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Polychlorinated Dibenzodioxins/
Polychlorinated Dibenzofurans SW-846 Method 8280
DATA Validation
Prepared by: Date:
Russell Arnone, Chemist HWSS
Peer Reviewed by: Date:
Muhammad Sheikh, Chemist HWSS
Concurred by: Date:
Michael Mercado, Acting Chief HWSS
Approved by: Date:
Robert Runyon, Chief, HWSB
Annual Review
Reviewed by: Date:
Reviewed by: Date:
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1.0 Introduction
1.1 The attached Standard Operating Procedure (SOP) is applicable to polychlorinated
dibenzodioxin and polychlorinated dibenzofuran (PCDD/PCDF) data. Its scope is to
facilitate the data validation process of the data reported by the contracting laboratory
and also to ensure that the data is being reviewed in a uniform manner.
1.2 The SOP is based upon the quality control and quality assurance requirements
specified in the analytical method PCDD/PCDF Protocol, Statement Of Work 9/91
(DFLM01.1) and its ensuing revision.
2.0 Responsibilities
2.1 The reviewer must be knowledgeable of the analytical method and its QC Criteria.
2.2 The reviewer must complete and/or file the following:
2.2.1 Data Assessment Checklist - The data reviewer must read each item carefully and
must check yes if there is compliance, no if there is non compliance and N/A if the
question is not applicable to the data.
2.2.2 Data Assessment Narrative - The data reviewer must present professional
judgement and must express concerns and comments on the validity of the overall
data package. The reviewer must explain the reasons for rejecting and/or qualifying the
data.
2.2.3 Rejection Summary Form - The reviewer must submit the completed form using a
ratio format. The numerator indicates the number of dioxins/furans data rejected; the
denominator indicates the number of dioxins/furans fractions containing rejected
compounds.
2.2.4 Organic Regional Data Assessment Summary - The data reviewer is also required
to submit the completed Organic Regional Data Assessment Form.
2.2.5 Telephone Record Log - All phone conversations must be initiated by the technical
project officer through SMO. If a phone call has been made, the reviewer must transcribe
the conversation. After the data review has been completed, the white copy of the
telephone log is mailed to the laboratory and the pink copy to SMO. The yellow copy is
filed in the appropriate folder. A photocopy of the Telephone Record Log is attached to
the Data Assessment Narrative.
2.2.6 Forwarded Paperwork - Upon completion of the review the following are to be
forwarded to the Regional Sample Control Center (RSCC):
a. data package
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b. completed data assessment checklist and narrative (original)
The reviewer will forward one copy of the completed Data Assessment and one copy of
the Organic Regional Data Assessment to the appropriate Regional TPO.
2.2.7 Filed Paperwork - The following are to be submitted to the Monitoring Management
Branch (MMB) files:
a. a photocopy of the Data Assessment Narrative
b. a photocopy of the Regional Data Assessment Summary
c. Telephone record Log (copy)
d. Rejection Summary Form
2.3 Rejection of Data - All values determined to be unacceptable on the Organic Analysis
Data Sheet (Form I) must be flagged with an "R". The qualifier R means that due to
significant QA/QC problems the analysis is invalid and it provides no information as to
whether the compound is present or not. Once the data are flagged with R any further
review or consideration is unnecessary.
The qualifier "J" is used to indicate that due to QA/QC problems the results are
considered to be estimated.
The qualifier "NJ" indicates that there is presumptive evidence for the presence of the
compound at an estimated value.
The data reviewer must explain in the data assessment narrative why the data was
qualified. He or she must also indicate all items of contract non-compliance.
When 2,3,7,8- substituted TCDD, TCDF, PnCDD and PnCDF data are rejected (flagged
"R") or qualified "J" the project officer must be notified promptly. If holding times have not
been exceeded reanalysis of the affected samples may be requested.
All qualifications and corrections to reviewed data must be made in red pencil.
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PACKAGE COMPLETENESS AND DELIVERABLES
CASE NUMBER:
LAB:
SITE:
1.0 Data Completeness and Deliverables YES NO N/A
1.1 Are the Traffic Report Forms present for all samples? [ ]
1.2 Is the Narrative or Cover letter present? [ ]
1.3 Are the Case Number and/or SAS numbers
contained in the case narrative? [ ]
1.4 Do the Traffic Reports or Lab Case Narrative indicate
problems with sample receipt, sample condition,
analytical problems, or other comments affecting the
quality of the data? [ ]
ACTION: Use professional judgement to evaluate the
effect of the noted problems on the quality
of the data.
2.0 Reporting Requirements and Deliverables
2.1 All deliverables must be clearly labeled with the SMO
number and the associated sample/traffic number.
Missing or illegible or incorrectly labeled items must
be identified. The contractor must immediately be
contacted and requested to submit the missing or
incorrect items.
2.2 Are the following forms present?
a. Sample Data Summary (Form I PCDD-1) [ ]
b. PCDD/PCDF Toxicity Equivalency Factor (Form I, PCDD-2) [ ]
c. Second Column Confirmation Summary (Form I, PCDD-3) [ ]
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d. Total Homologue Concentration Summary (Form II PCDD) [ ]
e. PCDD/PCDF Spiked Sample Summary (Form III PCDD-1) [ ]
f. PCDD/PCDF Duplicate Sample Summary (Form III PCDD-2) [ ]
g. PCDD/PCDF Method Blank Summary (Form IV-PCDD) [ ]
h. PCDD/PCDF Window Defining Mix Summary (Form V-PCDD-1) [ ]
i. Chromatographic Resolution Summary (Form V PCDD-2) [ ]
j. PCDD/PCDF Analytical Sequence Summary (Form V PCDD-3) [ ]
k. Initial Calibration (Form VI, PCDD-1, PCDD-2) [ ]
I. Continuing Calibration (Form VII,PCDD-1, Form VII,PDD-2) [ ]
2.3 GC/MS Displays
a. Standard and sample SIM chromatograms. SIM and TIC
chromatograms must list date and time of analysis; the file
name; sample number; and instrument I.D. number. [ ]
b. Percent peak resolution valley [ ]
c. PCDD/PCDF window defining mix raw data [ ]
d. SIM mass chromatograms must display quantitation ion,
confirmation ion, daughter ion (M-COC1) and polychlorinated
diphenylether ion where applicable. [ ]
e. Integrated area and peak height must be listed for all
peaks 2.5 times above background. [ ]
f. All peaks must show retention time at the maximum height.[ ]
2.4 Chain of Custody Records and in-house Laboratory Control
Documents
a. EPA Chain of Custody Records [ ]
b. SMO Sample Shipment Records [ ]
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c. Sample log-in sheets [ ]
d. GC/MS Standard and Sample Run Log in
chronological order [ ]
e. Sample Extraction Log [ ]
2.5 The Sample Package Data must be paginated.
ACTION: If deliverables are missing call the lab for
explanation/resubmittal. If the lab cannot
provide missing deliverables, assess the effect
on the validity of the data. Note in the
reviewers narrative.
3.0 Holding Times
3.1 Have any holding times been exceeded?
a. For aqueous samples 30 days from sample collection
to extraction. [ ]
b. For soil/sediment samples 30 days from sample collection
to extraction. [ ]
c. For all samples 40 days from time of extraction to time
of analysis. [ ]
ACTION: If holding times are exceeded, flag all data as
estimated ("J"). Holding time criteria do not apply
to PE samples.
4.0 Instrument Performance
4.1 Mass Calibration - Mass calibration of the MS is recommended
prior to analyzing calibration solutions, blanks, samples, and
QC samples. The lab is not required to submit mass calibration
data.
4.2 Window Defining Mixture/Column Performance Mixtures
4.2.1 The Window Defining Mixture and the Column Performance
Mixture must be analyzed prior to the initial calibration. It must
also be analyzed whenever the retention time of either recovery
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standard in any analysis varies by more than 10 seconds from
the most recent continuing calibration standard.
4.2.2 The window defining mix must contain the first and the
last isomers of each homologue PCDD/PCDF, (the internal
and recovery standards are optional).
4.2.3 All peaks must be labeled and identified on the SICPs.
ACTION: If the window defining mix was not analyzed at the
required frequency use professional judgement to
determine the effect on the quality of the data.
4.3 Chromatographic Resolution
4.3.1 For analyses on a DB-5 (or equivalent) GC column, the
chromatographic resolution is evaluated by the analysis of
the CC3 Standard Solution during the initial and continuing
calibration.
4.3.2 For analyses on a SP-2331 (or equivalent) GC column the
chromatographic resolution is evaluated before the analysis
of initial calibration by the analysis of the column
performance mixture. This commercially available solution
contains the 2378-TCDD and the isomers eluting immediately
prior and after the 2378-TCDD on SP-2331 or equivalent.
4.3.3 For SP-2331 or equivalent, the peak separation between the
unlabeled 2378-TCDD and the peaks of 1468-TCDD and the
1237/1238-TCDD isomer pair shall be resolved with a valley
of < 25 percent.
Valley = (x/y)x (100)
Y = The peak height of 2,3,7,8-TCDD isomer or any
TCDD isomer
X = The distance from the baseline to the bottom of the
valley between the adjacent peaks.
ACTION: If the percent valley criteria are not met, qualify all
positive data J. Do not qualify non-detects.
5.0 Initial 5-Point Calibration - The initial calibration standard
solutions (CC1-CC5) must be analyzed prior to any sample
analysis. They do not have to be analyzed daily provided the
continuing calibration standard met all criteria. However,
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initial calibration should be analyzed at least once every
week and/or whenever the continuing calibration standard
does not meet all criteria.
The calibration standards must be analyzed on the same instrument
using the same GC/MS conditions that were used to analyze
the window defining mix. The CC3 solution must contain the
supplemental calibration solution (see analytical method - Table 3).
5.1 The following MS/DS conditions must be used:
5.1.1 Scanning time was < 1 second. [ ]
5.1.2 SIM data were acquired for each of the ions listed in Table 5
including interfering ions (see analytical method) [ ]
5.2 The following GC criteria must be met:
5.2.1 The chromatographic resolution between the 13Ci22378-TCDD
and 13Ci2l234-TCDD isomers must be resolved with a valley
of < 25 percent method.
5.2.2 In the CC3 solution, the chromatographic peak separation
between 1,2,3,4,7,8-HxCDD and 1,2,3,6,7,8-HxCDD shall
be resolved with a valley of < 50 percent.
5.2.3 For all calibration solutions the retention times of the isomers
must fall within the retention time windows established by
the window defining mix. In addition the absolute retention
time of recovery standards, 13Ci2l234-TCDD and
13Ci2-123789HxCDD shall not change by more than 10
seconds between the initial CC3 analysis and the analysis of
any other standard.
5.2.4 The three SIM ions for each homolog must maximize
simultaneously and within 3 seconds of the corresponding
labeled isomer ions.
5.2.5 The relative ion abundance criteria for PCDDs/PCDFs listed
in table 6 (see analytical method) must be met.
5.2.6 The relative ion abundance criteria for the labeled internal and
recovery standards listed in table 6 must be met.
5.2.7 For all calibration solutions, including CC3, the signal to noise
ration (S/N) for all ions of the unlabeled PCDDs/PCDFs must
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be greater than 2.5.
5.2.8 For the internal and recovery standards, the signal to noise
ratio for all ions must be greater than 10.
5.2.9 The percent relative standard deviation (% RSD) of the five
RRFs (CC1-CC5) for the unlabeled PCDDs/PCDFs and the
internal standards must not be greater than 15 percent.
ACTION: 1. If the 25% percent valley for TCDD and 50%
valley for HxCDD requirement is not met, quality
positive data J. Do not qualify non-detects. The
tetra, pentas and hexas (dioxins and furans) are
affected. Heptas and Octas are not affected.
2. If the %RSD for each isomer exceeds 20%
percent, flag the associated sample positive
results for that specific isomer as estimated
("J"). No effect on the non-detect data.
3. If the ion abundance ratio for an analyte
is outside the limits flag the results for
that analyte R (reject).
4. If the ion abundance ratio for an internal or
recovery standard falls outside the QC limits
flag the associated positive hits with J. No
effect on the non-detects.
5. If the signal to noise ratio (S/N) is below control
limits, use professional judgement to determine
quality of the data.
6. If the selected monitoring ions specified in Table 5
were not used for data acquisition, the lab must be
asked for an explanation. If an incorrect ion was used,
reject all the associated data.
5.2.10 Spot check response factor calculations and ion ratios. Ensure
that the correct quantitation ions for the unlabeled PCDDs/PCDFs
and internal standards were used. In addition verify that the
appropriate internal standard was used for each isomer.
To recalculate the response factor use the equation:
RRFn = (An1 + An2) x Ck
(Ajs + Ajs ) X Qn
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RRFis = (Aig1 + Ak2) x Qrg
(Ars + Ars ) X Qjs
Where:
An1 and An2 = integrated areas of the two quantitation
ions of isomer of interest (Table 5).
Ais1 and Ais2 = integrated areas of the two quantitation
ions of the appropriate internal
standard (Table 5).
Ars1 and Ars2 = integrated areas of the two quantitation
ions of the appropriate recovery
standard (Table 5).
Qn = quantity of the unlabeled PCDD/PCDF analyte
injected (ng)
Qis = quantity of the appropriate internal standard
injected (ng)
Qrs = quantity of the appropriate recovery standard
injected (ng)
6.0 Continuing Calibration - The continuing calibration consists of two
parts: evaluation of the chromatographic resolution and verification
of the RRF values to be used for quantitation.
6.1 Chromatographic Resolution - At the beginning of each 12 hour
period the chromatographic resolution is verified in a similar
fashion as in the initial calibration: through the analysis of CC3
Standard Solution on the DB-5 (or equivalent) column or through
the analysis of the column performance solution on the SP2331
(or equivalent) column.
6.1.2 Was the continuing calibration and the column performance
solution (when applicable) run at the required frequency? [ ]
6.1.3 Was the chromatographic peak separation on DB-5 (or
equivalent) column between 13Ci2-2378TCDD and C12
1234-TCDD isomers resolved with a valley of <25 percent? [ ]
6.1.4 Was the chromatographic peak separation on the SP-2331
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(or equivalent) column between the unlabeled 2378-TCDD
and the adjacent TCDD isomers resolved with a valley of <25
percent?
YES NO N/A
[ ]
In addition, was the chromatographic peak separation between
the 123478-HxCDD and the 123678-HxCDD in the CC3 solution
resolved with a valley of <50 percent? [ ]
ACTION 1. If the continuing calibration standard was not analyzed
at the required frequency, reject all the data. Contact
TPO to initiate reanalysis.
2. If the 25 percent valley and 50 percent valley criteria are
not met qualify all positive data with J. Do not qualify
non-detects.
Note: The tetras, pentas and hexas (dioxins and furans) are affected.
Heptas and octas are not affected. If the percent valley is >75
percent and 2378-TCDD is non-detect but 1234-TCDD or an
adjacent TCDD isomer is present, the data is questionable.
The sample must be reanalyzed. Contact TPO. If the valley
criteria for HxCDD are not met but the valley criteria for TCDD
are met or vice-versa, use professional judgement to determine
which data must be qualified.
6.2 Continuing Calibration (CC3): The CC3 shall be analyzed at the
beginning of a 12 hour period.
6.2.1 The following MS/DS conditions were used:
6.2.2 Scanning time was < 1 second. [ ]
6.2.2.1 SIM data were acquired for each of the ions listed in
Table 5 including diphenylether interfering ions (see
analytical method). [ ]
6.2.3 The following GC criteria must be met:
6.2.3.1 For all calibration solutions the retention time of the
isomers must fall within the retention time windows
established by the window defining mix. [ ]
6.2.3.2 The absolute retention time of the recovery standards
13Ci21234-TCDD and 13Ci2123679-HxCDD shall not
change by more than 10 seconds between the initial
CC3 and ending CC1 standard analyses. [ ]
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6.2.3.3 The three SIM ions for each homolog must maximize
simultaneously (+ 2 sec) and within 3 seconds of the
corresponding ions of the labeled isomers.
6.2.3.4 For the CC3 standard solution, the signal to noise ratio
(S/N) for the unlabeled PCDD/PCDF ion shall be greater
than 2.5.
6.2.3.5 For the internal standards and the recovery standards,
the signal to noise ratio (S/N) shall be greater than 10.
6.2.3.6 The relative ion abundance criteria (Table 6 - analytical
method) for all PCDD/PCDF shall be met.
6.2.3.7 The relative ion abundance criteria for all internal and
recovery standards (Table 6 - analytical method) must
be met.
6.2.3.8 The measured RRF of each analyte and internal standard
in the CC3 solution must be within + 30 percent of the
mean RRF established during the initial calibration and
within + 30 percent of the single point RRFs obtained
during initial calibration for the supplemental calibration
standards.
Spot check response factor calculations and ion ratios.
Verify that the appropriate quantitation ions for the
unlabeled PCDD/PCDFs and internal standards were used. [ ]
6.2.3.9 Was the same internal standard used to calculate RRF
for each PCDD/PCDF homolog in the initial calibration? [ ]
ACTION: 1. If any of the requirements listed in sections 6.2.2,
6.2.2.1, 6.2.3.1, 6.2.3.2, and 6.2.3.9 are not met,
use professional judgement to determine the validity
of the data.
2. If any requirements listed in sections 6.2.3.3,
6.2.3.4, 6.2.3.5, 6.2.3.6, and 6.2.3.7 are not met
reject all data (flag R) directly affected by each
specific problem.
3. When the %D of the RRF is in between 30% and 50%
all the data for the outlier congeners are flagged J.
Data with %D above 50% are rejected (R).
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J
[ ]
[ ]
[ ]
[ ]
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6.2.3.10 To recalculate RRFs for the unlabeled target analytes,
and the RRFs for the five labeled internal standards,
use the following equations:
RRFn = (An1 + An2) x Qis
(Ais1 + Ais2) x Qn
RRFis = (Ais1 + Ais2) x Qrs
(Ars1 + Ars2) x Qis
An1, An2, Ais1, Ais2, Ars1, Ars2, Qn, Qis and Qrs are
defined in Section 5.2.10.
To calculate percent difference, use the following equation:
% Difference = (RRFi - RRFc) x 100
RRFi
Where
RRFi = Relative response factor established during
initial calibration
RRFc = Relative response factor established during
continuing calibration
6.3 Instrument Sensitivity - In order to demonstrate that the GC/MS
system has retained adequate sensitivity, during the course of
sample analysis, the lowest of the initial calibration standards
(CC1) is analyzed at the end of each 12-hour period.
6.3.1 Did all analytes in the CC1 solution meet ion abundance
criteria? [ ]
6.3.2 Did the retention time of the two recovery standards
13Ci21234-TCDD and 13Ci2123678HxCDD change by
more than +/-10 seconds? [ ]
6.3.3 For CC1 was the S/N ratio for all unlabeled PCDD/PCDF
ions greater than 2.5 and greater than 10 for the labeled
internal and recovery standards? [ ]
ACTION: If the CC1 standard did not meet criteria examine the
samples which were analyzed prior to this standard and
use professional judgement to determine if data qualification
is necessary. (See Recovery Standard areas - Section 9.0)
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7.0 Sample Data
7.1 The following MS/DS conditions were used:
7.1.1 Scanning time was < 1 second. [ ]
7.1.2 SIM data were acquired for each of the ions listed inTable 5
(see analytical method) including diphenylether interfering ions. [ ]
7.2 Identification Criteria
7.2.1 For the 2378 substituted isomers found present and for which
an isotopically labeled internal standard is present in the sample
extract, the absolute retention time at the maximum peak height
of the analyte must be within 3 seconds of the retention time of
the corresponding labeled standard. [ ]
7.2.2 For the 2378 substituted isomer reported present, and for which
a labeled standard does not exist, the relative retention time
(RRT) of the analyte must be within +.05 RRT units of the RRT
established by the continuing calibration standard (CC3). [ ]
7.2.3 For non-2378 substituted compounds (tetra through hepta) found
present, the retention time must be within the window established
by the window defining mix for the corresponding homologue.
7.2.4 All specified ions listed in Table 5 (analytical method) for each
PCDD/PCDF isomer found present and the labeled standards
must be present in the SICP. The three SIM ions for the
analyte, the internal standards and recovery standards must
maximize simultaneously (+2 seconds).
7.2.5 The integrated ion current for each characteristic ion of the
analyte identified as positive must be at least 2.5 times
background noise and must have not saturated the detector.
If the M-[COC1 ]+ ion does not meet the 2.5 times S/N
requirement but meets all other criteria, the reviewer must use
professional judgement to determine whether the compound
is present.
7.2.6 The integrated ion current for the internal standard characteristic
ions must be at least 10 times background noise. [ ]
[ ]
[ ]
[ ]
7.2.7 The relative ion abundance criteria (Table 6 - analytical method)
for all PCDDs/PCDFs found present must be met. [ ]
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7.2.8 The relative ion abundance criteria for the internal standards
must be met (Table 6 - analytical method).
ACTION: 1. Reject (flag R)all positive data for the analytes
which do not meet criteria listed in Sections
7.2.1, 7.2.2, 7.2.3, and 7.2.4.
2. If the criteria listed in section 7.2.5 are not met
but all other criteria are met, qualify all positive
data of the specific analyte with J.
3. If the requirements listed in section 7.2.6 are not
met but all other requirements are met qualify the
positive data of the corresponding analytes with "J'
4. If the analytes reported positive do not meet ion
abundance criteria, section 7.2.7, reject (R) all
positive data for these analytes. Change the
positive values to EMPC (estimated maximum
possible concentration).
5. If the internal standards and recovery standards
do not meet ion abundance criteria (Table 6 -
analytical method) but they meet all other criteria
flag all corresponding data with "J".
6. If PCDF is detected but an interfering PCDPE is
also detected reject the PCDF data (R). The
reported value of PCDF is changed to EMPC.
7. If the lab did not monitor for PCDE's qualify all
positive furan data N.
7.2.9 Spot check calculations for positive data and verify that the
same internal standards used to calculate RRFs were used to
calculate concentration and EMPC. Ensure that the proper
PCDDs/PCDFs and internal standards were used.
To recalculate the concentration of individual PCDD/PCDF
isomers in the sample use the following equation:
ALL MATRICES OTHER THAN WATER
Cn (ug/kg) = Qis x (An1 + An2)
W x (Ais1 +Ais2)xRRFn
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WATER
Cn (ng/L) = Qis x (An1 + An2)
V x (Ais1 + Ais2) x RRFn
Where:
An1 and An2 = integrated ion abundances (peak areas) of
The quantitation ions of the isomer of interest
(Table 5).
Ais1 and Ais2 = integrated ion abundances (peak areas) of
the quantitation ions of the appropriate
internal standard (Table 5).
W= Weight (g) of sample extracted
V= Volume (ml) of sample extracted
Qis= Quantity (ng) of the appropriate internal standard
added to the sample prior to extraction
RRFn= Calculated relative response factor from continuing
calibration (see Section 7.3).
Note: See SOW, Section 15.3 for calculations when any internal
standard in a diluted sample is less than 10% of the internal
standard area in the continuing calibration standard.
7.3 Estimated Detection Limits (EDL)
7.3.1 Was an EDL calculated for each 2,3,7,8-substituted isomer that
was not identified regardless of whether other non-2378
substituted isomers were present? [ ]
7.3.2 Use the equation below to check EDL calculations:
ALL MATRICES OTHER THAN WATER
EDL (ug/kg) = 2.5 x Qis x (Hx1 + Hx2) x D
Wx (His1 + His2) x RRFn
WATER
EDL (ng/L) = 2.5 x Qis x (Hx1 + Hx2) x D
V x (His1 + His2) x RRFn
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Where:
Hx1 and Hx2 = peak heights of the noise for both
quantitation ions of the 2,3,7,8-substituted
isomer of interest.
His1 and His2 = peak heights of both the quantitation ions
of the appropriate internal standards.
D = dilution factor (see Paragraph 10.4.3).
Qis, RRFn, Wand V are defined in Section 5.2.10
NOTE: The validator should check the EDL data to verify that
peak heights and not areas were used for this calculation.
If the area algorithm was used, the validator should
contact the laboratory for recalculation. The TPO must
be notified.
7.4 Estimated Maximum Possible Concentration (EMPC)
7.4.1 Was an EMPC calculated for 2378-substituted isomers that had
S/N ratio for the quantitation and confirmation ions greater than
2.5, but did not meet all the identification criteria? [ ]
7.4.2 Use the equation below to check EMPC calculations:
ALL MATRICES OTHER THAN WATER
EMPC (ug/L) = (Ax1 + Ax2) x Qis x D
(Ais1 + Ais2) x RRFn x W
WATER
EMPC (ng/L) = (Ax1 + Ax2) x Qis x D
(Ais1 + Ais2) x RRFn x V
Where:
Ax1 and Ax2 = areas of both quantitation ions.
Ais1, Ais2, Qis, RRF, D, W, and V are defined in
Paragraph 7.3.3 and 10.4.3 and Section 15.1.
Action: 1. If EDL or EMPC of an analyte which was not reported as
present is missing, contact the laboratory for correction.
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2. If the spot check calculations yielded EDLs or EMPCs
different from those reported in Form I, contact the
laboratory for an explanation.
3. If EDLs or EMPCs for the most toxic analytes
(TEF> 0.05) are above CRQLs contact TPO for
sample reanalysis.
7.5 Method Blanks
7.5.1 Has a method blank per matrix been extracted and analyzed with
each batch of 20 samples? [ ]
7.5.2 If samples of some matrix were analyzed in different events
(i.e. different shifts or days) has one blank for each matrix been
extracted and analyzed for each event? [ ]
7.5.3 Acceptable method blanks must not contain any signal of
2378-TCDD, or2378-TCDF, equivalent to a concentration
of > 0.1 ppb for soils or 1 ppt for water samples. [ ]
7.5.4 For other 2378- substituted PCDD/PCDF isomers of each
homologue, the allowable concentration in the method blank is
less than 1/10 of the CRQL listed in the SOW or the area must
be less than 2% of the area of the nearest internal standard. [ ]
7.5.5 For the peak which does not meet identification criteria as
PCDD/PCDF in the method blank, the area must be less than
5% of the area of the nearest Internal Standard. [ ]
ACTION: 1. If the proper number of method blanks were not analyzed,
notify the contractor. If they are unavailable, reject all
positive sample data. However, the reviewer may also use
professional judgement to accept or reject positive sample
data if no blank was run.
2. If the method blank is contaminated with 2378-TCDD,
2378-TCDF, 12378PeCDD, 12378PeCDFor
23478 PeCDF at a concentration higher than the CRQL
listed in the SOW, reject all contaminant compound
positive data for the associated samples (flag R) and
contact the technical project officer to initiate reanalysis
if it is deemed necessary.
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Polychlorinated Dibenzodioxins/
Polychlorinated Dibenzofurans SW-846 Method 8280
DATA Validation
Prepared by:
VW\ —<
, Chemist "HWSS
RusseU Arnorfe,
Peer Reviewed by: 16 r^- j Or L-k i (*
Concurred bj
Approved by:
ist HWSS
mad-Sheikh
' Michael Merdfedp, Acting Chielf H
Roberjj/Ruriyon, Chief, HWSB
Annual Review
Date: ' <~
Date:
Date: / ILIU
Reviewed by:
Date:
Reviewed by:
Date:
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YES NO N/A
3. If the method blank is contaminated with any of the above
isomers at a concentration of less than the CRQL or of any
other 2378-substituted isomer at any concentration and the
concentration in the sample is less than five times the
concentration in the blank, transfer the sample results to
the EMPC/EDL column and cross-out the value in the
concentration column. If the concentration in the sample
is higher than five times the concentration in the blank, do
not take any action.
7.6 Rinsate Blank
7.6.1 One rinsate blank must be collected for each batch of 24 soil
samples or one per day whichever is more frequent. [ ]
7.6.2 Do any rinsate blanks show the presence of 2378-TCDD,
2378-TCDF, and 12378PeCDD at amounts > .5 ug/L or any
other analyte at levels > 1 |jg/L? [ ]
ACTION: If any rinsate blank was found to be contaminated with
any of the PCDDs/PCDFs notify the technical project
officer to discuss what proper action must be taken.
7.7 Field Blanks
7.7.1 The field blanks are PEM samples (blind blanks) supplied by
EPA from EMSL-LV at the frequency of one field blank per 24
samples or less collected over a period of one week whichever
comes first. A typical "field blank" will consist of
uncontaminated soil. The field blanks are used to monitor
possible cross contamination of samples in the field and in
the laboratory. [ ]
7.7.2 Acceptable field blanks must not contain any signal of
2378-TCDD and 2378-TCDF equivalent to a concentration of
> 0.1 ppb. [ ]
7.7.3 For other 2378-substituted PCDD/PCDF isomers of each
homologue the allowable concentration in the field blank is less
than 1/10 the CRQL listed in the SOW. [ ]
ACTION: When the field blank is found to be contaminated with
target compounds apply the same action as described for
the method blank (section 7.5).
NOTE: Contact EPA EMSL/LV to verify that the PEM blank (field blank)
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did not contain any PCDD/PCDF isomers and ask their
assistance in the evaluation of the PE field blank.
8.0 Internal Standard Recoveries (Form I)
8.1 Were the samples spiked with all the internal standards as
specified in the method?
8.2 Were internal standard recoveries within the required limits?
8.3 If not, were samples reanalyzed?
ACTION: 1. If the internal standard recovery was below 25 percent,
reject (R) all associated non-detect data (EMPC/EDL)
and flag with "J" all positive data.
2. If the internal standard recovery is above the upper limit
(150 percent) flag all associated data (positive and
non-detect data) with "J".
3. If the internal standard recovery is less than 10% qualify
all associated data R (Reject). When highly toxic isomers
(TEF> 0.05) are affected, notify TPO to initiate reanalysis.
Calculate the percent recovery of internal standard (Ris) in
the sample extract using the following equation.
Recalculate the percent recovery for each internal standard
in the sample extract, Ris, using the formula:
Ris = (Ais1 + Ais2 x Qrs x 100%)
(Ars1 + Ars2 x RRFis x Qis)
Ais1, Ais2, Ars1, Ars2, Qis, Qrs and RRFis
are defined, previously.
9.0 Recovery Standards
There are no contractual criteria for the Recovery Standard area.
However, because it is very critical in determining instrument sensitivity,
the Recovery Standard area must be checked for every sample.
9.1 Are the recovery standard areas for every
sample and blank within the upper and lower limits of
each associated continuing calibration?
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YES NO N/A
[ ]
[ ]
[ ]
Area upper limit= +100% of recovery standard area.
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Area lower limit= -50% of recovery standard area.
9.2 Is the retention time of each recovery standard within
10 seconds of the associated daily calibration standard?
ACTION: 1. If the recovery standard area is outside
the upper or lower limits flag all related
positive and non-detect data (EMPC/EDL)
with "J" regardless whether the internal
standard recoveries met specifications or not.
2. If extremely low area counts (<25%) are
reported flag all associated non-detect data
as unusable (R) and the positive data J.
3. If the retention time of the recovery
standard differs by more than 10 seconds
from the daily calibration use professional
judgement to determine the effect on the results.
A time shift of more than 10 seconds may
cause certain analytes to elute outside the
retention time window established by the window
defining mix.
10.0 Matrix Spikes (PEM Blanks)
10.1 One known blank usually an interference fortified
soil/sediment sample, supplied by EPA, EMSL-LV, is
designated by the sampling team for the laboratory
for spiking. The frequency of this QC sample is one
per group of 24 environmental samples or less collected
over a period of one week whichever is first.
The sample is spiked by the laboratory with
the appropriate volume of the matrix spiking solution
specified in the analytical protocol (SOW) and then
extracted and analyzed with the other samples.
10.2 Was a fortified PEM blank analyzed at the frequency
described above?
10.3 Was the percent recovery of 2378-TCDD and other 2378-
substituted compounds within the 50 to 150 percent
control limit?
ACTION: 1. If the recovery of a 2,3,7,8-substituted
isomer falls outside the 50-150 percent control
limit, flag all positive and non-detect date of
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the same and related isomers in the same homolog
series with J. However, if the recovery is below
20 percent qualify all associated non-detects R.
Notify the Technical Project Officer. Reanalysis
may be initiated.
2. If no fortified PEM blank was analyzed
use professional judgement to assess data
validity.
11.0 Matrix Spike (Field Sample)
11.1 Was a matrix spike analyzed at the frequency of one per
SDG samples per matrix?
11.2 Was the percent recovery of 2378-TCDD and other 2378-
substituted PCDDs/PCDFs within the same 50 to 150 percent?
ACTION: If problems such as interferences are observed,
use professional judgement to assess the quality
of the data. The 50-150% limits of the matrix spike
data may be used to flag data of the spiked sample
only. The matrix spike data of the PE blank sample
are more important and must be used primarily in
data validation.
12.0 Environmental Duplicate Samples
12.1 For every batch of 24 samples or less collected over a
period of one week whichever comes first there
must be a sample designated as duplicate.
Results of the duplicate samples must agree within 50%
relative difference.
ACTION: The duplicate results must be used in
conjunction of other QC data. If no hits
are reported, precision may be assessed
from the internal standard recoveries.
13.0 Performance Evaluation Samples
13.1 Included among the samples are sets of performance evaluation
samples containing known amounts of unlabeled 2378-TCDD
or a mixture of 2378-TCDD and other PCDD/PCDF isomers.
The PE samples are provided by the Region, and must be
analyzed at the frequency of one set per batch of 24 samples
or less collected over a period of one week whichever
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occurs first.
13.2 The analytical results must be within the EPA 99%
acceptance criteria.
ACTION: 1 .The PE samples must be validated as if
they were environmental samples.
There is no holding time for PE samples.
2. PE samples containing only 2378-TCDD
When 2378-TCDD was not qualitatively
identified, or if the reported concentration
is outside the 99% acceptance window all
positive and negative (EMPC/EDL) data for
all associated samples are rejected.
3. PE samples containing a mixture of PCDD/PCDF
isomers
When the reported concentration of any
analyte is outside the EPA 99% confidence
interval, all positive and negative (EMPC/EDL)
data of the 2378 substituted isomers within
the same homologue for all associated
samples are rejected.
4. When PCDD/PCDF data are rejected because
of PE results, the EPA technical project officer
must be notified. Reanalysis may be initiated.
5. For PE blind blanks see 7.7 (Field Blanks)
14.0 Second Column Confirmation
14.1 Was a second column confirmation performed?
14.2 Was the sample extract reanalyzed on a 60m SP-2330 or
SP-2331 GC column for better GC resolution and better
identification of the individual 2378-substituted isomers?
14.3 Did the second column meet the calibration and linearity
specification in the SOW (See sections 5.0 and 6.0).
14.4 Was the % D of the quantitation results of the two
columns less than 50?
ACTION: Use professional judgement to decide which
quantitation data to use. The two quantitation
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data should not be combined.
NOTE: If the sample extract was analyzed on a single GC
column capable of resolving all 2378-substituted
isomers, confirmation is not necessary.
15.0 Sample Reanalvsis
15.1 The Region II TPO will evaluate the need for reanalyzing the
samples with qualified data based on site-specific Regional
Data Quality Objectives. The rerun may be billable or non
billable as specified in the SOW. SMO should be notified of
all reruns.
15.2 Due to a variety of situations that may occur during sample
analysis the laboratory is required to reanalyze or reextract
and reanalyze certain samples. If a reanalysis was required
but as not performed, contact TPO to initiate reanalysis.
List below all reextractions and reanalyses and identify the
PCDD/PCDF sample data summaries (Form I) which must be used
by the data user (when more than one is submitted).
16.0 Isomer Specificity and Toxicity Equivalency Factor (TEF) -
When calculating the 2378-TCDD Toxicity Equivalency of a
sample only those 2378 substituted isomers that were
positively identified in the sample must be included in the
calculations. The sum of the TEF adjusted concentration is
used to determine when a second column confirmation is
required to achieve isomer specificity.
16.1 The lab did not include EMPC or EDL values in the toxicity
equivalency calculations.
16.2 All samples whose toxicity equivalency exceeded the required
values were reanalyzed on a confirmation column to establish
isomer specificity.
ACTION: 1. If the toxicity equivalency calculations were
not performed properly notify TPO.
2. If the toxicity equivalency exceeded the required
limits (0.7 ppb for soil/sediment, 7ppt for
aqueous and 7ppb for chemical waste samples), and the
lab failed to reanalyze the samples on a specific
secondary column, notify TPO.
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PCDFs/PCDDs Data Assessment
CASE NO. LABORATORY
Site
SAMPLE
NO.
DATA ASSESSMENT:
All data are valid and acceptable except those values which have been qualified R (rejected)
or qualified "J" (estimated). Rejected data does not imply the analyte is not present. It means
that due to significant QC problems the analysis is invalid and it provides no information as
to whether the compound is present or not.
All action is detailed below and on the attached sheets.
Reviewer's Signature:
Date: / 120
Verified By:
Date: / 120
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Case#
Site:
Lab:
Overall Assessment
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Case#
Site:
Lab:
Contract Problems/Non-Compliance
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