Region I preservation and/or technical holding time criteria are not met.
For VOA aqueous samples containing excessive headspace (bubbles greater than 2 mm in diameter); J-detects, R-non-detects
A1’PENDIX E - 1 DRAFT 12/96
-------
APPENDIX E VOA/SV ACTION TABLES
Table VOA/SV-lll- 1
QUALIFICATION OF VOA/SV ANALYTES BASED ON THE iNITIAL CALIBRATION
Sample Results
QC Criterion
0.05
%RSD 30.0%
Situation 1
RRF <0.05
%RSD 30.0%
Situation 2**
RRF 0.05
%RSD >30.0%
Situation 3
RRF < 0 05
%RSD > 30.0%
Detects
A
J
J
J
Non-detects
A
R
Ui
R
** See Table VOAISV-III-2 for additional guidance.
Table VOAISV-JII-2:
EXPANDED INITIAL CALIBRATION VOA/SV ANALYTE QUALIFICATIONS
Sample Results
Elimination of
Elimination of
Elimination of
High or Low
High
Low
Calibration
Calibration
Calibration
Points
Points
Points
%RSD > 30.0%
%RSD 30.0%
% Q 30.0%
RRF 0.05 —
RRF 0.05
Detects
J
A: On linear
A: On linear
portion of curve
portion of
curve
On high end of
curve outside
J: On low end of
linear portion
curve outside
linear portion
Non-detects
UI
A
UI
Table VOAJSV-IV-I:
QUALIFICATION CF VOA/SV ANALYTES BASED ON THE CONTINUING CALIBRATION
Sample Results
QC Criteria
RRF 0.05
%D ± 25.0%
Situation I
RRF < 0.05
%D ± 25.0%
Situation 2
RRF 0.05
%D> ± 25.0%
Situation 3
RRF < 0.05
%D> ± 25.0%
Detects
A
J
I
I
Non-Detects
A
R
UJ
R
APPENDII( E - 2 DRAFI’ 12/96
-------
APPENDEX E
Table VOAJSv-vj.1:
VOA/SV ACTION TABLES
QUALIFICATION OF VOLATILE/SEMIVOLATILE ANALYTES BASED ON
SURROGATE COE tPOIJN1) RECOVERIES
Surrogate Compound Recovery
Sample
Results
one or more
surrogates < 10%
one VOA, two BIN or two
acid surrogates
10% %Rec < LI.
all VOA, one BIN or
one acid Surrogate
LL %Rec UL
one VOA, two BIN or
two acid surrogates
> jj
Detects
I
I
A
j
Non4eiects
R
UI
A
A
LL - Lower Limit of method QC acceptance crieria
UL - Upper Limit of method QC acceptance criteria
Table VOAISV-VII-1:
QUALIFICATION OF VOA/SV ANALYTES BASED ON INTERNAL STANDARD AREA COUNTS
Internal Standard Area Counts
Sample
Results
Area Counts <20%
of associated
calibration std. area
20% Area Counts < LL
LL Area Counts UL
Area Counts > UL
Detects
J
I
A
I
Non-detects
R
UJ
A
A
LL - Lower Limit of method QC acceptance cxiteria based on associated calibration standard area
UL - Upper Limit of method QC acceptance criteria based on associated calibration standard area
Table VOA/SV-Vffl -1:
QUALIFICATION OF ORGANIC ANALYTFS IN THE UNSPYKED FIELD SAMPLE
BASED ON MATRIX SPIKE RECOVERIES AND RPDs
Sample Results
Recovery < 10%
10% Recovery <
Lower QC Limit
Recovery>
RPD > QC Limit
Lower QC Limit
Recovery
Upper QC
Upper QC Limit
Limit
Detects
3
3
— A
3
3
Note that qualification and rejection generally are limited to the spiking compounds, however, the validator
may use professional judgment to qualify or rejec: i positive detects or non-detects n the unspiked sample
if the majority of spike compound recoveries and/or RPDs are outsiue the method QC acceptance criteria.
APPENDIX E - 3
DRAFF 12/96
-------
APPENDLX E
VOA/SV ACTION TABLES
Table VOA/SV-VlII-2
QUALIFiCATION OF ORGANIC ANALYFES IN THE UNSP [ KED FIELD SAMPLE
BASED ON MS , MSD, AND UNSPIKED SAMPLE %RSD
Sample Results
%RSD 50%’
%RSD> 50%’
Two out of three sample
results reported as non-detects
Detects
A
.
Professional Judgment
Non-detects
A
Professional Judgment
Professional Judgment
* If a non-detected result is reported for a compound in one of the samples in the MS. MSD or unspiked
sample set, then the validator should use the sample quantitation limit value for that compound to calculate
the %RSD
Table VOAJSV-IX- 1:
OUALIFICATION OF ORGANIC ANALYFES IN FIELD DUPLICATES -
SiTUATION 1: POSITIVE DETECTS IN BOTH FIELD DUPLICATES
Relative
Percent
Difference
Aqueous > 30%
Non-Aqueous > 50%
AqutotLi > 30%
Non-Aqueous > 50%
Aqueous > 30
I Non-Aqueous > 50%
Sample Results
Both duplicate sample
coocs 2XQL
QL both duplicate samples
con . <2XQL
One sample conc. 2 X QL
QL Othersaznulecouc. <2XQL
Detects
I
Professional Judgment
Pmfess onaj Judgmcrn
L Non-detects
NA
NA
NA I
* QL = Sample Quantitacion Limit
Note: Qualification refers to field duplicate sample results only. Professional judgment may be utilized to apply
field duplicate actions to all samples of the same matrix.
Table VOAJSV-IX-2
QUALIFICATION OF ORGANIC ANALYTES IN FIELD DUPLICATES -
SiTUATION 2: POSITIVE DETECT IN ONLY ONE FIELD DUPLICATE**
* QL = Sample Quantitation Limit
RPD should not be evaluated for these duplicate pairs
Note Qualification refers to field duplicate sample results only Professional judgment may be utilized to aDpiv
field duplicate actions to all samples of the same matrix.
.%oueous and Non-Aqueous
Results One Sample Conc. = ND (or value reported as
less than the QL)
QL Other Sample Cone. < 2 X QL
One sample cone. = ND (or value
reported as less than the QL)
Other sample cone. 2 X QL
Professional Judgment
J
Professional Judgment
tJI
APPENDIX E - 4
DRAFF 12/96
-------
APPENDIX E VOA/SV ACTION TABLES
Table VOAJSV.X-1.
QUALIFICATION OF ORGANIC ANALYTES BASED ON I’1DL STUDY RESULTS
Sample Results
Mean % Recovery
%Rec < 10%
10% %Rec < 30%
J 80% %Rec 120% %Rec> 120%
Detects
3
Professional Judgment’
A Professional
Non-Detects
R
Professional Judgment’
A A
Saniple Resiiits
%
RSD
>25%
zs
Detects
Professional Judgment”
A
Non-detects
—
Professional Judgment”
A
* Taking into consideration LFB results.
Taking into consideration initial caiibration %RSDs.
Table VOA/SV-X.2:
OMALIFICATION OF ORGANIC ANALYZES BASED ON LFB* RECOVERIES WHERE:
ONE -fl J,F OF LFB COMPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE LIMITS
Samole
Results
%Recovery
%Rec < 10%
10% %Rec <60%
60% %Rec 140%
%Rec> 140%
Detects
j
J
A
j
Non-detects
R
UJ
A
A
* LFB = Laboratory fortified blank spiked with several or all of the method target compounds at or below
the quancitacion limit.
Table VOAJSV -X 3•
QUALIFICATION OF ORGANIC ANALYTES BASED ON LFB RECOVERIES WHERE:
> ONE-HALF OF LFB COMPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE LIMITS**
[ Sample Results
L
%Reco
%Rec < 10%
10% %Rec <60%
60% %Rec 140%
%Re’> 140%
!jDececcs
J
J
A J
All Non-detects
R
—
Ui
A
A
* LFB = Laboracori fortified blank spiked with several or all of the method target compounds at or beiow
the quanutauon limit.
Professional Jud2menc should be used when a combination of low recoveries and high recoveries are
obtained
APPENDIX E - 5 DRAFT 12196
-------
APPENDIX E VOA/SV ACTION TABLES
Table VOAJSV-XI-L
QUALIFICATION OF INDIVIDUAL ORGANIC ANALYTES BASED ON LCS RECOVERIES WHERE:
ONE-HALF OF LCS COMPOUNDS OUTSIDE UPPER OR LOWER ACCEFFANCE LIMITS
Sam pie Results
%_Recovery
%Rec < 10%
10% %Rec tJL
Detects
J
J
A
j
Non-detects
R
UI
A
A
LL - Lower Limit of method QC acceptance criteria
UL , Upper Limit of method QC acceptance criteria
Table V/SV-XI-2:
JALIFICATION OF ORGANIC ANALYTES BASED ON LCS RECOVERIES WHERE:
> ONE-HALF OF LCS COMPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE LTh,IITS*
Sample Results
%_Recovery
%Rec < 10%
10% %Rec UL
AllDetects
I
I
A
J
Non-detects
R
UI
A
A
* Professional judgment should be used when a combination of low recoveries and high recoveries are
obtained.
LL - Lower Lirmt of method QC acceptance criteria
UL Upper Limit of method QC acceptance criteria
Table VOA/SV-XI-3:
QUALIFICATION OF INDIVIDUAL ORGANIC ANALYTES BASED ON PES RESULTS WHERE:
ONE-HALF OF PES COMPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE LIMITS
Sample Results
•Single Blind
‘Double Blind
PES < Lower Limit
“Action Low”
‘Single Blind
‘Double Blind
PES “Within Warning Limits”
“Wariiing High/Warning Low”
‘Single Blind
‘Double Blind
PES > Upper Limit
“Action High”
Detects
J
A
I
Non-Detects
R
A
A
APPENDIX E - 6 DRAfl’ 12/96
-------
APPENDEX E VOA/SV ACTION TABLES
Table VOA/SV..XI -4:
UAL1FICATION OF ORGANIC ANALYFES BASED ON PES RESULTS WHERE:
> ONE-HALF OF PES COMPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE LIMITS *
Sample Results
•Single Blind
•Single Blind
•Single Blind
•Double Blind
•Double Blind
•Double Blind
PES < Lower Limit
PES “Within Warning Limits”
PES > Upper Limit
“Action Low”
“Warning High/Warning Low”
“Action High”
Detects
J
A
j
Al! Non-Detects
R
A
A
Professional judgment should be used when a combination of low recoveries and high recoveries are
obtained.
Table VOA/SV-XIll- 1:
Q!JALIFICATION OF YOLATILE/SEMIVOLATILE ORGANIC ANALYTES BASED ON
SAMPLE PERCENT SOLIDS
Sample Result % Solids > 30
10% % Solids 30%
% Solids < 10%
Detects
A
3
R
Non-detects
A
R
R
Table SV-XV- 1:
QUALIFICATION OF SEMIVOLATILE ANALYTES BASED ON
GPC CALIBRATION oU.&LrrY CONTROL
Criteria
Action
Peak
As per method QC acceptance criteria.
Professional Judgment
Resolution
Peak
Peak shapes must be symmetrical.
Professional Judgment
Shape
Retention
Retention time shifts between GPC calibration
Professional Judgment
Time Shift
checks must not exceed ± 5%
GPC Instrument
Target analytes must be < QL and surrogate
Refer to Section V for Blank
Blank
compound recoveries and IS area counts and/or
Actions
RTs (if added) must meet method QC acceptance
criteria. (NoteS CLP SOW OLMO3.2 does not
require the addition of surrogate compounds to the
GPC instrument blank)
APPENDIX E - 7 DRAFF 12/96
-------
APPENDIX E VOA/SV ACTION TABLES
Table VOA/SV-Xj-2.
QUALIFICATION OF SEMIVOLATILE ANALYTES BASED ON GPC CLEANUP QUALITY CONTROL
WHERE: ONE-HALF OF GPC CALIBRATION CHECK COMPOUNDS OUTSIDE UPPER OR
LOWER ACCEPTANCE LIMITS
Sample Results
% Recovery
%Rec < 10%]
10% %Rec UL
Detects
J J
J
A
j
Ion -detects J
R
UJ
A
A
LL i Lower Limit of method QC acceptance criteria
UL Upper Limit of method QC acceptance crIteria
Table V/SV-XI-3
QUALIFICATION OF SEMTVOLATILE ANALYTES BASED ON GPC CLEANUP QUALITY CONTROL
WHERE: > ONE-HALF OF GPC CALIBRATION CHECK COMPOUNDS OUTSIDE UPPER OR
LOWER ACCEPTANCE LIMiTS
Sample Results
% Recovery
1
%Rec <_10%_ [ 10% %Rec UL
AilDetects
J
J
A
J
All Non-detects
R
UJ
A
A
Note: Professional judgment should be used when a combination of low recoveries and high recoveries are
obtained.
LL - Lower Limit of method QC acceptance criteria
UL - Upper Limit of method QC acceptance criteria
APPENDIX E - S DRAFI’ 12/96
-------
APPENDIX E
VOA/SV ACTION TABLES
Table SV-XV4:
QUALIFICATION OF SEMIVOLATILE AINALYTES BASED ON SILICA GEL
CLEANUP OUALITY CONTROL WFIERE ONE HALF OF SILICA GEL CHECK SOLUTION
COMPOUNDS OUTSIDE UPPER OR LOWER ACCEPTANCE CRITERIA
Sample Results
% Recovery
%Rec < 10%
10% %Rec LL LL %Rec UL
%Rec > UL
Detects
J
J
A
j
Non-detects
R
UJ
A
A
Silica Gel Column
Blank
Target analytes must be < QL and surrogate compound
recoveries and IS area counts and/or RTs (if added) must meet
method QC acceptance criteria.
Refer to Section
V for Blank
Actions
Note: Professional judgment should be used in applying the guidance above to qualify or reject sample data.
- Lower Limit of method QC acceptance criteria.
- Upper Limic of method QC acceptance criteria.
QUALIFICATION OF SEMIVOLATILE ANALYTES BASED ON SILICA GEL CLEANUP QUALITY
CONTT nT. WHERE: > O ’F-HALF OF SIT I A GEL C ’TC SOLUTION COMPOUNT)S OUTSJT)F
UPPER OR LOWER ACCEPTANCE LIMITS
Resutts
% Recovery
% ec < 10%
10% %Rec UL
I
I
A
J
Non-detects
R
UI
A
A
Note: Professional judgment should be used when a combination of low recoveries and high recoveries are
obtained -
- Lower Limit of method QC acceptance criteria
- Upper Limit of method QC acceptance criteria
LL
UL
Table V/SV-XI-5:
LL
UL
APPENDEX E - 9
DRAFT 12/96
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