SOP HW-16
Revision 2.1
December 2010
Page 1 of 25
Validation of Data
Nitroaromatics and Nitroamines by HPLC, SW-846, Method 8330A
Prepared by:
Peer Reviewed by: ~
Concurred by:
Approved by
.jjJ jO^A/vy
I Arnorie, Chemist HWSS
((tfn-i " ^ ^i\ CJ i ^ l(y
heikh^Chemis
HWSS
de\ Mentado, Acting dhief H^fVSS
Robert Runyon, Chi efW/SB
Annual Review
Date: ' 2, i °l I < o
Date: [&
Date: /£/&/&
Date: I
Reviewed by:.
Date:
by
Name
-------
Scope and Applicability
This SOP offers detailed guidance in evaluating laboratory data generated
according to "SW846-Method 8330A" January 1998. Method 8330A is used to
determine the concentration of nitroaromatics and nitroamines organic
compounds in extracts prepared from many types of solid waste matrices,
soils, and water samples. The validation methods and actions discussed in
this document are based on the requirements set forth in SW846 Method 8330A,
Method 8000C and the "USEPA Contract Laboratory Program National Functional
Guidelines for Organic Data Review," January 2005. This document covers
technical problems specific to each fraction and sample matrix; however,
situations may arise where data limitations must be assessed based on the
reviewer's professional judgement.
Summary of Method
To ensure a thorough evaluation of each result in a data case, the
reviewer must complete the checklist within this SOP, answering specific
questions while performing the prescribed "ACTIONS" in each section.
Qualifiers (or flags) are applied to questionable or unusable results as
instructed. The data qualifiers discussed in this document are defined on
page 4.
The reviewer must prepare a detailed data assessment to be submitted
along with the completed SOP checklist. The Data Assessment must list all
data qualifications, reasons for qualifications, instances of missing data
and contract non-compliance.
Reviewer Qualifications
Data reviewers must possess a working knowledge of SW846 Analytical
Methods and National Functional Guidelines mentioned above.
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SOP HW-16
Revision 2.1
December 2010
Page 1 of 25
Validation of Data
Nitroaromatics and Nitroamines by HPLC, SW-846, Method 8330A
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: _
Name
Reviewed by: Date:
Name
-------
Scope and Applicability
This SOP offers detailed guidance in evaluating laboratory data generated
according to "SW846-Method 8330A" January 1998. Method 8330A is used to
determine the concentration of nitroaromatics and nitroamines organic
compounds in extracts prepared from many types of solid waste matrices,
soils, and water samples. The validation methods and actions discussed in
this document are based on the requirements set forth in SW846 Method 8330A,
Method 8000C and the "USEPA Contract Laboratory Program National Functional
Guidelines for Organic Data Review," January 2005. This document covers
technical problems specific to each fraction and sample matrix; however,
situations may arise where data limitations must be assessed based on the
reviewer's professional judgement.
Summary of Method
To ensure a thorough evaluation of each result in a data case, the
reviewer must complete the checklist within this SOP, answering specific
questions while performing the prescribed "ACTIONS" in each section.
Qualifiers (or flags) are applied to questionable or unusable results as
instructed. The data qualifiers discussed in this document are defined on
page 4.
The reviewer must prepare a detailed data assessment to be submitted
along with the completed SOP checklist. The Data Assessment must list all
data qualifications, reasons for qualifications, instances of missing data
and contract non-compliance.
Reviewer Qualifications
Data reviewers must possess a working knowledge of SW846 Analytical
Methods and National Functional Guidelines mentioned above.
-------
USEPA Region II
SW846 Method 8330A
DEFINITIONS
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
Acronyms
CLP - Contract Laboratory Program
CRQL - Contract Required Quantitation Limit
%D - percent difference
DoC - Date of Collection
GC - gas chromatography
HPLC - high performance liquid chromatography
IS - internal standard
kg - kilogram
[ig - microgram
MS - matrix spike
MSD - matrix spike duplicate
i - liter
mfi - milliliter
PE - performance evaluation
PEM - Performance Evaluation Mixture
QC - quality control
RAS - Routine Analytical Services
RIC - reconstructed ion chromatogram
RPD - relative percent difference
RRF - relative response factor
RRF - average relative response factor (from initial calibration)
RRT - relative retention time
RSD - relative standard deviation
RT - retention time
RSCC - Regional Sample Control Center
SDG - sample delivery group
SMC - system monitoring compound
SOP - standard operating procedure
SOW - Statement of Work
SVOA - semivolatile organic acid
TCL - Target Compound List
TIC - tentatively identified compound
TOPO - Task Order Project Officer
TPO - Technical Project Officer
VOA - Volatile organic
VTSR - Validated Time of Sample Receipt
Data Qualifiers
U -The analyte was analyzed for, but was not detected above the reported
sample quantitation limit.
J -The analyte was positively identified; the associated numerical value
is the approximate concentration of the analyte in the sample.
N -The analysis indicates the presence of an analyte for which there is
presumptive evidence to make a "tentative identification."
-Nitro Aromatics/Amines 3 -
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USEPA Region II Date: December 2010
SW846 Method 8330A SOP HW-16 Rev. 2.1
YES NO N/A
NJ -The analysis indicates the presence of an analyte that has been
"tentatively identified" and the associated numerical value represents its
approximate concentration.
UJ -The analyte was not detected above the reported sample quantitation
limit. However, the reported quantitation limit is approximate and may or
may not represent the actual limit of quantitation necessary to accurately
and precisely measure the analyte in the sample.
R -The sample results are rejected due to serious deficiencies in the
ability to analyze the sample and meet quality control criteria. The
presence or absence of the analyte cannot be verified.
LAB QUALIFIERS:
D - The positive value is the result of an analysis at a secondary
dilution factor.
B - The analyte is present in the associated method blank as well as
in the sample. This qualifier has a different meaning when
validating inorganic data.
E - The concentration of this analyte exceeds the calibration range
of the instrument.
A - Indicates a Tentatively Identified Compound (TIC) is a suspected
adol-condensation product.
X,Y,Z- Laboratory defined flags. The data reviewer must change these
qualifiers during validation so that the data user may
understand their impact on the data.
-Nitro Aromatics/Amines 4 -
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
PACKAGE COMPLETENESS AND DELIVERABLES
CASE NUMBER:
SDG#
LAB:
SITE:
1.0 Introduction
1.1 The attached Standard Operating Procedure (SOP) is applicable to nitro substituted
aromatic and nitro substituted amines by High Performance Liquid Chromatography
(HPLC)data. Its scope is not only to facilitate the data validation process of the data
reported by the contracting laboratory, but also to ensure the data is being reviewed in a
uniform manner.
1.2 This SOP is based upon the quality control assurance requirements specified in
analytical SW 846 Method 8330A Revision 1, January 1998, and the National Function
Guidlines, January 2005.
2.0 Responsibilities
2.1 The reviewer must be knowledgeable of the analytical method and its criteria.
2.2 The reviewer must complete and/or file the following:
Data Assessment Checklist - The data reviewer evaluates Each criterion carefully and
checks if data is in compliance, non-compliace or not applicable.
Data Assessment Narrative - The data reviewer must present professional judgement,
address areas of concern and comment on the validity of the overall data package. The
reviewer must explain the reasons for rejecting and or qualifying the data.
Telephone Record Log - All phone conservations must be transcribed by the reviewer.
Upon completion of the data review, the original telephone log is attached to the data
assessment narrative.
-Nitro Aromatics/Amines 5 -
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USEPA Region II Date: December 2010
SW846 Method 8330A SOP HW-16 Rev. 2.1
YES NO N/A
3.0 Data Completeness and Deliverables
3.1 Has all the data been submitted in CLP deliverable format?
3.2 Have any missing deliverables been received and added to the data package?
ACTION: Call lab for explanation/resubmittal of any missing deliverables. If
lab cannot provide them, note the effect on review of the data in the
reviewer narrative.
4.0 Cover Letter, SPG Narrative
4.1 Is a laboratory narrative or cover letter present?
4.2 Are the case number and/or SDG number contained
in the narrative or cover letter?
5.0 Data Validation Checklist
5.1 Does this data package contain:
Water data?
Waste data?
Soil/solid data?
6.0 Traffic Reports and Laboratory Narrative
6.1 Are traffic report and chain-of-custody forms present for all samples?
J_L
ACTION: If no, contact lab for replacement of missing or illegible copies.
6.2 Do the traffic reports, chain-of-custody forms or SDG narrative indicate any
problems with sample receipt, condition of the samples, analytical problems or
-Nitro Aromatics/Amines 6 -
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USEPA Region II Date: December 2010
SW846 Method 8330A SOP HW-16 Rev. 2.1
YES NO N/A
special circumstances affecting the quality of the data?
ACTION: If any sample analyzed as a soil, contains 50%-90% water, all data should be
qualified as estimated, "J." If a soil sample contains more than 90% water, non
detects shall be qualified as unusable, "R."
ACTION: If samples were not iced or if the ice was melted upon arrival at the laboratory and the
temperature of the cooler was elevated (> 10° C), flag all positive results "J" and all
non-detects "UJ".
7.0 Special QC
7.1 Prior to preparation of stock solutions; acetonitrile, methanol, and water should be
analyzed to determine possible interferences with analyte peaks. A different batch of
solvent should be used if contamination is present.
7.2 Chromatograms are to be submitted showing that there are no interferences with
analyte peaks.
Are these chromatograms present in package?
Are the chromatograms free of interferences?
Action: Ask lab for resubmittals. If deliverables are unavailable, judge the effect of the
validity of the data. If questionable, contact SMO and note in data assessment.
8.0 Holding Times
8.1 Have any nitroaromatics and nitroamines technical holding times, determined from date
of collection to date of extraction, been exceeded?
Water and waste samples must be properly perseved (cooled to 4° +/- 2°),
and nitro substituted aromatics and amines analysis must be extracted within
7 days of the date of collection. Extracts must be analyzed within 40 days of
-Nitro Aromatics/Amines 7 -
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
the date of extraction. Soils and solid samples must be extracted within 14
days of collection and analyzed within 40 days of extraction.
ACTION: If technical holding times are exceeded, flag all positive results as estimated, "J,"
and sample quantitation limits "UJ" and document in the narrative that holding times
were exceeded. If analyses were done more than 14 days beyond holding time,
either on the first analysis or upon re-analysis, the reviewer must use professional
judgement to determine the reliability of the data and the effects of additional
storage on the sample results. At a minimum, all the data should at least be
qualified "J", but the reviewer may determine that non-detects are unusable,"R."
(Table 1)
Table 1. Holding Time Criteria
Matrix
Preserved
Criteria
Action
Detected
compounds
Non-detected
compounds
No
< 7 days(extraction)
< 40 days(analysis)
Use professional judgement
No
> 7 days(extraction)
>14 days(analysis)
Use professional judgement
Aqueous
Yes
< 7 days(extraction)
< 40 days(analysis)
No qualification
Yes
> 7 days(extraction)
> 40 days(analysis)
J
UJ
Yes/No
Grossly exceeded
J
UJ orR
No
< 14d ays (extraction)
< 40 days (analysis)
Use professional judgement
No
> 14days(extraction)
>40 days(analysis)
Use professional judgement
Non-aqueous
Yes
< 14d ays (extraction)
< 40 days(analysis)
No qualification
Yes
> 14days(extraction)
> 40 days(analysis)
J
UJ
Yes/No
Grossly Exceeded
J
UJ orR
-Nitro Aromatics/Amines 8 -
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USEPA Region II Date: December 2010
SW846 Method 8330A SOP HW-16 Rev. 2.1
YES NO N/A
Surrogate Recovery (Form II)
9.1 The analyst most monitor the performance of the extraction and analytical system as well as the
effectiveness of the method in dealing with each sample matrix by spiking each sample,
standard and reagent water blank with one or two surrogates (e.g., analytes not expected to be
present in the sample).
9.2 Were the recoveries of the surrogate spikes presented on CLP
Surrogate Recovery Summary forms (Form II), or equivalent, for each of the
following matrices?
a. Water/Waste
b. Soil/Solid
ACTION: Call lab for explanation/resubmittals. If missing deliverables or information are
unavailable, document the effect in the data assessment.
9.3 Are all the pesticide samples listed on the
appropriate surrogate recovery form for each of
the following matrices?
a. Water
b. Waste
c. Soil/Solid
9.4 The laboratory must evaluate the surrogate data from individual samples versus the surrogate
control limits developed by the laboratory. Method 8000C, Sec 9.0 details evaluating surrogate
data and updating surrogate limits. If laboratory established recovery limits are not established,
use surrogate recovery between 70 - 130% for all samples, including MS, MSDs, LCSs, and all
blanks. Are surrogate recovery limits met?
ACTION: Circle all outliers in red. Follow surrogate action Table 2.
-Nitro Aromatics/Amines 9 -
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
9.5Were surrogate retention times (RT) within the windows established during the initial
5-point analysis? _LJ
ACTION: Follow surrogate action, Table 2 below.
Table 2. Surrogate Recovery Criteria
Criteria
Action
Detected Target Compounds
Non-detected Target
Compounds
%R > 200%
J
Use professional judgement
130% < %R < 200%
J
No qualification
70% < %R< 130%
No qualification
10% < %R < 70%
J
UJ
%R < 10% (sample
dilution not a factor)
J
R
%R < 10% (sample
dilution is a factor)
Use professional judgement
RT out of RT window
Use professional judgement
RT within RT window
No qualification
9.6 Are there any transcription/calculation errors between raw data and Form II?
.O.
ACTION: If large errors exist, call lab for explanation/resubmittal. Make any
necessary corrections and document the effect in data assessments.
10.0 Laboratory Control Sample
10.1 Is the LCS prepared, extracted, analyzed, and reported once for every 20 field samples
of a similar matrix, per SDG. _LJ
-Nitro Aromatics/Amines 10 -
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
ACTION: If any Laboratory Control Sample data are missing, call the lab for
explanation/ resubmittals. Make note in the data assessment.
10.2 Are raw data and percent recoveries present for all Laboratory Control samples as
required by Method 8000C (section 9.5). _LJ
Verify that QC check samples were extracted
and analyzed by the same procedures used for
the actual samples.
ACTION: If any Laboratory Control Sample data are missing, call the lab for
explanation/ resubmittals. Make note in the data assessment.
Note: When the results for matrix spike analysis indicates a problem due to sample matrix effects,
the LCS results are used to verify the laboratory can perform the analysis
in a clean sample.
10.3 Were the Laboratory Control Samples analyzed for all the nitroaromatics and nitroamines
analytes that the samples are analyzed for.
.O.
10.4 Were Laboratory Control Samples analyzed at the required concentration as specified
in Method 8000C(sec 9.5)(near the middle of the calibration range) for all target analytes.
J_L
ACTION: If Laboratory Control Samples were not analyzed at the required
concentration or the required frequency, make note in the data
assessment and use professional judgement to determined the affect
on the data.
10.5 Did laboratory calculate in-house performance criteria for LCS recoveries according to
Method 8000C section 9.7, and were recoveries met?
J_L
10.6 If in house LCS recoveries performance criteria were not generated, the laboratory
should use 70 -130% criteria, and was this criteria met? _LJ
10.7 If LCS recovery criteria were not met, were Laboratory Control Samples re-analyzed?
.O.
-Nitro Aromatics/Amines 11 -
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
ACTION: If QC check samples were not re-analyzed, or a general system problem is
indicated by repeated failure to meet the QC acceptance criteria specified in
the method, make note in the data assessment and use Table 3 recovery
actions criteria.
Table 3. LCS Recovery Actions
Criteria
Action
Detected Associated
Compounds
Non-Detected Compounds
%R > Upper Acceptance Limit
J
No qualification
%R < Lower Acceptance Limit
J
R
Lower Acceptance Limit < %R
< Upper Acceptance
Limit
No qualifications
11.0 Matrix Spikes (Form III)
11.1 Are all data for one matrix spike and matrix duplicate (unspiked) pair (MS/Dup) or matrix
spike/matric spike duplicate (MS/MSD)present and complete for each matrix.
J_L
NOTE: For soil and waste samples showing detectable amounts of organics, the lab may
substitute replicate samples in place of the matrix spike spike.
11.2 Have MS/Dup or MS/MSD results been summarized on modified CLP Form III?
J_L
ACTION: If any data are missing take action as specified in section 3.2 above.
11,3Were matrix spikes analyzed at the required frequency for each of the following matrices?
(One MS/Dup, MS/MSD must be performed for every 20 samples of similar matrix or
concentration level.
a. Water
b. Waste
c. Soil/Solid
ACTION: If any MS/Dup or MS/MSD data are missing,take the action specified in 3.2
above.
11.4Were the Matrix Spike Samples spiked and analyzed for all the nitroaromatics and nitroamines
analytes that the samples are analyzed for (Same analytes as LCS). _LJ
-Nitro Aromatics/Amines 12 -
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
ACTION: If no, did the lab use the optional QC acceptance criteria discussed in Method
8000C(section 9.7)?
List the criteria used and make note in data assessment.
Criteria used
11,5Were Laboratory Control Samples analyzed at the required concentration as specified in
Method 8000C(sec (9.5)(Same concentration as LCS) for all target analytes.
J_L
11.6Did laboratory calculate in-house performance criteria for matrix spike recoveries according to
Method 8000C section 9.7, and were recoveries met? _LJ
11.7 If in house LCS recoveries performance criteria were not generated, the laboratory should use
70 -130% criteria, and was this criteria met? _LJ
11,8How many matrix spike recoveries are outside the in-house performance criteria or QC limits
of 70- 130%?
Water Soil
out of out of
11,9How many RPDs for the Matrix Spike and Matrix Spike Duplicate (if applicable)recoveries are
greater than the QC limit of 20%?
Water Soil
out of out of
11.8Were the matrix spike and matrix spike duplicate recovery and RPD limits met as specified in
Table 4. Note: No qualification of the data is necessary on MS and MSD data alone. Use
professional judgement to use the MS and MSD results in conjunction with other QC criteria to
determine the need for some qualification of the data. If any MS and MSD, percent recovery, or
RPD results in the nitroaromatics and nitroamines fraction is out of specification (Table 4), use
professional judgement to qualify data to include the consideration of the existence interference in
the raw data. In some instances it may be determined that only the replicate or spiked samples
are affected. Alternatively, the data may suggest that the laboratory is having a systematic
problem with one or more analytes, thereby affecting all associated samples. Use professional
judgement to determine the need for qualification of detects of non-spiked compounds.
-Nitro Aromatics/Amines 13 -
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USEPA Region II Date: December 2010
SW846 Method 8330A SOP HW-16 Rev. 2.1
YES NO N/A
Table 4. MS/MSD Actions for Analysis
Criteria
Action
Detected Associated
Compounds
Non-Detected Compounds
%R or RPD > Upper
Acceptance Limit
J
No qualification
20% < %R < Lower
Acceptance Limit
J
UJ
%R < 20%
J
Use professional judgement
Lower Acceptance Limit
< %R < Upper
Acceptance Limit
No qualifications
12.0 Blanks (Form IV)
12.1 Was reagent blank data reported on CLP equivalent Method Blank Summary form(s) (Form
IV)?
12.2 Frequency of Analysis: Has a reagent blank been analyzed for every 20 (or less)
samples of similar matrix or concentration or each extraction batch?
ACTION: If any blank data are missing, take action as specified above (section 3.2). If blank
data is not available, reject (R) all associated positive data. However, using
professional judgement, the data reviewer may substitute field blank data for
missing method blank data.
12.3Chromatography: review the blank raw data - chromatograms, quant reports or data system
printouts.
Is the chromatographic performance (baseline stability) for each instrument acceptable
for nitroaromatics and nitramines?
13.0 Contamination
-Nitro Aromatics/Amines 14 -
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
NOTE: "Water blanks", "distilled water blanks" and "drilling water blanks" are validated like
any other sample and are not used to qualify the data. Do not confuse them with the
other QC blanks discussed below.
13.1 Do any method/instrument/reagent/cleanup blanks have positive results for
nitroaromatics or nitramines?When applied as described below, the contaminant
concentration in these blanks are multiplied by the sample Dilution Factor and corrected
for % moisture when necessary.
J_L
13.2Do any field/rinse blanks have positive nitroaromatics or nitramines results?
J_L
ACTION: Prepare a list of the samples associated with each of the contaminated blanks.
(Attach a separate sheet.)
NOTE: All field blank results associated to a particular group of samples (may exceed one
per case or one per day) may be used to qualify data. Blanks may not be qualified
because of contamination in another blank. Field blanks must be qualified for
surrogate, or calibration QC problems.
ACTION: Follow the directions in Table 5 below to qualify sample results due to
contamination. Use the largest value from all the associated blanks.
Table 5. Blank Contamination Criteria
-Nitro Aromatics/Amines 15 -
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
Blank Type
Blank Result
Sample Result
Action for Samples
Detects
Not detected
No qualification
< CRQL
< CRQL
Report CRQL value with a U
> CRQL
Use professional judgement
< CRQL
Report CRQL value with a U
Method,
Clean up,
Instrument,
Field
> CRQL
> CRQL and <
blank
contamination
Report the concentration
for the sample with a
U, or quanity the data
as unusable R
> CRQL and >
blank
contamination
Use professional judgement
= CRQL
< CRQL
Report CRQL value with a U
> CRQL
Use professional judgement
Gross
contamination
Detects
Qualify results as unusable
R
NOTE: If gross blank contamination exists(e.g., saturated peaks, "hump-o-grams," "junk"
peaks), all affected positive compounds in the associated samples should be qualified as
unusable "R", due to interference. Non-detected pesticide target compounds do not require
qualification unless the contamination is so high that it interferes with the analyses of non-
detected compounds.
13.3Are there field/rinse/equipment blanks associated with every sample?
.O.
ACTION: For low level samples, note in data assessment that there is no associated
field/rinse/ equipment blank. Exception: samples taken from a drinking water tap
do not have associated field blanks.
14.0 HPLC Apparatus and Materials
-Nitro Aromatics/Amines 16 -
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USEPA Region II Date: December 2010
SW846 Method 8330A SOP HW-16 Rev. 2.1
YES NO N/A
14.1 Was the proper HPLC chromatographic column used for the analysis of
nitroaromatics or nitramines?
Action: Check raw data, instrument logs, or contact the lab to determine what type of columns
were used. (Method 8330A, section 4.1) _LJ
14.2 Indicate the specific type of HPLC column.
column 1:
column 2:
ACTION: Note any changes to the suggested materials in section 14.1 above in the data
assessment. Also note the impact (positive or negative) such changes have on
the analytical results.
15.0 Calibration and HPLC Performance
15.1 Are the following liquid chromatograms and data systems printouts for both columns present
for all samples, blanks, MS, replicates?
a. Samples
b. All blanks
c. Matrix spike samples
d. 5 pt. initial calibration standards
e. Calibration verification standards
f. Laboratory Control samples (LCS)
ACTION: If no, take action specified in 3.2 above.
15.2Are data summary forms (containing calibration factors or response factors) for the initial 5 pt.
calibration and daily calibration verification standards present and complete for each column
and each analytical sequence?
NOTE: External standard calibration procedures are used (Method 8000C (section
11.4.2), therefore calibration factors must be used.
ACTION: If any data are missing or it cannot be determined how the laboratory calculated
calibration factors, contact the lab for explanation/resubmittals. Make necessary
corrections and note any problems in the data assessment.
-Nitro Aromatics/Amines 17 -
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
15.3Are there any transcription/calculation errors between raw data and data summary forms?
ACTION: If large errors exist, call lab for explanation/resubmittal, make necessary
corrections and document the effect in data assessments.
15.4Are standard retention time (RT) windows for each nitroaromatics and nitramines peak of
interest presented on modified CLP summary forms?
ACTION: If any data are missing, or it cannot be determined how RT windows were
calculated, call the lab for explanation/resubmittals. Note any problems in the
data assessment.
NOTE: Retention time windows for all nitroaromatics and nitramines are established
using retention times from three calibration standards analyzed during the entire
analytical sequence (Method 8000C section 11.6).
Best results are obtained using retention times which span the entire
sequence; i.e., using the calibration verification/continuing calibration
standards analyzed every 12 hours.
15.5Were RT windows on the confirmation column established using three standards as described
above?
NOTE: RT windows for the confirmation column should be established using a 3 pt.
calibration, preferably spanning the entire analytical sequence as described in 15.4
above. If RT windows on one column are tighter than the other, this may result in
false negatives when attempting to identify compounds in the samples.
ACTION: Note potential problems, if any, in the data assessment.
15.6Do all standard retention times in each level of the initial 5 pt. calibrations for nitroaromatics
and nitramines fall within the windows established during the initial calibration sequence?
ACTION i:lf no, all samples in the entire analytical sequence are potentially affected. Check to see if
three standards spanning the entire sequence were used to obtained RT windows. If the lab
used three standards from the 5 pt.,RT windows may be too tight. If so, RT windows should
be recalculated as per Method 80000C(section 11.6).
ii. Alternatively, check to see if the chromatograms contain peaks within an expanded
window surrounding the expected retention times.
-Nitro Aromatics/Amines 18 -
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
If no peaks are found and the surrogates are visible, non-detects are valid.
If peaks are present but cannot be discerned through pattern recognition
or by using revised RT windows, qualify all positive results and
non-detects as unusable, "R".
15.7Has the linearity criteria for the initial calibration standards been satisfied for both columns?
(% RSD for the calibration factors (CFs)must be < 20.0% for all analytes).
J_L
ACTION: If no, follow Table 6 criteria.
Table 6. Initial Calibration CF Action for
Nitroaromatic and
Nitramine Analysis
Action
Criteria
Detected Associated
Compounds
Non-Detected
Associatedd
Compounds
% RSD > 20%
J
UJ
% RSD within allowable limits
No qualifications
15.8Does the calibration verification/continuing calibration standard contain the nitroaromatics or
nitramines peaks of interest, analyzed on each working day, prior to sample analyses?
J_L
15.9Has a calibration verification/continuing calibration standard been analyzed after every 10
samples and at the end of each analytical sequence
J_L
ACTION: If no, take action as specified in section 3.2 above.
15.10 Has the percent difference (%D) between the Calibration Factor (CF) of the peaks used to
identify the nitroaromatics and nitramines in the CCV and the CF from these peaks in the initial
calibration exceeded + 15%. __ _LJ
15.11 Has a new 5 pt. initial calibration curve been generated for those nitroaromatics and
nitramines analytes which failed in the calibration verification/continuing calibration
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USEPA Region II Date: December 2010
SW846 Method 8330A SOP HW-16 Rev. 2.1
YES NO N/A
standard (8000C, section 11.7.3), and all samples which followed the out-of-control
calibration verification/standard continuing calibration standard?
ACTION: If the %D for any analyte exceeded the + 15% criterion and the instrument was
not recalibrated for those analytes, qualify positive results for all associated
samples (those which followed the out-of-control standard) "J" and sample
quantitation limits "UJ". (Table 7)
15.12 Have retention time (RT) windows been properly calculated for each analyte of interest
(Method 8000C, section 11.6), using RTs from the associated calibration
verification/continuing standard? _LJ
ACTION: If no, take action specified in section 3.2 above
15.13 Do all standard retention times for each calibration verification/continuing calibration
standard fall within the windows established during the initial calibration sequence?
15.14 Do all standard retention times for each mid-concentration standard (analyzed after
every 10 samples) fall within the daily RT windows.
ACTION: If the answer to either 15.12 or 15.13 above is no, check the chromatograms of all samples
which followed the last in-control standard. All samples analyzed after the last in-control
standard must be re-injected, if initial analysis indicated the presence of the specific analyte
that exceeded the retention time criteria). If samples were not re-analyzed, document under
Contract Non-compliance in the Data Assessment.
Reviewer has two options to determine how to qualify questionable sample data.
First option is to determine if possible peaks are present within daily retention time
window. If no possible peaks are found, non-detects are valid. If possible peaks are
found (or interference), qualify positive hits as presumptively present "NJ" and non-
detects are rejected "R". Second option is to use the ratio of the retention time of
the analyte over the retention time of either surrogate. The passing criteria is + 0.06
RRT units of the RRT of the standard component. Reject "R" all questionable
analytes exceeding criteria, and "NJ" all other positive hits.
15.15 Has no more than 14 hours elapsed from the injection of the opening CCV and the end
of the analytical sequence (closing CCV). (Table 7)
J_L
Table 7. CCV Criteria
Criteria
Action
Detected Associated
Non-Detected Associated
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USEPA Region II Date: December 2010
SW846 Method 8330A SOP HW-16 Rev. 2.1
YES NO N/A
Compounds
Compounds
RT out of RT window
Use professional judgement (Sec 15.14)
%D not within +/-15%
J
UJ
Time elapsed greater
than section 15.15
criteria.
R
%D, time elapsed, RT
are all within
acceptable limits.
No qualifications
15.16 Are there any transcription/calculation errors between raw data and data summary
forms?
ACTION: If large errors exists call lab for explanation/resubmittal, make any
necessary corrections and document the effect in data assessments
under "Conclusions".
16.0 Analytical Sequence Check (Form Vlll-nitroaromatics and nitramines)
16.1 Have all samples been listed on CLP Form VIII or equivalent, and are separate forms present
for each column? _LJ
ACTION: If no, take action specified in 3.2 above.
16.2Was the proper analytical sequence followed for each initial calibration and subsequent
analyses? _LJ
Note: Sequence is as follows: 5 point initial calibration, method blank, LCS, CCS, 10 sample
extracts, CCV, 10 sample extract, and so on. The sequence must always end with a CCV. As
long as the first CCV is within QC, the initial calibration does not have to be rerun.
ACTION: If no, use professional judgement to determine the severity of the effect on the
data and qualify it accordingly. Generally, the effect is negligible unless the
sequence was grossly altered or the calibration was also out of limits.
16.3 Were the surrogate RTs for the samples within the mean surrogate RT from the initial
calibration? _LJ
Action: If no, see "Action" in section 15.14 above
17.0 Extraction Techniques for Sample Preparation
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USEPA Region II Date: December 2010
SW846 Method 8330A SOP HW-16 Rev. 2.1
YES NO N/A
Method 8330A permits a variety of extraction techniques to be used for sample preparation. Which
extraction procedure was used?
17.1 Aqueous samples:
1. Low Level (salting-out extraction))
2. High-level (Sample filtration)
3. Solid phase extraction (Method 3535)
4. Other
17.2 Soil and sediment samples:
1. Sonication
2. Other
18.0 Nitroaromatics and Nitramines Identification
18.1 Has CLP Form X or equivalent, showing retention time data for positive results on the two
HPLC columns, been completed for every sample in which a nitroaromatics or nitramines was
detected?
ACTION: If no, take action specified in 3.2 above, or compile a list comparing the retention
times for all sample hits on the two columns.
18.2 Are there any transcription/calculation errors between raw data and data summary forms
(initial calibration summaries, calibration verification summaries, analytical sequence
summaries.
ACTION: If large errors exist, call lab for explanation/resubmittal, make necessary
corrections and note error in the data assessment.
18.3Are retention times (RT) of sample compounds within the established RT windows for both
columns/analyses? _LJ
ACTION: Qualify as unusable (R) all positive results which were not confirmed by second
HPLC column analysis. Also qualify "R", unusable, all positive results not within RT
windows unless associated standard compounds are similarly biased. The reviewer
should use professional judgement to assign an appropriate quantitation limit.
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
18.4Check chromatograms for false negatives, especially if RT windows on each column were
established differently.Were there any false negatives?
ACTION: Use professional judgement to decide if the compound should be reported. If
there is reason to believe that peaks outside retention RT windows should be
reported, make corrections to data summary forms (Form I) and note in data
assessment.
18.51s the percent difference (%D) calculated for the positive sample results on the two HPLC
columns<25.0%?
NOTE: The method requires quantitation from one column. The second column is to
confirm the presence of an analyte. It is the reviewer's responsibility to verify from
the project plan what the lab was required to report. If the lab was required to report
concentrations from both columns, continue with validation for % Difference. If
required, but not reported, either contact the lab for results or calculate the
concentrations from the calibration. If not required, skip this section. Document
actions in Data Assessment.
ACTION: If the reviewer finds neither column shows interference for the positive hits, the
data should be qualified as follows:
% Difference
0-25%
26-70%
71-100%
101-200% (No Interference)
101-200% (Interference detected)**
>50% (Analyte value is 200%
Qualifier
none
"J"
"NJ"
MR"
"NJ"
"U"
"R"
Note: The lower of the two values is reported on Form I. If using professional judgement,the
reviewer determines that he higher result was more acceptable, the reviewer should
replace the value and indicate the reason for the change in the data assessment.
19.0 Compound Quantitation and Reported Detection Limits
19.1 Are there any transcription/calculation errors in Form I results? Check at least two positive
values. Were any errors found?
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
NOTE: Nitroaromatics and Nitramines peak results can be checked for rough agreement
between quantitative results obtained on the two HPLC columns. The reviewer
should use professional judgement to decide whether a much larger concentration
obtained on one column versus the other indicates the presence of an interfering
compound. If an interference is suspected, the lower of the two values should be
reported and qualified according to section 18.5 above. This necessitates a
determination of an estimated concentration on the confirmation column. The
narrative should indicate that the presence of interferences has led to the
quantitation of the second column confirmation results.
19.2Are the EDLs (Estimated Detection Limits) adjusted to reflect sample dilutions and, for soils,%
moisture? _LJ
ACTION: If errors are large, call lab for explanation/resubmittal, make any necessary
corrections and document effect in data assessments.
ACTION: When a sample is analyzed at more than one dilution, the lowest EDLs are used
(unless a QC exceedance dictates the use of the higher EDL data from the diluted
sample analysis). Replace concentrations that exceed the calibration range in the
original analysis by crossing out the value on the original Form I and substituting it
with data from the analysis of diluted sample. Specify which Form I is to be used,
then draw a red "X" across the entire page of all Form I's that should not be used,
including any in the summary package.
ACTION: EDLs affected by large, off-scale peaks should be qualified as unusable, "R". If the
interference is on-scale, the reviewer can provide a modified EDL flagged "UJ" for
each affected compound.
14.0 Chromatogram Quality
14.1 Were baselines stable? _LJ
14.2Were any electropositive displacement (negative peaks) or unusual peaks seen?
.O.
ACTION: Note all system performance problems in the data assessment.
15.0 Field Duplicates
15.1 Were any field duplicates submitted for Nitroaromatics and Nitramines.
J_L
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USEPA Region II
SW846 Method 8330A
Date: December 2010
SOP HW-16 Rev. 2.1
YES NO N/A
ACTION: Compare the reported results for field duplicates and calculate the relative
percent difference.
ACTION: Any gross variation between field duplicate results must be addressed in the
reviewer narrative. However, if large differences exist, the identity of the field
duplicates is questionable. An attempt should be made to determine the proper
identification of field duplicates.
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