US EPA Contract Laboratory Program National Functional Guidelines for Inorganic Superfund Data Review Final


Office of Superfund Remediation and Technology Innovation (OSRTI)
United States Environmental Protection Agency (USEPA)
Washington, DC 20460
  OSWER 9240.1-51
USEPA-540-R-10-011

   January 2010
                                            USEPA Contract Laboratory Program
                                            National
                                            Functional
                                            Guidelines
                                            for Inorganic Superfund Data Review
                                  Final

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                                          NOTICE
The policies and procedures set forth here are intended as guidance to the United States Environmental
Protection Agency (hereafter referred to as USEPA) and other governmental employees.  They do not
constitute rule making by USEPA, and may not be relied upon to create a substantive or procedural right
enforceable by any other person.  The Government may take action that is at variance with the policies
and procedures in this manual.
This document can be obtained from the USEPA's Contract Laboratory Program (CLP) Web site at:
                     http://www.epa.gov/superfund/programs/clp/guidance.htm
January 2010

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                                 TABLE OF CONTENTS
ACRONYMS	iv
TARGET ANALYTE LIST	v
INTRODUCTION	1
DATA QUALIFIER DEFINITIONS	2
DATA PACKAGE INSPECTION	2
PRELIMINARY REVIEW	3
DATA REVIEW NARRATIVE	4

ICP-AES DATA REVIEW	5
   I.     Preservation and Holding Times	7
   II.    Calibration	9
   III.   Blanks	12
   IV.   Inductively Coupled Plasma - Interference Check Sample (ICP-ICS)	15
   V.    Laboratory Control Sample (LCS)	18
   VI.   Duplicate Sample Analysis	20
   VII.   Spike Sample Analysis	22
   VIII.  ICP Serial Dilution	25
   IX.   Regional Quality Assurance (QA) and Quality Control (QC)	27
   X.    Overall Assessment	28
   Calculations for ICP-AES	30
ICP-MS DATA REVIEW	32
   I.     Preservation and Holding Times	34
   II.    ICP-MS Tune Analysis	36
   III.   Calibration	38
   IV.   Blanks	41
   V.    Inductively Coupled Plasma - Interference Check Sample (ICP-ICS)	44
   VI.   Laboratory Control Sample (LCS)	47
   VII.   Duplicate Sample Analysis	49
   VIII.  Spike Sample Analysis	51
   IX.   ICP Serial Dilution	54
   X.    ICP-MS Internal Standards	56
   XI.   Regional Quality Assurance (QA) and Quality Control (QC)	58
   XII.   Overall Assessment	59
   Calculations for ICP-MS	61

MERCURY DATA REVIEW	62
   I.     Preservation and Holding Times	64
   II.    Calibration	66
   III.   Blanks	69
   IV.   Duplicate Sample Analysis	72
   V.    Spike Sample Analysis	74
   VI.   Regional Quality Assurance (QA) and Quality Control (QC)	76
   VII.   Overall Assessment	77
   Calculations for Mercury	79
January 2010

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                           TABLE OF CONTENTS (CON'T)

CYANIDE DATA REVIEW	80
   I.    Preservation and Holding Times	82
   II.   Calibration	84
   III.   Blanks	87
   IV.   Duplicate Sample Analysis	90
   V.   Spike Sample Analysis	92
   VI.   Regional Quality Assurance (QA) and Quality Control (QC)	95
   VII.  Overall Assessment	96
   Calculations for Cyanide	98
APPENDIX A:  GLOSSARY	99
APPENDIX B: INORGANIC DATA REVIEW SUMMARY	102
January 2010

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LIST OF TABLES
Table 1. Technical Holding Time Actions for ICP-AES Analysis 8
Table 2. Acceptance Criteria for ICVs and CCVs, 9
Table 3. Calibration Actions for ICP-AES Analysis 11
Table 4. Blank Actions for ICP-AES Analysis 14
Table 5. Interference Check Actions for ICP-AES Analysis 17
Table 6. LCS Actions for ICP-AES Analysis 19
Table 7. Duplicate Sample Actions for ICP-AES Analysis 21
Table 8. Spike Sample Actions for ICP-AES Analysis 24
Table 9. Serial Dilution Actions for ICP-AES Analysis 26
Table 10. Technical Holding Time Actions for ICP-MS Analysis 35
Table 11. ICP-MS Tune Actions for ICP-MS Analysis 37
Table 12. Acceptance Criteria for ICV and CCV Standards 38
Table 13. Calibration Actions for ICP-MS Analysis 40
Table 14. Blank Actions for ICP-MS Analysis 43
Table 15. Interference Check Actions for ICP-MS Analysis 46
Table 16. LCS Actions for ICP-MS Analysis 48
Table 17. Duplicate Sample Actions for ICP-MS Analysis 50
Table 18. Spike Sample Actions for ICP-MS Analysis 53
Table 19. Serial Dilution Actions for ICP-MS Analysis 55
Table 20. Internal Standard Actions for ICP-MS Analysis 57
Table 21. Technical Holding Time Actions for Mercury Analysis 65
Table 22. Acceptance Criteria for ICVs and CCVs 66
Table 23. Calibration Actions for Mercury Analysis 68
Table 24. Blank Actions for Mercury Analysis 71
Table 25. Duplicate Sample Actions for Mercury Analysis 73
Table 26. Spike Sample Actions for Mercury Analysis 75
Table 27. Technical Holding Time Actions for Cyanide Analysis 83
Table 28. Acceptance Criteria for ICVs and CCVs 84
Table 29. Calibration Actions for Cyanide Analysis 86
Table 30. Blank Actions for Cyanide Analysis 89
Table 31. Duplicate Sample Actions for Cyanide Analysis 91
Table 32. Spike Sample Actions for Cyanide Analysis 94
January 2010 iii

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                                       ACRONYMS
AA         Atomic Absorption
ASB        Analytical Services Branch
CCB        Continuing Calibration Blank
CCS        Contract Compliance Screening
CCV        Continuing Calibration Verification
CLP        Contract Laboratory Program
CO         Contracting Officer
CRQL      Contract Required Quantitation Limit
CSF        Complete SDG File
CVAA      Cold Vapor AA
DAT        Data Assessment Tool
DF         Dilution Factor
DQO       Data Quality Objective
ICB        Initial Calibration Blank
ICP        Inductively Coupled Plasma
ICP-AES   Inductively Coupled Plasma - Atomic Emission Spectroscopy
ICP-MS    Inductively Coupled Plasma - Mass Spectrometry
ICS        Interference Check Sample
ICV        Initial Calibration Verification
LCS        Laboratory Control Sample
MDL       Method Detection Limit
NIST       National Institute of Standards and Technology
OSRTI     Office of Superfund Remediation and Technology Innovation
OSWER    Office of Solid Waste and Emergency Response
PE         Performance Evaluation
%D        Percent Difference
%R        Percent Recovery
%RI        Percent Relative Intensity
%RSD      Percent Relative Standard Deviation
%S         Percent Solids
PO         Project Officer
QA         Quality Assurance
QAPP      Quality Assurance Project Plan
QC         Quality Control
RPD        Relative Percent Difference
RSCC      Regional Sample Control Center Coordinator
SDG        Sample Delivery Group
SMO       Sample Management Office
SOP        Standard Operating Procedure
SOW       Statement of Work
TAL        Target Analyte List
TR/COC    Traffic Report/Chain of Custody Documentation
USEPA     United States Environmental Protection Agency
January 2010
IV

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                               TARGET ANALYTE LIST
Al        Aluminum
Sb        Antimony
As        Arsenic
Ba        Barium
Be        Beryllium
Cd        Cadmium
Ca        Calcium
Cr        Chromium
Co        Cobalt
Cu        Copper
CN       Cyanide
Fe        Iron
Pb        Lead
Mg       Magnesium
Mn       Manganese
Hg        Mercury
Ni        Nickel
K        Potassium
Se        Selenium
Ag        Silver
Na        Sodium
Tl        Thallium
V        Vanadium
Zn        Zinc
January 2010

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January 2010                                                                                    vi

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                                       INTRODUCTION
This document is designed to offer the data reviewer guidance in determining the usability of analytical
data generated through the USEPA Contract Laboratory Program (CLP) Statement of Work (SOW)
ISM01.X Inorganic Superfund Methods (Multi-Media, Multi-Concentration), hereinafter referred to as
the ISM01.2 SOW, and any future editorial revisions of ISM01.2. This guidance is somewhat limited in
scope and is intended to be used as an aid in the formal technical review process. It should not be used to
establish specific contract compliance; use of this document to evaluate data generated under Inorganic
SOWs other than ISM01.2 is cautioned. Definitive guidance is provided where performance should be
fully under a laboratory's control [e.g., blanks, calibration verification standards, Interference Check
Samples (ICSs), Quality Control (QC) audit samples, and instrument performance checks (tuning)], while
general guidance is provided for evaluating subjective data that is affected by site conditions.
The guidelines presented in the document will aid the data reviewer in establishing (a) if data meets the
specific technical and QC criteria established in the SOW, and (b) the usability and extent of bias of any
data not meeting the specific technical and QC criteria established in the SOW.  It must be understood by
the reviewer that acceptance of data not meeting technical requirements is based upon many factors,
including, but not limited to site-specific technical requirements, the need to facilitate the progress of
specific projects, and availability for re-sampling. To make judgments at this level requires the reviewer
to have a complete understanding of the intended use of the data. The reviewer is strongly encouraged to
establish a dialogue with the user prior to and after data review, to discuss usability issues and to answer
questions regarding the review. It should also be understood that in all cases, data which do not meet
specified criteria are never to be fully acceptable without qualification.
The reviewer should note that while this document is to be  used as an aid in the formal data review
process, other sources of guidance and information, as well as professional judgment, should also be used
to determine the ultimate usability of data, especially in those cases  where all data does not meet specific
technical criteria. The  reviewer should also be aware that minor modifications to some of the analytical
methods may be made through the "Request for Quote (RFQ) for Modified Analysis" to meet site-
specific requirements, and that these modifications could affect certain validation criteria such as Contract
Required Quantitation Limits (CRQLs) and Target Analyte Lists (TALs). A copy of any modification
request made to the analytical method should be included in the data package by the laboratory.
Please visit the CLP Web site at http://www.epa.gov/superfund/programs/clp/index.htm for more
information on how to obtain service through the CLP.
January 2010

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DATA QUALIFIER DEFINITIONS

The following definitions provide brief explanations of the national qualifiers assigned to results in the
data review process. If the Regions choose to use additional qualifiers, a complete explanation of those
qualifiers should accompany the data review.
U
The analyte was analyzed for, but was not detected above the level of the reported sample
quantitation limit.
The result is an estimated quantity. The associated numerical value is the approximate
concentration of the analyte in the sample.
J+
The result is an estimated quantity, but the result may be biased high.
J-
The result is an estimated quantity, but the result may be biased low.
R
The data are unusable. The sample results are rejected due to serious deficiencies in meeting
Quality Control (QC) criteria. The analyte may or may not be present in the sample.
UJ
The analyte was analyzed for, but was not detected. The reported quantitation limit is
approximate and may be inaccurate or imprecise.
DATA PACKAGE INSPECTION
For data obtained through the Contract Laboratory Program (CLP), the Data Assessment Tool (DAT)
report is a useful tool in the data review process. The DAT report incorporates Contract Compliance
Screening (CCS) and National Functional evaluation results, and is transmitted electronically via email.
For more information about DAT, please refer to the following CLP Web site:
http://www.epa.gov/superfund/programs/clp/data assessment.htm
The DAT report will identify any missing and/or incorrect information in the data package. The CLP
laboratory may submit a reconciliation package for any missing items or to correct data.
If there are any concerns regarding the data package, contact the CLP Project Officer (CLP PO) from the
Region where the samples were taken. For personnel contact information, please refer to the following
CLP Web site:
http://www.epa.gov/superfund/programs/clp/contacts.htm
January 2010

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PRELIMINARY REVIEW
This document is for the review of analytical data generated through the ISMO1.2 SOW and any future
editorial revisions of ISM01.2. To use this document effectively, the reviewer should have an
understanding of the analytical method and a general overview of the Sample Delivery Group (SDG) or
sample Case at hand. The exact number of samples, their assigned numbers, their matrix, and the number
of laboratories involved in the analysis are essential information.
It is suggested that an initial review of the data package be performed, taking into consideration all
information specific to the sample data package [e.g., Modified Analysis requests, Traffic Report/Chain
of Custody (TR/COC) documentation, SDG Narratives, etc.].
The reviewer should also have a copy of the Quality Assurance Project Plan (QAPP) or similar document
for the project for which the samples were analyzed. The reviewer should contact the appropriate
Regional Contract Laboratory Program Project Officer (CLP PO) to obtain copies of the QAPP and
relevant site information. This information is necessary in determining the final usability of the analytical
data.
The SDGs or Cases routinely have unique samples that require special attention from the reviewer. These
include field blanks and trip blanks, field duplicates, and Performance Evaluation (PE) samples which
must be identified in the sampling records. The sampling records (e.g., TR/COC records, field logs,
and/or contractor tables) should identify:
1. The Region where the samples were taken, and
2. The complete list of samples with information on:
a. Sample matrix;
b. Field blanks*;
c. Field duplicates*;
d. Field spikes*;
e. PE samples*;
f Shipping dates;
g. Preservatives;
h. Types of analysis; and
i. Laboratories involved.
* If applicable.
The TR/COC documentation includes sample descriptions and date(s) of sampling. The reviewer must
consider lag times between sampling and start of analysis when assessing technical sample holding times.
The laboratory's SDG Narrative is another source of general information. Notable problems with
matrices, insufficient sample volume for analysis or reanalysis, samples received in broken containers,
preservation, and unusual events should be documented in the SDG Narrative. The reviewer should also
inspect any email or telephone/communication logs detailing any discussion of sample or analysis issues
between the laboratory, the CLP Sample Management Office (SMO), and the USEPA Region.
January 2010

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                                DATA REVIEW NARRATIVE

A Data Review Narrative, including the Inorganic Data Review Summary form (see Appendix B), must
accompany the laboratory data forwarded to the intended data recipient (client) or user to promote
communication. A copy of the Data Review Narrative should be submitted to the CLP PO assigned
oversight responsibility for the laboratory producing the data.
The Data Review Narrative should include comments that clearly identify the problems associated with a
Case or SDG and state the limitations of the data.  Documentation should also include the CLP Sample
Number, analytical method, extent of the problem, and assigned qualifiers.
January 2010

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Inorganic Data Review                                                               ICP-AES

                                ICP-AES DATA REVIEW
The inorganic data requirements for Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-
AES) to be reviewed during validation are listed below:
I.      Preservation and Holding Times	7
II.     Calibration	9
III.    Blanks	12
IV.    Inductively Coupled Plasma - Interference Check Sample (ICP-ICS)	15
V.     Laboratory Control Sample (LCS)	18
VI.    Duplicate Sample Analysis	20
VII.   Spike Sample Analysis	22
VIII.   ICP Serial Dilution	25
IX.    Regional Quality Assurance (QA) and Quality Control (QC)	27
X.     Overall Assessment	28
Calculations for ICP-AES	30
January 2010

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Inorganic Data Review                                                        ICP-AES

                     An Example Analytical Sequence for ICP-AES
SO
s
s
s
s
s
ICV
ICB
ICSA
ICSAB
CCV
CCB
samples
CCV
CCB
samples
CCV
CCB, etc.
January 2010

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Inorganic Data Review ICP-AES

Preservation and Holding Times
A. Review Items:
Form IA-IN, Form IB-IN, Form XII-IN, Form XIII-IN, Traffic Report/Chain of Custody (TR/COC)
documentation, Form DC-1, raw data, and the Sample Delivery Group (SDG) Narrative checking for:
pH; cooler temperature; holding time; and other sample conditions.

B. Objective:
The objective is to ascertain the validity of the analytical results based on the sample condition, and
the holding time of the sample from the date of collection to the date of analysis.
C. Criteria:
1. The technical holding time criteria for aqueous/water metal samples is 180 days, preserved (with
nitric acid) to pH < 2. The addition of nitric acid to adjust the pH is only required for
aqueous/water samples.
2. The technical holding time criteria for soil/sediment metal samples is 180 days, based on the
technical holding time criteria for aqueous/water samples.
3. The technical holding time criteria for wipe and air filter samples is 180 days, based on the
technical holding time criteria for aqueous/water samples.
4. Aqueous/water and soil/sediment samples shall be maintained at 4°C (±2°C) until preparation.
Wipe and air filter samples may be maintained at room temperature until preparation.
D. Evaluation:
Technical holding times are established by comparing the sampling date(s) on the TR/COC
documentation with the dates of analysis on Form XIII-IN and the raw data. Information contained in
the Complete SDG File (CSF) should also be considered in the determination of holding times.
Verify that the analysis dates on the Form XIIIs and the raw data are identical. Review the SDG
Narrative and raw data preparation logs to determine if samples were properly preserved. If there is
an indication that there were problems with the samples, the integrity of the samples may be
compromised and professional judgment should be used to evaluate the effect of the problem on the
sample results.
E. Action:
NOTE: Apply the action to each sample for which the preservation or holding time criteria was
not met.
1. If the pH of aqueous/water metal samples is > 2 at the time of sample receipt, determine if the
laboratory adjusted the pH of the sample to < 2 at the time of sample receipt. If not, use
professional judgment to qualify the samples based on the pH of the sample and the chemistry of
the metal(s) of interest. Qualify results that are > Method Detection Limit (MDL) as estimated
low (J-), and qualify non-detects as unusable (R).
2. If technical holding times are exceeded, use professional judgment to determine the reliability of
the data, based on the magnitude of the additional time compared to the technical requirement and
whether the samples were properly preserved. The expected bias would be low. Qualify results
that are > MDL as estimated low (J-), and qualify non-detects as unusable (R).
3. Due to limited information concerning holding times for soil/sediment, wipe, and filter samples, it
is left to the discretion of the data reviewer whether to apply aqueous/water holding time criteria
to soil/sediment, wipe, or filter samples. If they are applied, it must be clearly documented in the
Data Review Narrative.
4. When the holding times are exceeded, the reviewer should comment in the Data Review
Narrative on any possible consequences for the analytical results.
5. When holding times are grossly exceeded, note it for Contract Laboratory Program Project
Officer (CLP PO) action.
January 2010 7

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Inorganic Data Review
ICP-AES
                Table 1.  Technical Holding Time Actions for ICP-AES Analysis
Preservation & Holding Time Results
Aqueous/water metals samples received with
pH > 2 and pH not adjusted
Aqueous/water and soil/sediment metals
samples not maintained at 4°C (±2°C)
Technical Holding Time exceeded:
Aqueous/water Metals > 180 day
Technical Holding Time exceeded:
Soil/sediment, wipe, filter Metals > 180 days
Action for Samples
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
January 2010

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Inorganic Data Review
ICP-AES
Calibration
A. Review Items:
Form II-IN (Part A), Form XI-IN, Form XIII-IN, Form XVI-IN, preparation logs, calibration standard
logs, instrument logs, instrument printouts, and raw data.

B. Objective:
Method requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable quantitative data for the metals on the Inorganic Target
Analyte List (TAL). Initial Calibration Verification (ICV) demonstrates that the instrument is
capable of acceptable performance at the beginning of the analytical run. Continuing Calibration
Verification (CCV) demonstrates that the initial calibration is still valid by checking the performance
of the instrument on a continuing basis.
C. Criteria:
1. Initial Calibration
The instruments shall be successfully calibrated each time the instrument is set up and after
Continuing Calibration Verification (CCV) failure. The calibration date and time shall be
included in the raw data.
a. A blank and at least five calibration standards shall be used to establish each analytical curve.
At least one of these standards shall be at or below the CRQL. All measurements shall be
within the instrument working range where the interelement correction factors are valid. A
minimum of three replicate exposures are required for standardization, all Quality Control
(QC), and sample analyses. The average result of all the multiple exposures for the
standardization, QC, and sample analyses shall be used. The calibration curve shall be fitted
using linear regression or weighted linear regression. The curve may be forced through zero.
The curve must have a correlation coefficient > 0.995. The percent differences calculated for
all of the non-zero standards must be within ±30% of the true value of the standard. The y-
intercept of the curve must be less than the CRQL.
2. Initial and Continuing Calibration Verification (ICV and CCV)
The acceptance criteria for the ICVs and CCVs are presented in Table 2:

Table 2. Acceptance Criteria for ICVs and CCVs,
Analytical
Method
ICP-AES
Inorganic
Analytes
Metals
ICV/CCV
Low Limit
(% of True Value)
90
ICV/CCV
High Limit
(% of True Value)
110
a. Initial Calibration Verification (ICV)
1) Immediately after each system has been calibrated, the accuracy of the initial calibration
must be verified and documented for each target analyte by the analysis of an ICV
solution(s). If the ICV %R falls outside of the control limits, the analysis should be
terminated, the problem corrected, the instrument recalibrated, and all affected samples
reanalyzed.
2) Only if the ICV is not available from USEPA, analyses shall be conducted using a
certified solution of the analytes from an independent commercial standard source, at a
concentration level other than that used for instrument calibration, but within the
calibrated range.
3) The ICV solution shall be run at each analytical wavelength used for analysis.
January 2010

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Inorganic Data Review ICP-AES

b. Continuing Calibration Verification (CCV)
1) To ensure accuracy during the course of each analytical run, the CCV shall be analyzed
and reported for each wavelength used for the analysis of each analyte.
2) The CCV standard shall be analyzed at a frequency of every two hours during an
analytical run. The CCV standard shall also be analyzed at the beginning of the run, and
again after the last analytical sample.
3) The analyte concentration(s) in the CCV standard(s) shall be different than the
concentration used for the ICV, and at a concentration equivalent to the mid level of their
respective calibration curves.
4) The same CCV standard solution shall be used throughout the analysis runs for a Sample
Delivery Group (SDG).
5) The CCV shall be analyzed in the same fashion as an actual sample. If the %R of the
CCV was outside of the control limits, the analysis should be terminated, the problem
corrected, the instrument recalibrated, and all analytical samples analyzed since the last
compliant CCV reanalyzed.
D. Evaluation:
1. Verify that the instrument was calibrated each time the instrument was set up, utilizing a blank
and at least five calibration standards, one of which was at or below the CRQL.
2. Confirm that the measurements were within the working range, and were the average result of at
least three replicate exposures.
3. Verify that the ICV and CCV standards were analyzed for each analyte at the proper frequency
and at the appropriate concentration. Verify that acceptable %R results were obtained.
4. Recalculate one or more of the ICV and CCV %R using the following equation and verify that
the recalculated value agrees with the laboratory-reported values on Form IIA-IN.

%R= Found (value) xlQQ
True (value)
Where,
Found (value) = Concentration (in (ig/L) of each analyte measured in the analysis of the
ICV or CCV solution
True (value) = Concentration (in (ig/L) of each analyte in the ICV or CCV source

E. Action:
NOTES: For initial calibrations or ICVs that do not meet the technical criteria, apply the action to
all samples reported from the analytical run.
For CCVs that do not meet the technical criteria, apply the action to all samples analyzed
between a previous technically acceptable analysis of the QC sample and a subsequent
technically acceptable analysis of the QC sample in the analytical run.
1. If the instrument was not calibrated each time the instrument was set up, qualify the data as
unusable (R). If the instrument was not calibrated with at least the minimum number of
standards, or if the calibration curve does not include standards at required concentrations (e.g., a
blank and at least one at or below CRQL), use professional judgment to qualify results that are
> Method Detection Limit (MDL) as estimated (J) or unusable (R), and non-detects as estimated
(UJ) or unusable (R).
2. If the correlation coefficient is <0.995, percent differences are outside the ±30% limit, or the y-
intercept >CRQL, qualify sample results that are >MDL as estimated (J) and non-detects as
estimated (UJ).
January 2010 10

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Inorganic Data Review
                                       ICP-AES
    3.  If the ICV or CCV %R falls outside the acceptance windows, use professional judgment to
       qualify all associated data. If possible, indicate the bias in the review. The following guidelines
       are recommended:
       a.  If the ICV or CCV %R is < 75%, qualify non-detects as unusable (R). Use professional
           judgment to qualify all results that are > MDL as estimated low (J-) or unusable (R).
       b.  If the ICV or CCV %R falls within the range of 75-89%, qualify sample results that are
           > MDL as estimated low (J-), and qualify non-detects as estimated (UJ).
       c.  If the ICV or CCV %R falls within the range of 111-125%, qualify sample results that are
           > MDL as estimated high (J+).
       d.  If the ICV or CCV %R is within the range of 111-125%, non-detects should not be qualified.
       e.  If the ICV or CCV %R is > 125%, use professional judgment to qualify results that are
           > MDL as estimated high (J+) or unusable (R). Non-detects should not be qualified.
       f  If the %R is > 160%, qualify all results that are > MDL as unusable (R).
    4.  If the laboratory failed to provide adequate calibration information, the Region's designated
       representative should contact the laboratory and request the necessary information. If the
       information is not available, the reviewer must use professional judgment to assess the  data.
    5.  Note the potential effects on the  reported data due to exceeding the calibration criteria in the Data
       Review Narrative.
    6.  If calibration criteria are grossly exceeded, note this for CLP Project Officer (CLP PO) action.
    NOTE:    For truly critical samples, a further in-depth evaluation of the calibration curve may be
               warranted to determine if additional  qualification is necessary.

                       Table 3. Calibration Actions for ICP-AES Analysis
Calibration Result
Calibration not performed
Calibration incomplete
Correlation coefficient <0.995;
%D outside ±30%; y-intercept
>CRQL
ICV/CCV%R<75%
ICV/CCV%R75-89%
ICV/CCV %R 1 1 1-125%
ICV/CCV%R>125%
ICV/CCV %R> 160%
Action for Samples
Qualify all results as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated (J) or unusable (R)
Qualify non-detects as estimated (UJ) or unusable (R)
Qualify results that are >MDL as estimated (J)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated low (J-) or unusable
(R)
Qualify all non-detects as unusable (R)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated high (J+)
Qualify results that are > MDL as estimated high (J+) or unusable
(R)
Qualify results that are > MDL as unusable (R)
January 2010
11

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Inorganic Data Review ICP-AES

Blanks
A. Review Items:
Form I-IN, Form III-IN, Form XII-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, and raw data.

B. Objective:
The objective of blank analysis results assessment is to determine the existence and magnitude of
contamination resulting from laboratory (or field) activities. The criteria for evaluation of blanks
apply to any blank associated with the samples (e.g., method blanks, calibration blanks, field blanks,
etc.). If problems with any blank exist, all associated data must be carefully evaluated to determine
whether or not there is an inherent variability in the data, or if the problem is an isolated occurrence
not affecting other data.

C. Criteria:
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed after the analytical standards, but not before
analysis of the Initial Calibration Verification (ICV) during the initial calibration of the
instrument (see Section II.C.I).
3. A Continuing Calibration Blank (CCB) shall be analyzed at each wavelength used for the
analysis, immediately after every Continuing Calibration Verification (CCV). The CCB shall be
analyzed at a frequency of every two hours during the run. The CCB shall be analyzed at the
beginning of the run, and again after the last CCV that was analyzed after the last analytical
sample of the run. The CCB result (absolute value) shall not exceed the Contract Required
Quantitation Limit (CRQL) of each analyte for which analysis is performed.
4. At least one Preparation Blank shall be prepared and analyzed for each matrix, with every Sample
Delivery Group (SDG), or with each batch of samples digested, whichever is more frequent. The
Preparation Blank consists of reagent water or a clean wipe or filter processed through the
appropriate sample preparation and analysis procedure.
5. If any analyte concentration in the Preparation Blank is > CRQL, the lowest concentration of that
analyte in the associated samples must be > 10 times (lOx) the Preparation Blank concentration.
Otherwise, all samples associated with that Preparation Blank with the analyte's concentration
< lOx the Preparation Blank concentration, and > CRQL, should be redigested and reanalyzed for
that analyte (except for an identified field blank). The laboratory is not to correct the sample
concentration for the blank value.
6. If the concentration of the Preparation Blank for a certain analyte is < (-CRQL) all samples
reported < lOx the CRQL (associated with that analyte in that blank), should be redigested and
reanalyzed.
D. Evaluation:
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the proper
frequency and location during the run, and Preparation Blanks were prepared and analyzed as
appropriate for the SDG (e.g., total number of samples, various types of matrices present, number
of digestion batches, etc.).
2. Review the results reported on the Blank Summary (Form III-IN), as well as the raw data for all
blanks, and verify that the results were accurately reported.
3. Evaluate all of the associated blanks for the presence of target analytes. Verify that if target
analytes were present in a Preparation Blank or if a concentration was < (-CRQL) the affected
samples were redigested and reanalyzed. Verify that if target analytes were present in an ICB or a
CCB, the analysis was terminated, the problem corrected, the instrument recalibrated, and the
preceding 10 analytical samples or all analytical samples analyzed since the last compliant
calibration blank reanalyzed.

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Inorganic Data Review ICP-AES

E. Action:
NOTES: For ICBs that do not meet the technical criteria, apply the action to all samples reported
from the analytical run.
For CCBs that do not meet the technical criteria, apply the action to all samples analyzed
between a previous technically acceptable analysis of the CCB and a subsequent
technically acceptable analysis of the CCB in the analytical run.
For Preparation Blanks that do not meet the technical criteria, apply the action to all
samples prepared in the same preparation batch.
1. If the appropriate blanks were not analyzed with the correct frequency, the data reviewer should
use professional judgment to determine if the associated sample data should be qualified. The
reviewer may need to obtain additional information from the laboratory. The situation should
then be recorded in the Data Review Narrative, and noted for Contract Laboratory Program
Project Officer (CLP PO) action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the blank.
The reviewer should note that in instances where more than one blank is associated with a given
sample, qualification should be based upon a comparison with the associated blank having the
highest concentration of contaminant.
3. Some general "technical" review actions include:
a. Any blank (including Preparation Blanks) reported with a negative result, whose value is
< (-MDL) but > (-CRQL), should be carefully evaluated to determine its effect on the sample
data. The reviewer shall then use professional judgment to assess the data. For any blank
(including Preparation Blanks) reported with a negative result, whose value is < (-CRQL)
qualify results that are > CRQL as estimated low (J-) and non-detects as estimated (UJ).
b. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil/sediment sample results reported on Form I-IN will not
be on the same basis (units, dilution) as the calibration blank data reported on Form III-IN.
The reviewer may find it easier to work with the raw data.
4. Specific "method" actions include:
a. If the absolute value of an ICB or a CCB result is > CRQL, the analysis should be terminated.
If the analysis was not terminated and the affected samples were not reanalyzed, report non-
detects and results that are > MDL, but < CRQL as CRQL-U. For results that are > CRQL
but < Blank Result, use professional judgment to qualify the data as unusable (R) or to report
the results at the level of the blank with a "U" qualifier. Use professional judgment to qualify
results that are > Blank Result. Note this situation for CLP PO action and record it in the
Data Review Narrative.
b. If the absolute value of the concentration of the Preparation Blank is < CRQL, report non-
detects and results that are > MDL but < CRQL as CRQL-U. Use professional judgment to
quality results that are > CRQL.
c. If any analyte concentration in the Preparation Blank is > CRQL, the lowest concentration of
that analyte in the associated samples must be lOx the Preparation Blank concentration.
Otherwise, all samples associated with that blank with concentrations < lOx the Preparation
Blank concentration and > CRQL should be redigested and reanalyzed. Raise the CRQL to
the concentration found in the Preparation Blank and report those samples that do not require
redigestion (that are > MDL but < CRQL) as CRQL-U. Note for CLP PO action and record
in the Data Review Narrative if the laboratory failed to redigest and reanalyze the affected
samples. The reviewer shall then use professional judgment to assess the data.
January 2010 13

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Inorganic Data Review
                                    ICP-AES
                        Table 4. Blank Actions for ICP-AES Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
Preparation
Blank
Preparation
Blank
Preparation
Blank
Blank Result
> MDL but <
CRQL
>CRQL
< (-MDL) but
> (-CRQL)
< (-CRQL)
>CRQL
> MDL but <
CRQL
< (-CRQL)
Sample Result
Non-detect
> MDL but < CRQL
>CRQL
> MDL but < CRQL
> CRQL but < Blank Result
> Blank Result
> MDL, or non-detect
< 1 Ox the CRQL
> MDL but < CRQL
> CRQL but < lOx the Blank
Result
> 1 Ox the Blank Result
Non-detect
> MDL but. < CRQL
>CRQL
< 1 Ox the CRQL
Action for Samples
No action
Report CRQL value with a "U"
Use professional judgment
Report CRQL value with a "U"
Report at level of Blank Result with a
"U" or qualify data as unusable (R)
Use professional judgment
Use professional judgment
Qualify results that are > CRQL as
estimated low (J-)
Qualify non-detects as estimated (UJ)
Report CRQL value with a "U"
Use professional judgment to qualify
results as unusable (R) or estimated
high (J+)
No action
No action
Report CRQL value with a "U"
Use professional judgment
Qualify results that are > CRQL as
estimated low (J-)
Qualify non-detects as estimated (UJ)
January 2010
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Inorganic Data Review ICP-AES

Inductively Coupled Plasma - Interference Check Sample (ICP-ICS)
A. Review Items:
Form FVA-IN, Form XIII-IN, instrument printouts, and raw data.

B. Objective:
The Inductively Coupled Plasma (ICP) - Interference Check Sample (ICS) verifies the analytical
instrument's ability to overcome interferences typical of those found in samples.
NOTE: The laboratory should have analyzed and reported ICS results for all elements being
reported from the analytical run and for all interferents (target and non-target) for these
reported elements.

C. Criteria:
1. The ICS consists of two solutions: Solution A and Solution AB. Solution A consists of the
interferents, and Solution AB consists of the analytes mixed with the interferents. An ICS
analysis consists of analyzing both solutions consecutively, starting with Solution A, for all
wavelengths used for each analyte reported by Inductively Coupled Plasma - Atomic Emission
Spectroscopy (ICP-AES).
2. An ICS must be run at the beginning of each sample analysis run. The ICS is not to be run prior
to the Initial Calibration Verification (ICV), and is to be immediately followed by a Continuing
Calibration Verification (CCV), which will be followed by a Continuing Calibration Blank
(CCB).
3. Results for the analysis of ICS Solution A must fall within the control limits of ± Contract
Required Quantitation Limit (CRQL), or ± 20% of the true value (whichever is greater) for the
analytes and interferents.
4. Results for the analysis of ICS Solution AB must fall within the control limits of ± CRQL, or
± 20% of the true value (whichever is greater) for the analytes and interferents included in the
solution.
5. If the value of an ICS result exceeds ± CRQL, or ± 20% of true value (whichever is greater)
criteria, the analysis shall be terminated, the problem corrected, the instrument recalibrated, the
new calibration then reverified, and the affected samples reanalyzed.
6. The ICS should be obtained from USEPA if available, and analyzed according to the instructions
supplied with the solutions. The ICS may be prepared with the interferents at 2x the level
specified in the Statement of Work (SOW) if high levels of interferents are found in the field
samples. If the ICS is not available from USEPA, an independent ICS solution shall be prepared
with the interferent and analyte concentrations at the levels specified in the method.
D. Evaluation:
1. Verify using the raw data (ICP instrument printout) that the ICS was analyzed at the proper
frequency and location during the analytical run.
2. Evaluate the ICS raw data for results with an absolute value that is > Method Detection Limit
(MDL) for those analytes which are not present in the ICS solution.
3. Recalculate using the raw data and the following equation, one or more of the analyte Percent
Recoveries (%R), and verify that the recalculated value agrees with the laboratory-reported
values on Form IV-IN.
January 2010 15

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Inorganic Data Review ICP-AES
o/0R = x 100
True (value)
Where,
„ j / i x Concentration (in ug/L) of each analyte interferent measured in the
Found (value) = , . --,„„ c , .. . Tr,c c , .. Ar> -
v ' analysis of ICS Solution A or ICS Solution AB
„ , , , _ Concentration (in (ig/L) of each analyte or interferent in ICS Solution
1 rue (value) - A or ICS Solutlon AB

4. If the value of an ICS result exceeds the ± CRQL, or ± 20% of true value (whichever is greater)
criteria, and the laboratory failed to terminate the analysis, and take the appropriate corrective
action, note this for Contract Laboratory Program Project Officer (CLP PO) action and record in
the Data Review Narrative. Use professional judgment to assess the data.
E. Action:
NOTE: For an ICS that does not meet the technical criteria, apply the action to all samples
analyzed in the analytical run.
1 . The raw data should, but may not, contain results for interferents. If not, the reviewer shall use
professional judgment to qualify the data. If the data does contain results for interferents, the
reviewer should apply the following actions to samples with concentrations of interferents that
are comparable to, or greater than, their respective levels in the ICS:
a. If the ICS %R for an analyte or interferent is > 120% (or greater than the true value + CRQL,
as applicable) and the sample results are non-detects, the data should not be qualified.
b. If the ICS %R for an analyte or interferent is > 120% (or greater than the true value + CRQL,
as applicable) qualify sample results that are > MDL as estimated high (J+). If the ICS %R
(or true value) grossly exceeds the limits, use professional judgment to qualify the data.
c. If the ICS %R for an analyte or interferent falls within the range of 50-79% (or less than the
true value - CRQL, as applicable) qualify sample results that are > MDL as estimated low
(J-).
d. If the ICS recovery for an analyte falls within the range of 50-79% (or less than the true value
- CRQL, as applicable), the possibility of false negatives exists. Qualify sample non-detects
as estimated (UJ).
e. If the ICSAB %R for an analyte or interferent is < 50%, qualify all sample results that are
> MDL as estimated low (J-) and all sample non-detects as unusable (R).
2. If results that are > MDL are observed for analytes that are not present in the ICS solution, the
possibility of false positives exists. An evaluation of the associated sample data for the affected
elements should be made. For samples with comparable or higher levels of interferents and with
analyte concentrations that approximate those levels found in the ICS, qualify sample results that
are > MDL as estimated high (J+). Non-detects should not be qualified.
3. If negative results are observed for analytes that are not present in the ICS solution, and their
absolute value is > MDL, the possibility of false negatives in the samples exists. An evaluation
of the associated sample data for the affected analytes should be made. For samples with
comparable or higher levels of interferents, qualify non-detects for the affected analytes as
estimated (UJ), and results that are > MDL but < lOx the absolute value of the negative result as
estimated low (J-).
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ICP-AES
4. In general, ICP-AES sample data can be accepted if the concentrations of Al, Ca, Fe, and Mg in
the sample are found to be less than or equal to their respective concentrations in the ICS. If
these elements are present at concentrations greater than the level in the ICS, or other elements
are present in the sample at > 10 mg/L, the reviewer should investigate the possibility of other
interference effects as given in the ICP-AES method or as indicated by the laboratory's
interelement correction factors reported on Forms XA-IN and XB-IN for that particular
instrument. The analyte concentration equivalents presented in the method should be considered
only as estimated values since the exact value of any analytical system is instrument-specific.
Therefore, estimate the concentration produced by an interfering element. If the estimate is > 2x
the CRQL, and also > 10% of the reported concentration of the affected element, qualify the
affected results as estimated (J).
5. If the raw data does not contain results for the interferents, note it in the Data Review Narrative.
6. Actions regarding the interpretation and/or the subsequent qualification of ICP data due to the
ICS analytical results can be extremely complex. Use professional judgment to determine the
need for the associated sample data to be qualified. The reviewer may need to obtain additional
information from the laboratory. All interpretive situations should then be recorded in the Data
Review Narrative.
7. If the ICS acceptance criteria are grossly exceeded, note the specifics for CLP PO action.

Table 5. Interference Check Actions for ICP-AES Analysis
Interference Check Sample Results
ICS %R > 120% (or greater than true value +
CRQL)
ICS %R 50-79% (or less than true value -
CRQL)
ICSAB%R<50%
Potential false positives in field samples with
interferents
Potential false negatives in field samples with
interferents
Action for Samples
Qualify results that are > MDL as estimated high
(J+)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Qualify results that are > MDL as estimated high
(J+)
Qualify results that are > MDL but < 10x( negative
value |) as estimated low (J-)
Qualify non-detects as estimated (UJ)
January 2010
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Inorganic Data Review ICP-AES

Laboratory Control Sample (LCS)
A. Review Items:
Form VII-IN, Form XII-IN, preparation logs, instrument printouts, and raw data.

B. Objective:
The Laboratory Control Sample (LCS) serves as a monitor of the overall performance of each step
during the analysis, including the sample preparation.

C. Criteria:
1. Aqueous/water, soil/sediment, wipe, and filter LCSs shall be analyzed for each analyte utilizing
the same sample preparations, analytical methods, and Quality Assurance/Quality Control
(QA/QC) procedures as employed for the samples.
a. One LCS shall be prepared and analyzed for every group of aqueous/water or soil/sediment
samples in a Sample Delivery Group (SDG), or with each batch of samples digested,
whichever is more frequent. The LCS shall be spiked such that the final digestate contains
each analyte at two times the CRQL for the associated matrix.
b. All LCS Percent Recoveries (%R) must fall within the control limits of 70-130%, except for
Sb and Ag which must fall within the control limits of 50-150%. If the %R for the
aqueous/water and soil/sediment LCS falls outside of the control limits, the analysis should
be terminated, the problem corrected, and the samples prepared with that LCS redigested and
reanalyzed.
c. One LCS shall be prepared and analyzed for each group of wipe or filter samples in an SDG,
or with each batch of wipe or filter samples digested, whichever is more frequent. The wipe
or filter LCS shall be spiked such that the final digestate contains each analyte at two times
the CRQL for the associated matrix.
d. All wipe or filter sample LCS %R shall fall within the control limits of 70-130%.
D. Evaluation:
1. Verify using Form VII-IN, Form XII-IN, and raw data that the appropriate number of required
LCSs were prepared and analyzed for the SDG.
2. Evaluate Form VII-IN and verify that all results for each analyte fall within the established
control limits.
a. Check the raw data to verify that the %Rs on Form VII-IN were accurately transcribed.
Recalculate one or more of the reported %Rs using the following equation:

o/oR = Found(value) x 100
True (value)
Where,
Found (value) = Concentration of each analyte (in (ig/L, mg/kg, or ug) measured in the
analysis of the LCS
True (value) = Concentration of each analyte (in (ig/L, mg/kg, or ug) in the LCS

3. Verify that the LCS was prepared at the same time as the associated samples using the same
procedures.
E. Action:
If the LCS criteria are not met, the laboratory performance and method accuracy are in question.
Professional judgment should be used to determine if the data should be qualified or rejected. The
following guidance is suggested for qualifying sample data associated with an LCS that does not meet
the required criteria.

January 2010 18

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Inorganic Data Review
                                       ICP-AES
    For an LCS that does not meet the technical criteria, apply the action to all samples in the same
    preparation batch.
    1.  Aqueous/Water and Soil/Sediment LCS:
       a.  If the LCS %R falls within the range of 40-69% (20-49% for Ag and Sb), qualify sample
           results that are > Method Detection Limit (MDL) as estimated low (J-). If the LCS %R is >
           130% (150% for Ag and Sb), qualify sample results that are > MDL as estimated high (J+).
       b.  If the LCS recovery is > 130% (150% for Ag and Sb) and the sample results are non-detects,
           the data should not be qualified.
       c.  If the LCS recovery falls within the range of 40-69% (20-49% for Ag and Sb), qualify non-
           detects as estimated (UJ).
       d.  If LCS  %R is < 40% (<20% for Ag and Sb), qualify all results that are > MDL as estimated
           low (J-) and all non-detects as unusable (R).
       e.  If the LCS %R is > 15 0% (170% for Ag and Sb), qualify all affected data (both detects and
           non-detects) as unusable (R).
    2.  Wipe/Filter LCS:
       a.  If the LCS %R is in the range of 40-69%, qualify sample results that are > MDL as estimated
           low (J-) and qualify non-detects as estimated (UJ).
       b.  If the LCS %R is < 40%, qualify all results that are > MDL as estimated low (J-) and all non-
           detects as unusable (R).
       c.  If the LCS %R is > 130% and the sample results are non-detects, do not qualify the data.
       d.  If the LCS %R is > 130%, qualify all results > MDL as estimated high (J+).
    3.  If a laboratory fails to analyze an LCS with each SDG, or if a laboratory consistently fails to
       generate acceptable LCS recoveries, note this for CLP Project Officer (CLP PO) action.
    4.  Whenever possible, the potential effects on the  data due to out-of-control LCS results should be
       noted in the Data Review Narrative.

                          Table 6. LCS Actions  for ICP-AES Analysis
LCS Result
Aqueous/Water and Soil/Sediment %R 40-69%
(20-49% Ag, Sb)
Aqueous/Water and Soil/Sediment %R > 130%
(150% Ag, Sb)
Aqueous/Water and Soil/Sediment %R < 40%
(<20% Ag, Sb)
Aqueous/Water and Soil/Sediment %R > 150%
(>170%Ag, Sb)
Wipe/Filter %R 40-69%
Wipe/Filter %R> 130%
Wipe/Filter %R< 40%
Action for Samples
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated high (J+)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Qualify all results as unusable (R)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated high (J+)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
January 2010
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Inorganic Data Review ICP-AES

Duplicate Sample Analysis
A. Review Items:
Cover Page, Form VI-IN, Form XII-IN, instrument printouts, and raw data.

B. Objective:
The objective of duplicate sample analysis is to demonstrate acceptable method precision by the
laboratory at the time of analysis. Duplicate analyses are also performed to generate data that
determines the long-term precision of the analytical method on various matrices. Non-homogenous
samples can impact the apparent method precision. However, aqueous/water samples are generally
homogenous and most soil/sediment samples are homogenous within a factor of two or three.

C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
duplicate sample analysis.
2. At least one duplicate sample shall be prepared and analyzed from each group of samples of a
similar matrix type (e.g., water or soil) or for each Sample Delivery Group (SDG). Duplicates are
not required for wipe or filter samples. Duplicates cannot be averaged for reporting on Form I-
IN. Additional duplicate sample analyses may be required by USEPA Regional request.
Alternately, the Region may require that a specific sample be used for the duplicate sample
analysis.
3. A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original and
duplicate sample values > five times (5x) the Contract Required Quantitation Limit (CRQL).
4. A control limit of the CRQL shall be used if either the sample or duplicate value is < 5x the
CRQL. The absolute value of the control limit (CRQL) shall be entered in the "Control Limit"
column on Form VI-IN. If both samples are non-detects, the RPD is not calculated for Form VI-
IN.
NOTE: The above control limits are method requirements for duplicate samples, regardless of
the sample matrix type. However, it should be noted that laboratory variability arising
from the sub-sampling of non-homogenous soil samples is a common occurrence.
Therefore, for technical review purposes only, Regional policy or project Data Quality
Objectives (DQOs) may allow the use of less restrictive criteria (e.g., 35% RPD, 2x the
CRQL) to be assessed against duplicate soil samples.
D. Evaluation:
1. Verify from the Cover Page, Form XII-IN, and the raw data that the appropriate number of
required duplicate samples were prepared and analyzed for the SDG.
2. Evaluate Form VI-IN and the raw data to verify that all duplicate results for each analyte and
method fall within the established control limits.
3. Verify that a field blank or PE sample was not used for duplicate analysis.
4. Check the raw data and recalculate one or more of the RPD values using the following equation
to verify that the results were correctly reported on Form VI-IN:
IS-D
RPD = J x 100
(S + D)/2
Where,
RPD = Relative Percent Difference
S = Sample Result (original)
D = Duplicate Result
January 2010 20

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Inorganic Data Review
ICP-AES
E. Action:
NOTE:
1.
2.
For a duplicate sample analysis that does not meet the technical criteria, apply the action
to all samples of the same matrix if the reviewer considers the samples to be sufficiently
similar. The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make use of all available data when determining
similarity, including: site and sampling documentation (e.g., location and type of sample,
descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity, chlorine);
and laboratory data for other parameters [e.g., Total Suspended Solids (TSSs), Total
Dissolved Solids (TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity,
reactive sulfide, anions]. The reviewer should also use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG. The
reviewer may determine that only some of the samples in the SDG are similar to the
duplicate sample, and that only these samples should be qualified. Or, the reviewer may
determine that no samples are sufficiently similar to the sample used for the duplicate,
and thus that only the field sample used to prepare the duplicate sample should be
qualified.
If the appropriate number of duplicate samples was not analyzed for each matrix using the correct
frequency, use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the laboratory. Note the
situation in the Data Review Narrative, and for CLP Project Officer (CLP PO) action.
If the results from a duplicate analysis for a particular analyte fall outside the appropriate control
limits, qualify sample results that are > Method Detection Limit (MDL) as estimated (J) and non-
detects as estimated (UJ).
If a field blank or PE sample was used for the duplicate sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked and
professional judgment exercised by the data reviewer when evaluating the data.
Note the potential effects on the data due to out-of-control duplicate sample results in the Data
Review Narrative.

Table 7. Duplicate Sample Actions for ICP-AES Analysis
Duplicate Sample Results
Both original sample and duplicate sample > 5x
the CRQL and RPD > 20%*
Original sample or duplicate sample < 5x the
CRQL (including non-detects) and absolute
difference between sample and duplicate
> CRQL*
Action for Samples
Qualify those results that are > MDL that
professional judgment determines to be affected as
estimated (J) and non-detects as estimated (UJ)
Qualify those results that are > MDL that
professional judgment determines to be affected as
estimated (J) and non-detects as estimated (UJ)
The above control limits are method requirements for duplicate samples, regardless of the sample
matrix type. However, it should be noted that laboratory variability arising from the sub-sampling of
non-homogenous soil samples is a common occurrence. Therefore, for technical review purposes
only, Regional policy or project Data Quality Objectives (DQOs) may allow the use of less
restrictive criteria (e.g., 35% RPD, 2xthe CRQL) to be assessed against duplicate soil samples.
January 2010
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Inorganic Data Review ICP-AES

Spike Sample Analysis
A. Review Items:
Cover Page, Form V-IN (Part A & B), Form XII-IN, instrument printouts, and raw data.

B. Objective:
The spiked sample analysis is designed to provide information about the effect of each sample matrix
on the sample preparation procedures and the measurement methodology. Non-homogenous samples
can impact the apparent method recovery. However, aqueous/water samples are generally
homogenous and most soil/sediment samples are homogenous within a factor of two or three. If the
spike is added to the sample before the digestion (e.g., prior to the addition of other reagents), it is
referred to as a spiked sample, pre-digestion spike, or Matrix Spike. If the spike is added to the
sample after the completion of the digestion procedures, it is referred to as a post-digestion spike, or
analytical spike.

4. The spike Percent Recovery (%R) shall be within the established acceptance limits. However,
spike recovery limits do not apply when the sample concentration is > 4x the spike added. In
such an event, the data shall be reported unflagged, even if the %R does not meet the acceptance
criteria.
5. If the spiked sample analysis was performed on the same sample that was chosen for the duplicate
sample analysis, spike calculations shall be performed using the results of the sample designated
as the "original sample". The average of the duplicate results cannot be used for the purpose of
determining %R.

NOTE: The final spike concentrations required for the various target analytes are presented in the
methods described in the Statement of Work (SOW).
D. Evaluation:
1. Verify using the Cover Page, Form VA-IN, Form XII-IN, and raw data, that the appropriate
number of required spiked samples were prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
3. Evaluate Form VA-IN and the raw data to verify that all pre-digestion spiked sample results for
each required analyte fall within the established control limits. If not, verify that a post-
digestion/post-distillation spike was prepared and analyzed.
4. Recalculate using the raw data, one or more of the %R using the following equation, and verify
that the recalculated value agrees with the laboratory-reported values on Forms V (A & B)-IN:
January 2010 22

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Inorganic Data Review
ICP-AES
% Recovery =

Where,
SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added
SSR- SR
SA
100
NOTE: When the sample concentration is < Method Detection Limit (MDL), use SR = 0 only for
the purpose of calculating the %R. The actual spiked sample results, sample results, and
%R (positive or negative) shall still be reported on Forms VA-IN and VB-IN.
E. Action:
NOTE: For a Matrix Spike that does not meet the technical criteria, apply the action to all
samples of the same matrix, if the reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make use of all available data, including: site and
sampling documentation (e.g., location and type of sample, descriptive data, soil
classification); field test data (e.g., pH, Eh, conductivity, chlorine); and laboratory data
for other parameters [e.g., Total Suspended Solids (TSSs), Total Dissolved Solids
(TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
anions], in determining similarity. The reviewer should also use the sample data (e.g.,
similar concentrations of analytes) in determining similarity between samples in the
SDG. The reviewer may determine that only some of the samples in the SDG are similar
to the Matrix Spike sample, and that only these samples should be qualified. Or, the
reviewer may determine that no samples are sufficiently similar to the sample used for
the Matrix Spike, and thus that only the field sample used to prepare the Matrix Spike
sample should be qualified.
1. If the appropriate number of Matrix Spike samples was not analyzed for each matrix using the
correct frequency, use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the laboratory. Note the
situation in the Data Review Narrative, and for Contract Laboratory Program Project Officer
(CLP PO) action.
2. If a field blank or PE sample was used for the spiked sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked and
professional judgment exercised by the data reviewer when evaluating the data.
3. If the Matrix Spike recovery does not meet the evaluation criteria and a required post-digestion
spike was not performed, note this for CLP PO action.
4. If the Matrix Spike %R is < 30%, verify that a post-digestion spike was analyzed (if required). If
the post-digestion spike %R is < 75% or is not performed, qualify sample results that are >MDL
as estimated low (J-) and non-detects as unusable (R). If the post-digestion spike %R is > 75%,
qualify sample results that are > MDL as estimated (J) and non-detects as estimated (UJ).
5. If the Matrix Spike %R is 30-74% and the sample results are > MDL, verify that a post-digestion
spike was analyzed (if required). If the %R for the post-digestion is also < 75% or is not
performed, qualify the affected data as estimated low (J-). If the %R for the post-digestion spike
is > 75%, qualify the affected data as estimated (J).
6. If the Matrix Spike %R falls within the range of 30-74% and the sample results are non-detects,
qualify the affected data as estimated (UJ).
7. If the Matrix Spike %R is > 125% and the reported sample results are non-detects, the sample
data should not be qualified.
January 2010
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Inorganic Data Review
                                        ICP-AES
    8.  If the Matrix Spike %R is > 125% and the sample results are > MDL, verify that a post-digestion
       spike was analyzed if required. If the %R for the post-digestion spike is also > 125% or is not
       performed, qualify the affected data as estimated high (J+).  If the %R for the post-digestion spike
       is < 125%, qualify the affected data as estimated (J).
    9.  Note the potential effects on the data due to out-of-control spiked sample results in the Data
       Review Narrative.

                      Table 8. Spike Sample Actions for ICP-AES Analysis
Spike Sample Results
Matrix Spike %R < 30%
Post-digestion spike %R< 75%
Matrix Spike %R < 30%
Post-digestion spike %R> 75%
Matrix Spike %R 30-74%
Post-digestion Spike %R< 75%
Matrix Spike %R 30-74%
Post-digestion spike %R> 75%
Matrix Spike %R > 125%
Post-digestion spike %R> 125%
Matrix Spike %R > 125%
Post-digestion spike %R< 125%
Matrix Spike %R < 30%
No post-digestion spike performed
(e.g., not required for Ag)
Matrix Spike %R 30-74%
No post-digestion spike performed
(e.g., not required for Ag)
Matrix Spike %R > 125%
No post-digestion spike performed
(e.g., not required for Ag)
Action for Samples
Qualify affected results that are > MDL as estimated low
(J-) and affected non-detects as unusable (R)
Qualify affected results that are > MDL as estimated (J) and
affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated low
(J-) and affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated (J) and
affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated high
(J+)
Qualify affected results that are > MDL as estimated (J)
Qualify affected results that are > MDL as estimated low
(J-) and affected non-detects as unusable (R)
Qualify affected results that are > MDL as estimated low
(J-) and non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated high
(J+)
Non-detects are not qualified
January 2010
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Inorganic Data Review ICP-AES

ICP Serial Dilution
A. Review Items:
Form I-IN, Form VIII-IN, instrument printouts, and raw data.

B. Objective:
The serial dilution of samples quantitated by Inductively Coupled Plasma - Atomic Emission
Spectroscopy (ICP-AES) determines whether or not significant physical or chemical interferences
exist due to sample matrix.

C. Criteria:
1. An ICP Serial Dilution analysis shall be performed on a sample from each group of samples with
a similar matrix type (e.g., water, soil, wipe, or filter) or for each Sample Delivery Group (SDG),
whichever is more frequent.
2. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for the
ICP Serial Dilution analysis.
3. If the analyte concentration is sufficiently high [concentration in the original sample is > 50 times
(5 Ox) the Method Detection Limit (MDL)], the Percent Difference (%D) between the original
determination and the serial dilution analysis (a five-fold dilution) after correction for dilution
shall be less than 10.
NOTE: The above criteria are method requirements for serial dilution samples, regardless of the
sample matrix type. However, for technical review purposes only, Regional policy or
project Data Quality Objectives (DQOs) may allow the use of less restrictive criteria
(e.g., %D < 15) to be assessed against serial dilution soil samples.
D. Evaluation:
1. Verify that a field blank or PE sample was not used for the serial dilution analysis.
2. Check the raw data and recalculate the %D using the following equation. Verify that the serial
dilution analysis results, and the calculated %D results agree with the values reported by the
laboratory on Form VIII-IN:
I I - S I
% Difference = J L x 100
I
Where,
I = Initial Sample Result
S = Serial Dilution Result

3. Check the raw data for any evidence of positive or negative interference (results from the diluted
sample which are significantly different than the original sample), possibly due to high levels of
dissolved solids in the sample, ionization effects, etc.
E. Action:
NOTE: For a serial dilution that does not meet the technical criteria, apply the action to all
samples of the same matrix if the reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make use of all available data, including: site and
sampling documentation (e.g., location and type of sample, descriptive data, soil
classification); field test data (e.g., pH, Eh, conductivity, chlorine); and laboratory data
for other parameters [e.g., Total Suspended Solids (TSSs), Total Dissolved Solids
(TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
anions], in determining similarity. The reviewer should also use the sample data (e.g.,
similar concentrations of analytes) in determining similarity between samples in the
SDG. The reviewer may determine that only some of the samples in the SDG are similar
January 2010 25

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ICP-AES
to the serial dilution sample, and that only these samples should be qualified. Or, the
reviewer may determine that no samples are sufficiently similar to the sample used for
serial dilution, and thus that only the field sample used to prepare the serial dilution
sample should be qualified.
If the required %D criteria are not met, qualify all affected results that are > MDL as
estimated (J) and all affected non-detects as estimated (UJ).
If evidence of positive or negative interference is found, use professional judgment to qualify the
associated sample data. Note the potential effects on the reported data in the Data Review
Narrative.
It should be noted for Contract Laboratory Program Project Officer (CLP PO) action and in the
Data Review Narrative if a field blank or PE sample was used for the serial dilution analysis.

Table 9. Serial Dilution Actions for ICP-AES Analysis
Serial Dilution Result
Sample concentration > 5 Ox MDL and %D >
10*
Interferences present
Action for Samples
Qualify affected results that are > MDL as estimated
(J)
Qualify affected non-detects as estimated (UJ)
Use professional judgment
* The above criteria are method requirements for serial dilution samples, regardless of the sample
matrix type. However, for technical review purposes only, Regional policy or project Data
Quality Objectives (DQOs) may allow the use of less restrictive criteria (e.g., %D < 15) to be
assessed against serial dilution soil samples.
January 2010
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Inorganic Data Review                                                                 ICP-AES


                   Regional Quality Assurance (OA) and Quality Control (OC)
A.  Review Items:
    Form I-IN, instrument printouts, and raw data.

B.  Objective:
    Regional QA/QC samples refer to any QA and/or QC sample initiated by the Region, including field
    duplicate samples, Performance Evaluation (PE) samples, blind spikes and blind blanks. The use of
    these QA/QC samples is highly recommended (e.g., the use of field duplicates can provide
    information on sampling precision and homogeneity).

C.  Criteria:
    Criteria are determined by each Region.
D.  Evaluation:
    Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data
    review. Each Region will handle the evaluation of PE samples on an individual basis. Compare
    results for PE samples to the acceptance  criteria for the specific PE samples if possible.
    Calculate the Relative Percent Difference (RPD) between field duplicates and provide this
    information in the Data Review Narrative.
E.  Action:
    Any action must be in accordance with Regional specifications and criteria for acceptable PE sample
    results. Note any unacceptable PE sample results for Contract Laboratory Program Project Officer
    (CLP PO) action.
January 2010                                    27

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Inorganic Data Review ICP-AES

Overall Assessment
A. Review Items:
Entire sample data package, data review results, preparation logs, calibration standard logs,
instrument logs, instrument printouts, and raw data (including any confirmation data).

B. Objective:
1. The objective is to ensure that the reported sample quantitation results are accurate. It is
appropriate for the data reviewer to make professional judgments and express concerns, as well as
to comment on the validity of the overall data for a Case. This is particularly appropriate when
there are several Quality Control (QC) criteria that are outside of the specification parameters.
The additive nature of QC factors that fall outside of specification parameters is difficult to assess
in an objective manner, but the reviewer has a responsibility to inform the user of data quality and
data limitations to assist that user to avoid inappropriate use of the data, while not precluding any
consideration of the data. If qualifiers other than those used in this document are necessary to
describe or qualify the data, it is necessary to thoroughly document/explain the additional
qualifiers used. The data reviewer would be greatly assisted in this endeavor if the acceptance or
performance criteria were provided. The Inorganic Review Summary (see Appendix B) and
supplementary documentation must be included with the review.

C. Criteria:
1. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
2. Reported analyte concentrations must be quantitated according to the appropriate analytical
method, as listed in the method.
D. Evaluation:
Examine the raw data to verify that correct calculations of the sample results were reported by the
laboratory. Digestion logs, instrument printouts, etc., should be compared to the reported sample
results recorded on the appropriate Inorganic Summary Forms (Form I-IN through Form XIII-IN).
1. Evaluate any technical problems not previously addressed.
2. Examine the raw data for any anomalies (e.g., baseline shifts, negative absorbance, omissions,
illegibility, etc.).
3. Verify that appropriate methods and amounts were used in preparing the samples for analysis. If
reduced volumes were used, verify that the laboratory had received Contract Laboratory Program
Project Officer (CLP PO) approval for the use of the reduced volume.
4. Verify that there are no transcription or reduction errors [e.g., dilutions, Percent Solids (%S),
sample weights, etc.] on one or more samples.
5. Verify that results fall within the calibrated range(s) of the Inductively Coupled Plasma (ICP)
instrument(s).
6. If appropriate information is available, the reviewer may assess the usability of the data to assist
the data user in avoiding inappropriate use of the data. Review all available information,
including the Quality Assurance Project Plan (QAPP), focusing specifically on the acceptance or
performance criteria, the Standard Operating Procedure(s) (SOPs), and communication with the
user concerning the intended use and desired quality of these data.
E. Action:
1. Use professional judgment to determine if there is any need to qualify data which were not
qualified based on the QC criteria previously discussed.
January 2010 28

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Inorganic Data Review                                                                    ICP-AES

    2.  Write a brief Data Review Narrative to give the user an indication of the analytical limitations of
       the data. Note any discrepancies between the data and the Sample Delivery Group (SDG)
       Narrative for Contract Laboratory Program Project Officer (CLP PO) action. If sufficient
       information on the intended use and required quality of the data is available, the reviewer should
       include an assessment of the data usability within the given context.
    3.  If any discrepancies are found, the laboratory may be contacted by the Region's designated
       representative to obtain additional information for resolution. If a discrepancy remains
       unresolved, the reviewer may determine that qualification of the data is warranted.
January 2010                                    29

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Inorganic Data Review                                                                 ICP-AES

                                  Calculations for ICP-AES
    Aqueous/Water Samples by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-
    AES):
       The concentrations determined in the digestate are to be reported in units of (ig/L:
                                                      Vf
                               Concentration (ug/L) = C x —±- x DF

       Where,
           C     =  Instrument value in |og/L (The average of all replicate exposures.)
           Vf    =  Final digestion volume (mL)
           V     =  Initial aliquot amount (mL)
           DF   =  Dilution Factor

    Soil/Sediment Samples by ICP-AES:
       The concentrations determined in the digestate are to be reported on the basis of the dry weight of
       the sample, in units of mg/kg:
                                                        Vf
                        Concentration (drywt.)(mg/kg) = C x —^x DF/1000
                                                      WxS
       Where,
           C     =  Instrument value in |og/L (The average of all replicate exposures).
           Vf    =  Final digestion volume (mL)
           W    =  Initial aliquot amount (g)
           S     =  % Solids/100 (see Exhibit D - Introduction to Analytical Methods, Section 1.6).
           DF   =  Dilution Factor

    Adjusted Method Detection Limit (MDL)/Adjusted Contract Required Quantitation Limit
    (CRQL) Calculation:
       To calculate the adjusted MDL or adjusted CRQL for aqueous/water samples, substitute the value
       of the MDL ((ig/L) or CRQL ((ig/L) into the "C" term in the equation above.
       Calculate the adjusted MDL or adjusted CRQL for soil/sediment samples as follows:

                     Adjusted Concentration (mg/kg) = C x	— x—- xDF
                                                        WxS  VM
       Where,
           C     =  MDL or CRQL (mg/kg)
           WM   =  Minimum method required aliquot amount (g) (1.00 g or 0.50 g)
           W    =  Initial aliquot amount (g)
           VM   =  Method required final sample digestion volume (mL) (100 mL or 50 mL)
           Vf    =  Final digestion volume (mL)
           S     =  % Solids/100 (see Exhibit D - Introduction to Analytical Methods, Section 1.6).
           DF   =  Dilution Factor
January 2010                                   30

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Inorganic Data Review                                                                  ICP-AES

    Wipe/Filter Mass:
                                   Mass (ug) = C x Vf x DF /1000
       Where,
           C     = Instrument value in jog/L (The average of all replicate exposures).
           Vf    = Final digestion volume (mL)
           DF    = Dilution Factor
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Inorganic Data Review                                                                ICP-MS

                                 ICP-MS DATA REVIEW
The inorganic data requirements for Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) to be
reviewed during validation are listed below:
I.      Preservation and Holding Times	34
II.     ICP-MS Tune Analysis	36
III.    Calibration	38
IV.    Blanks	41
V.     Inductively Coupled Plasma - Interference Check Sample (ICP-ICS)	44
VI.    Laboratory Control Sample (LCS)	47
VII.   Duplicate Sample Analysis	49
VIII.   Spike Sample Analysis	51
IX.    ICP Serial Dilution	54
X.     ICP-MS Internal Standards	56
XI.    Regional Quality Assurance (QA) and Quality Control (QC)	58
XII.   Overall Assessment	59
Calculations for ICP-MS	61
January 2010                                 32

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Inorganic Data Review                                                         ICP-MS


                      An Example Analytical Sequence for ICP-MS
Tune
SO
S
S
S
S
S
ICV
ICB
ICSA
ICSAB
CCV
CCB
samples
CCV
CCB
samples
CCV
CCB, etc.
January 2010                              33

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Inorganic Data Review ICP-MS

I. Preservation and Holding Times
A. Review Items:
Form IA-IN, Form IB-IN, Form XII-IN, Form XIII-IN, Traffic Report/Chain of Custody (TR/COC)
documentation, Form DC-1, raw data, and the Sample Delivery Group (SDG) Narrative checking for:
pH; cooler temperature; holding time; and other sample conditions.

B. Objective:
The objective is to determine the validity of the analytical results based on the sample condition, and
the holding time of the sample from the date of collection to the date of analysis.
C. Criteria:
1. The technical holding time criteria for aqueous/water metal samples is 180 days, preserved (with
nitric acid) to pH < 2. The addition of nitric acid to adjust the pH is only required for
aqueous/water samples.
2. The technical holding time criteria for soil/sediment metal samples is 180 days, based on the
technical holding time criteria for aqueous/water samples.
3. Samples shall be maintained at 4°C (±2°C) until preparation and analysis.
D. Evaluation:
Technical holding times are established by comparing the sampling date(s) on the TR/COC
documentation with the dates of analysis on Form XIII-IN, and the raw data. Information contained
in the Complete SDG File (CSF) should also be considered in the determination of holding times.
Verify that the analysis dates on the Form XIIIs and the raw data are identical. Review the SDG
Narrative and raw data preparation logs to determine if samples were properly preserved. Review the
SDG Narrative to determine if the aqueous/water samples were received in glass containers. If there
is an indication that there were problems with the samples, the integrity of the samples may be
compromised and professional judgment should be used to evaluate the effect of the problem on the
sample results.
E. Action:
NOTE: Apply the action to each sample for which the preservation or holding time criteria was
not met.
1. If the pH of aqueous/water metals samples is > 2 at the time of sample receipt, determine if the
laboratory adjusted the pH to <2 at the time of sample receipt. If not, use professional judgment
to qualify the samples based on the pH of the sample and the chemistry of the metal(s) of interest.
Qualify results that are > Method Detection Limit (MDL) as estimated low (J-), and qualify non-
detects as unusable (R).
2. If technical holding times are exceeded, use professional judgment to determine the reliability of
the data based on the magnitude of the additional time compared to the technical requirement and
whether the samples were properly preserved. The expected bias would be low. Qualify results
that are > MDL as estimated low (J-), and qualify non-detects as unusable (R).
3. Due to limited information concerning holding times for soil/sediment samples, it is left to the
discretion of the data reviewer whether to apply 180 day holding time criteria to soil/sediment
samples. If it is applied, it must be clearly documented in the Data Review Narrative.
4. When the holding times are exceeded, the reviewer should comment in the Data Review
Narrative on any possible consequences for the analytical results.
5. When holding times are grossly exceeded, note this for Contract Laboratory Program Project
Officer (CLP PO) action.
January 2010 34

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Inorganic Data Review
                                     ICP-MS
                Table 10. Technical Holding Time Actions for ICP-MS Analysis
Preservation & Holding Time Results
Aqueous/water metals samples received with
pH > 2 and pH not adjusted
Metals samples not maintained at
4°C(±2°C)
Technical Holding Time exceeded:
Aqueous/water Metals > 180 day
Technical Holding Time exceeded:
Soil/sediment Metals > 180 days
Action for Samples
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
January 2010
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Inorganic Data Review ICP-MS

ICP-MS Tune Analysis
A. Review Items:
Form XFV-IN, instrument printouts, and raw data.

B. Objective:
The Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) tune serves as an initial
demonstration of instrument stability and precision.

C. Criteria:
1. Prior to calibration, the laboratory shall analyze or scan the ICP-MS tuning solution at least five
times (5x) consecutively. The tuning solution contains 100 (ig/L of Be, Mg, Co, In, and Pb. The
solution shall contain all required isotopes of the above elements. The laboratory shall make any
adjustments necessary to bring peak width within the instrument manufacturer's specifications
and adjust mass resolution to within 0.1 u over the range of 6-210 u.
2. The Percent Relative Standard Deviation (%RSD) of the absolute signals for all analytes in the
tuning solution must be < 5%.
D. Evaluation:
1. Verify using the raw data and Form XIV-IN that the appropriate number of analyses or scans of
the ICP-MS tuning solution were performed, and that the appropriate analytes were present in the
solution.
2. Verify using the raw data and Form XIV-IN that the mass calibration falls within the limits for
each isotope of each analyte.
3. Verify using the raw data and Form XIV-IN that the %RSD is < 5% for each isotope of each
analyte.
4. Check the raw data to verify that the reported average mass and %RSD on Form XIV-IN was
accurately calculated. Recalculate one or more of the average masses and %RSDs for an isotope
using the following equations:
Mean =
Where,
x = Mass from analysis
n = Number of analyses
o , x 100
Percent Relative Standard Deviation = ——±=
x

Where,
x = Mean
on_i = Standard Deviation

E. Action:
NOTE: For ICP-MS tunes that do not meet the technical criteria, apply the action to all samples
reported from the analytical run.
1. If the ICP-MS instrument was not tuned prior to calibration, the sample data should be qualified
as unusable (R).
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Inorganic Data Review
ICP-MS
2. If the tuning solution was not analyzed or scanned at least 5x consecutively or the tuning solution
does not contain the required analytes spanning the analytical range, the reviewer should use
professional judgment to determine if the associated sample data should be qualified. The
reviewer may need to obtain additional information from the laboratory. The situation should be
recorded in the Data Review Narrative and noted for Contract Laboratory Program Project
Officer (CLP PO) action.
3. If the resolution of the mass calibration is not within 0.1 u for any isotope in the tuning solution,
qualify all analyte results that are > Method Detection Limit (MDL) associated with that isotope
as estimated (J), and all non-detects associated with that isotope as estimated (UJ). The situation
should be recorded in the Data Review Narrative and noted for CLP PO action.
4. If the %RSD exceeds 5% for any isotope in the tuning solution, qualify all sample results that are
> MDL associated with that tune as estimated (J), and all non-detects associated with that tune as
estimated (UJ). The situation should be recorded in the Data Review Narrative and noted for
CLP PO action.

Table 11. ICP-MS Tune Actions for ICP-MS Analysis
ICP-MS Tune Results
Tune not performed
Tune not performed properly
Resolution of mass calibration not within 0.1 u
%RSD > 5%
Action for Samples
Qualify all results as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated (J)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated (J)
Qualify non-detects as estimated (UJ)
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Inorganic Data Review
ICP-MS
Calibration
A. Review Items:
Form II-IN (Part A), Form XI-IN, Form XIII-IN, Form XVI-IN, preparation logs, calibration standard
logs, instrument logs, instrument printouts, and raw data.

B. Objective:
Method requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable quantitative data for the metals on the Inorganic Target
Analyte List (TAL). Initial Calibration Verification (ICV) demonstrates that the instrument is
capable of acceptable performance at the beginning of the analytical run. Continuing Calibration
Verification (CCV) demonstrates that the initial calibration is still valid by checking the performance
of the instrument on a continual basis.
C. Criteria:
1. Initial Calibration
The instruments shall be successfully calibrated each time the instrument is set up and after
Continuing Calibration Verification (CCV) failure. The calibration date and time shall be
included in the raw data.
a. A blank and at least five calibration standards shall be used to establish each analytical curve.
At least one standard shall be at or below the CRQL. All measurements shall be within the
instrument working range. A minimum of three replicate scans are required for
standardization and all Quality Control (QC) and sample analyses. The average result of all
the multiple scans for the standardization, QC, and sample analyses shall be used. The
calibration curve shall be fitted using linear regression or weighted linear regression. The
curve may be forced through zero. The curve must have a correlation coefficient of > 0.995.
The calculated percent differences for all of the non-zero standards must be within ±30% of
the true value of the standard. The y-intercept of the curve must be less than the CRQL.
2. Initial and Continuing Calibration Verification (ICV and CCV)
The acceptance criteria for the ICVs and CCVs are presented in Table 12:

Table 12. Acceptance Criteria for ICV and CCV Standards
Analytical
Method
ICP-MS
Inorganic
Analytes
Metals
ICV/CCV
Low Limit
(% of True Value)
90
ICV/CCV
High Limit
(% of True Value)
110
a. Initial Calibration Verification (ICV)
1) Immediately after each ICP-MS system has been calibrated, the accuracy of the initial
calibration must be verified and documented for each target analyte by the analysis of an
ICV solution(s). If the ICV Percent Recovery (%R) falls outside of the control limits, the
analysis should be terminated, the problem corrected, the instrument recalibrated, and all
affected samples reanalyzed.
2) Only if the ICV is not available from USEPA, analyses shall be conducted using a
certified solution of the analytes from an independent commercial standard source, at a
concentration level other than that used for instrument calibration, but within the
calibrated range.
3) The ICV solution shall be run at each analytical mass used for analysis.
January 2010
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Inorganic Data Review ICP-MS

b. Continuing Calibration Verification (CCV)
1) To ensure accuracy during the course of each analytical run, the CCV shall be analyzed
and reported for each mass used for the analysis of each analyte.
2) The CCV standard shall be analyzed at a frequency of every two hours during an
analytical run. The CCV standard shall also be analyzed at the beginning of the run, and
again after the last analytical sample.
3) The analyte concentration(s) in the CCV standard(s) shall be different than the
concentration used for the ICV, and at a concentration equivalent to the mid level of their
respective calibration curves.
4) The same CCV standard solution shall be used throughout the analysis runs for a Sample
Delivery Group (SDG).
5) The CCV shall be analyzed in the same fashion as an actual sample. If the %R of the
CCV was outside of the control limits, the analysis should be terminated, the problem
corrected, the instrument recalibrated, and all analytical samples analyzed since the last
compliant calibration verification reanalyzed.

D. Evaluation:
1. Verify that the instrument was calibrated each time the instrument was set up, utilizing a blank
and at least five calibration standards, one of which was at or below the CRQL.
2. Confirm that the measurements were within the working range, and were the average result of at
least three replicate exposures.
3. Verify that the ICV and CCV standards were analyzed for each analyte at the proper frequency
and at the appropriate concentration. Verify that acceptable %R results were obtained.
4. Recalculate one or more of the ICV and CCV %Rs using the following equation and verify that
the recalculated value agrees with the laboratory-reported values on Form IIA-IN.

%R= Found (value) xiQQ
True (value)

Where,
Found (value) = Concentration (in (ig/L) of each analyte measured in the analysis of the ICV
or CCV solution
True (value) = Concentration (in (ig/L) of each analyte in the ICV or CCV source

E. Action:
NOTE: For initial calibrations or ICVs that do not meet the technical criteria, apply the action to
all samples reported from the analytical run.
For CCVs that do not meet the technical criteria, apply the action to all samples analyzed
between a previous technically acceptable analysis of the QC sample and a subsequent
technically acceptable analysis of the QC sample in the analytical run.
1. If the instrument was not calibrated each time the instrument was set up, qualify the data as
unusable (R). If the instrument was not calibrated with at least the minimum number of
standards, or if the calibration curve does not include standards at required concentrations (e.g., a
blank and at least one at or below CRQL), use professional judgment to qualify results that are >
MDL as estimated (J) or unusable (R), and non-detects as estimated (UJ) or unusable (R).
2. If the correlation coefficient is <0.995, percent differences are outside the ±30% limit, or the y-
intercept >CRQL, qualify sample results that are >MDL as estimated (J) and non-detects as
estimated (UJ).
January 2010 39

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Inorganic Data Review
                                        ICP-MS
    3.  If the ICV or CCV %R falls outside the acceptance windows, use professional judgment to
       qualify all associated data. If possible, indicate the bias in the review. The following guidelines
       are recommended:
       a.  If the ICV or CCV %R is < 75%, qualify non-detects as unusable (R). Use professional
           judgment to qualify all results that are > MDL as estimated low (J-) or unusable (R).
       b.  If the ICV or CCV %R falls within the range of 75-89%, qualify sample results that are
           >MDL as estimated low (J-), and qualify non-detects as estimated (UJ).
       c.  If the ICV or CCV %R falls within the range of 111-125%, qualify sample results that are
           > MDL as estimated high (J+).
       d.  If the ICV or CCV %R falls within the range of 111-125%, non-detects should not be
           qualified.
       e.  If the ICV or CCV %R is > 125%, use professional judgment to qualify results that are
           > MDL as estimated high (J+) or unusable (R). Non-detects should not be qualified.
       f  If the %R is > 160%, qualify all results that are > MDL as unusable (R).
    4.  If the laboratory failed to provide adequate calibration information, the USEPA Region's
       designated representative should contact the  laboratory and request the necessary information.  If
       the information is not available, the reviewer must use professional judgment to assess the data.
    5.  Note the potential effects on the reported data due to exceeding the calibration criteria in the Data
       Review Narrative.
    6.  If calibration criteria are grossly exceeded, note this for Contract Laboratory Program Project
       Officer (CLP PO) action.
    NOTE:    For truly critical samples, a further in-depth evaluation of the calibration curve may be
               warranted to determine if additional  qualification is necessary.

                       Table 13. Calibration Actions for ICP-MS Analysis
Calibration Result
Calibration not performed
Calibration incomplete
Correlation coefficient <0.995;
%D outside ±30%; y-intercept
>CRQL
ICV/CCV%R<75%
ICV/CCV%R75-89%
ICV/CCV %R 1 1 1-125%
ICV/CCV%R>125%
ICV/CCV %R> 160%
Action for Samples
Qualify all results as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated (J) or unusable (R)
Qualify non-detects as estimated (UJ) or unusable (R)
Qualify results that are >MDL as estimated (J)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated low (J-) or unusable
Qualify all non-detects as unusable (R)
(R)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated (J)
Qualify results that are > MDL as estimated high (J+) or unusable
(R)
Qualify results that are > MDL as unusable (R)
January 2010
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Inorganic Data Review ICP-MS

Blanks
A. Review Items:
Form I-IN, Form III-IN, Form XII-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, and raw data.

C. Criteria:
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed after the analytical standards, but not before
analysis of the Initial Calibration Verification (ICV) during the initial calibration of the
instrument (see Section III.C.I).
3. A Continuing Calibration Blank (CCB) shall be analyzed at each mass used for the analysis,
immediately after every Continuing Calibration Verification (CCV). The CCB shall be analyzed
at a frequency of every two hours during the run. The CCB shall be analyzed at the beginning of
the run, and again after the last CCV that was analyzed after the last analytical sample of the run.
The CCB result (absolute value) shall not exceed the Contract Required Quantitation Limit
(CRQL) of each analyte for which analysis is performed.
4. At least one Preparation Blank shall be prepared and analyzed for each matrix, with every Sample
Delivery Group (SDG), or with each batch of samples digested, whichever is more frequent. The
Preparation Blank consists of reagent water processed through the appropriate sample preparation
and analysis procedure.
5. If any analyte concentration in the Preparation Blank is > CRQL, the lowest concentration of that
analyte in the associated samples must be > 10 times (lOx) the Preparation Blank concentration.
Otherwise, all samples associated with that Preparation Blank with the analyte's concentration <
1 Ox the Preparation Blank concentration, and > CRQL, should be redigested and reanalyzed for
that analyte (except for an identified field blank). The laboratory is not to correct the sample
concentration for the blank value.
6. If the concentration of the Preparation Blank for a certain analyte is < (-CRQL), all samples
reported < lOx the CRQL (associated with that analyte in that blank), should be redigested and
reanalyzed.
D. Evaluation:
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the proper
frequency and location during the run, and Preparation Blanks were prepared and analyzed as
appropriate for the SDG (e.g., total number of samples, various types of matrices present, number
of digestion batches, etc.).
2. Review the results reported on the Blank Summary (Form III-IN), as well as the raw data for all
blanks, and verify that the results were accurately reported.
3. Evaluate all of the associated blanks for the presence of target analytes. Verify that if target
analytes were present in a Preparation Blank or if a concentration was < (-CRQL), the affected
samples were redigested and reanalyzed. Verify that if target analytes were present in an ICB or a
CCB, the analysis was terminated, the problem corrected, the instrument recalibrated, and the
preceding 10 analytical samples or all analytical samples analyzed since the last compliant
calibration blank reanalyzed.

January 2010 41

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Inorganic Data Review ICP-MS

E. Action:
NOTES: For ICBs that do not meet the technical criteria, apply the action to all samples reported
from the analytical run.
For CCBs that do not meet the technical criteria, apply the action to all samples analyzed
between a previous technically acceptable analysis of the CCB and a subsequent
technically acceptable analysis of the CCB in the analytical run.
For Preparation Blanks that do not meet the technical criteria, apply the action to all
samples prepared in the same preparation batch.
1. If the appropriate blanks were not analyzed with the correct frequency, the data reviewer should
use professional judgment to determine if the associated sample data should be qualified. The
reviewer may need to obtain additional information from the laboratory. The situation should
then be recorded in the Data Review Narrative, and noted for Contract Laboratory Program
Project Officer (CLP PO) action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the blank.
The reviewer should note that in instances where more than one blank is associated with a given
sample, qualification should be based upon a comparison with the associated blank having the
highest concentration of contaminant.
3. Some general "technical" review actions include:
a. Any blank (including Preparation Blanks) reported with a negative result, whose value is
< (-MDL) but > (-CRQL), should be carefully evaluated to determine its effect on the sample
data. The reviewer shall then use professional judgment to assess the data. For any blank
(including Preparation Blanks) reported with a negative result, whose value is < (-CRQL),
qualify results that are > CRQL as estimated low (J-) and non-detects as estimated (UJ).
b. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil/sediment sample results reported on Form I-IN will not
be on the same basis (units, dilution) as the calibration blank data reported on Form III-IN.
The reviewer may find it easier to work with the raw data.
4. Specific "method" actions include:
a. If the absolute value of an ICB or a CCB result > CRQL, the analysis should be terminated.
If the analysis was not terminated and the affected samples were not reanalyzed, report non-
detect and results that are > MDL but < CRQL as CRQL-U. For results that are > CRQL but
< Blank Result, use professional judgment to qualify the data as unusable or to report the
results at the level of the blank with a "U" qualifier. Use professional judgment to qualify
results that are > Blank Result. Note this situation for CLP PO action and record it in the
Data Review Narrative.
b. If the absolute value of the concentration of the Preparation Blank is < CRQL, report non-
detects and results that are > MDL but < CRQL as CRQL-U. Use professional judgment to
qualify results that are > CRQL.
c. If any analyte concentration in the Preparation Blank is > CRQL, the lowest concentration of
that analyte in the associated samples must be lOx the Preparation Blank concentration.
Otherwise, all samples associated with that blank with concentrations < lOx the Preparation
Blank concentration and > CRQL should be redigested and reanalyzed. Raise the CRQL to
the concentration found in the Preparation Blank and report those samples that do not require
redigestion (that are > MDL but < CRQL) as CRQL-U. Note for CLP PO action and record
in the Data Review Narrative if the laboratory failed to redigest and reanalyze the affected
samples. The reviewer shall then use professional judgment to assess the data.
January 2010 42

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Inorganic Data Review
                                      ICP-MS
                        Table 14. Blank Actions for ICP-MS Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
Preparation
Blank
Preparation
Blank
Preparation
Blank
Blank Result
> MDL but <
CRQL
>CRQL
^(-MDL),
but ^(-CRQL)
< (-CRQL)
>CRQL
> MDL but <
CRQL
< (-CRQL)
Sample Result
Non-detect
^MDL but ^CRQL
>CRQL
^MDL but SCRQL
> CRQL but < Blank Result
> Blank Result
^MDL, or non-detect
< 1 Ox CRQL
^MDL but ^CRQL
> CRQL but < lOx the Blank
Result
^10x the Blank Result
Non-detect
^MDL but SCRQL
>CRQL
< 1 Ox CRQL
Action for Samples
No action
Report CRQL value with a "U"
Use professional judgment
Report CRQL value with a "U"
Report at level of Blank Result with
a "U" or qualify data as unusable
(R)
Use professional judgment
Use professional judgment
Qualify results that are ^CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
Report CRQL value with a "U"
Qualify results as unusable (R) or
estimated high (J+)
No action
No action
Report CRQL value with a "U"
Use professional judgment
Qualify results that are ^CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
January 2010
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Inorganic Data Review ICP-MS

Inductively Coupled Plasma - Interference Check Sample (ICP-ICS)
A. Review Items:
Form FVA-IN, Form IVB-IN, Form XIII-IN, instrument printouts, and raw data.

B. Objective:
The Inductively Coupled Plasma-Interference Check Sample (ICP-ICS) verifies the analytical
instrument's ability to overcome isobaric interferences typical of those found in samples.

C. Criteria:
1. The ICS consists of two solutions: Solution A and Solution AB. Solution A consists of the
interferents, and Solution AB consists of the analytes mixed with the interferents. An ICS
analysis consists of analyzing both solutions consecutively, starting with Solution A, for all
masses used for each analyte or interferent reported by Inductively Coupled Plasma-Mass
Spectrometry (ICP-MS).
2. An ICS must be run at the beginning of each analysis run. The ICS is not to be run prior to the
Initial Calibration Verification (ICV), and shall be immediately followed by a Continuing
Calibration Verification/Continuing Calibration Blank (CCV/CCB).
3. Results for the ICP-MS analysis of the ICS Solution A shall fall within the control limits of ± 2x
the CRQL, or ± 20% of the true value (whichever is greater) for the analytes included in the
solution.
4. Results for the ICP-MS analysis of the ICS Solution AB must fall within the control limits of ±
2x the CRQL, or ± 20% of the true value (whichever is greater) for the analytes included in the
solution.
5. If the value of an ICS result exceeds ± 2x the CRQL, or ± 20% of true value (whichever is
greater) criteria, the analysis shall be terminated, the problem corrected, the instrument
recalibrated, the new calibration then reverified, and all analytical samples analyzed since the last
compliant ICS reanalyzed.
6. The ICS should be obtained from USEPA, if available, and analyzed according to the instructions
supplied with the solutions. If the ICS is not available from USEPA, an independent ICS solution
shall be prepared with the interferent and analyte concentrations at the levels specified in the
method.
D. Evaluation:
1. Verify using the raw data (ICP instrumental printout) that the ICS was analyzed at the proper
frequency and location during the analytical run.
2. Evaluate the ICS raw data for results with an absolute value that is > Method Detection Limit
(MDL) for those analytes that are not present in the ICS solution.
3. Recalculate using the raw data and the following equation, one or more of the analyte Percent
Recoveries (%R), and verify that the recalculated value agrees with the laboratory-reported
values on Form IV-IN.

o/oR = Found(value) x 100
True (value)
Where,
Found (value) = Concentration (in (ig/L) of each analyte interferent measured in the
analysis of ICS Solution A or ICS Solution AB
True (value) = Concentration (in (ig/L) of each analyte or interferent in ICS Solution A
or ICS Solution AB
January 2010 44

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Inorganic Data Review ICP-MS

4. If the value of an ICS result exceeds ± 2x the CRQL, or ± 20% of true value (whichever is
greater) criteria, and the laboratory failed to terminate the analysis and take the appropriate
corrective action, note this for Contract Laboratory Program Project Officer (CLP PO) action and
record in the Data Review Narrative. Use professional judgment to assess the data.
E. Action:
NOTE: For an ICS for ICP-MS that does not meet the technical criteria, apply the action to all
samples reported from the analytical run.
1. The raw data may not contain results for interferents. In this case, the reviewer shall use
professional judgment to qualify the data. If the data does contain results for interferents, the
reviewer should apply the following actions to samples with concentrations of interferents that
are comparable to, or greater than, their respective levels in the ICS:
a. the ICS %R for an analyte is > 120% (or greater than the true value + 2x the CRQL as
applicable) and the sample results are non-detects, the data should not be qualified.
b. If the ICS %R for an analyte is > 120% (or greater than the true value + 2x the CRQL as
applicable) qualify sample results that are > MDL as estimated high (J+). If the ICS %R (or
true value) grossly exceeds the limits, use professional judgment to qualify the data.
c. If the ICS %R for an analyte falls within the range of 50-79% (or less than the true value - 2x
the CRQL as applicable) qualify sample results that are > MDL as estimated low (J-).
d. If the ICS recovery for an analyte falls within the range of 50-79% (or less than the true value
- 2x the CRQL as applicable), the possibility of false negatives exists. Qualify sample non-
detects as estimated (UJ).
e. If the ICSAB %R for an analyte or interferent is < 50%, qualify all sample results that are >
MDL and all sample non-detects as unusable (R).
2. If results that are > MDL are observed for analytes which are not present in the ICS solution, the
possibility of false positives exists. An evaluation of the associated sample data for the affected
elements should be made. For samples with comparable or higher levels of interferents and with
analyte concentrations that approximate those levels found in the ICS, qualify sample results that
are > MDL as estimated high (J+). Non-detects should not be qualified.
3. If negative results are observed for analytes that are not present in the ICS solution, and their
absolute value is > MDL, the possibility of false negatives in the samples exists. An evaluation
of the associated sample data for the affected analytes should be made. For samples with
comparable or higher levels of interferents, qualify non-detects for the affected analytes as
estimated (UJ), and results that are > MDL but < lOx the absolute value of the negative result as
estimated low (J-).
4. If the raw data does not contain results for the interferents, note this in the Data Review
Narrative.
5. Actions regarding the interpretation and/or the subsequent qualification of ICP data due to the
ICS analytical results can be extremely complex. Use professional judgment to determine the
need for the associated sample data to be qualified. The reviewer may need to obtain additional
information from the laboratory. All interpretive situations should then be recorded in the Data
Review Narrative.
6. If the ICS acceptance criteria are grossly exceeded, note the specifics for CLP PO action.
January 2010 45

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Inorganic Data Review
                                      ICP-MS
                  Table 15. Interference Check Actions for ICP-MS Analysis
Interference Check Sample Results
ICS %R > 120% (or > true value + 2x the
CRQL)
ICS %R 50-79% (or < true value - 2x the
CRQL)
ICSAB%R<50%
Potential false positives in field samples with
interferents
Potential false negatives in field samples with
interferents
Action for Samples
Qualify results that are > MDL as estimated high (J+)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify all sample data as unusable (R)
Qualify results that are > MDL as estimated high (J+)
Qualify results that are > MDL but < 10x( negative
value |) as estimated low (J-)
Qualify non-detects as estimated (UJ)
January 2010
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Inorganic Data Review ICP-MS

Laboratory Control Sample (LCS)
A. Review Items:
Form VII-IN, Form XII-IN, preparation logs, instrument printouts, and raw data.

B. Objective:
The Laboratory Control Sample (LCS) serves as a monitor of the overall performance of each step
during the analysis, including the sample preparation.

C. Criteria:
1. LCSs shall be analyzed for each analyte utilizing the same sample preparations, analytical
methods, and Quality Assurance/Quality Control (QA/QC) procedures as employed for the
samples.
a. LCS shall be prepared and analyzed for every group of aqueous/water or soil/sediment
samples in a Sample Delivery Group (SDG), or with each batch of samples digested,
whichever is more frequent. The aqueous/water and soil/sediment LCS shall be spiked such
that the final digestate contains each analyte at two times the CRQL for the associated matrix.
b. All LCS Percent Recoveries (%R) must fall within the control limits of 70-130%. If the %R
for the LCS falls outside of the control limits, the analysis should be terminated, the problem
corrected, and the samples prepared with that LCS redigested and reanalyzed.
D. Evaluation:
1. Verify using Form VII-IN, Form XII-IN, and raw data that the appropriate number of required
LCSs were prepared and analyzed for the SDG.
a. Check the LCSs documentation from the supplier and verify that the LCSs identification and
the control limits for it are listed on the Form VII-IN match those of the specific LCSs used
for the analysis.
b. Evaluate Form VII-IN and verify that all results for each analyte fall within the established
control limits.
2. Check the raw data to verify that the %Rs on Form VII-IN were accurately transcribed.
Recalculate one or more of the reported %Rs using the following equation:

_ Found (value)
True (value)
Where,
Found (value) = Concentration of each analyte (in fig/L or mg/kg) measured in the
analysis of the LCS
True (value) = Concentration of each analyte (in (ig/L or mg/kg) in the LCS

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Inorganic Data Review
                                        ICP-MS
    1.  LCS:
       a.  If the LCS %R falls within the range of 40-69%, qualify sample results that are > Method
           Detection Limit (MDL) as estimated low (J-). If the LCS %R is > 130%, qualify sample
           results that are > MDL as estimated high (J+).
       b.  If the LCS recovery is > 130% and the sample results are non-detects, the data should not be
           qualified.
       c.  If the LCS recovery falls within the range of 40-69%, qualify non-detects as estimated (UJ).
       d.  If LCS %R is < 40%, qualify all results that are > MDL as estimated low (J-) and all non-
           detects as unusable (R).
       e.  If the LCS %R is > 150%, qualify all affected data (both detects and non-detects) as unusable
           (R).
    2.  If a laboratory fails to analyze an LCS with each SDG, or if a laboratory consistently fails to
       generate acceptable LCS recoveries, note this for Contract Laboratory Program Project Officer
       (CLP PO) action
    3.  Whenever possible, the potential effects on the data due to out-of-control LCS results should be
       noted in the Data Review Narrative.

                           Table  16. LCS Actions for ICP-MS Analysis
LCS Result
Aqueous/Water and Soil/Sediment %R 40-69%
Aqueous/Water and Soil/Sediment %R > 130%
Aqueous/Water and Soil/Sediment %R < 40%
Aqueous/Water and Soil/Sediment %R > 150%
Action for Samples
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated high (J+)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Qualify all results as unusable (R)
January 2010
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Inorganic Data Review ICP-MS

Duplicate Sample Analysis
A. Review Items:
Cover Page, Form VI-IN, Form XII-IN, instrument printouts, and raw data.

C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
duplicate sample analysis.
2. At least one duplicate sample shall be prepared and analyzed from each group of samples of a
similar matrix type (e.g., water or soil) or for each Sample Delivery Group (SDG). Duplicates
cannot be averaged for reporting on Form I-IN. Additional duplicate sample analyses may be
required by USEPA Regional request. Alternately, the Region may require that a specific sample
be used for the duplicate sample analysis.
3. A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original and
duplicate sample values > five times (5x) the Contract Required Quantitation Limit (CRQL).
4. A control limit of the CRQL shall be used if either the sample or duplicate value is < 5x the
CRQL. The absolute value of the control limit (CRQL) shall be entered in the "Control Limit"
column on Form VI-IN. If both samples are non-detects, the RPD is not calculated for Form VI-
IN.
NOTE: The above control limits are method requirements for duplicate samples, regardless of
the sample matrix type. However, it should be noted that laboratory variability arising
from the sub-sampling of non-homogenous soil samples is a common occurrence.
Therefore, for technical review purposes only, Regional policy or project Data Quality
Objectives (DQOs) may allow the use of less restrictive criteria (e.g., 35% RPD, 2x the
CRQL) to be assessed against duplicate soil samples.
D. Evaluation:
1. Verify from the Cover Page, Form XII-IN, and the raw data that the appropriate number of
required duplicate samples were prepared and analyzed for the SDG.
2. Evaluate Form VI-IN and the raw data to verify that all duplicate results for each analyte and
method fall within the established control limits.
3. Verify that a field blank or PE sample was not used for duplicate analysis.
4. Check the raw data and recalculate one or more of the RPD values using the following equation
to verify that the results were correctly reported on Form VI-IN:
S-D
RPD
(S + D)/2
Where,
RPD = Relative Percent Difference
S = Sample Result (original)
D = Duplicate Result
x 100
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Inorganic Data Review
ICP-MS
E. Action:
NOTE:
2.
3.
4.
For a duplicate sample analysis that does not meet the technical criteria, apply the action
to all samples of the same matrix, if the reviewer considers the samples to be sufficiently
similar. The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make use of all available data, when determining
similarity, including: site and sampling documentation (e.g., location and type of sample,
descriptive data, soil classification); field test data (e.g., pH, Eh, conductivity, chlorine);
and laboratory data for other parameters [e.g., Total Suspended Solids (TSSs), Total
Dissolved Solids (TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity,
reactive sulfide, anions]. The reviewer should also use the sample data (e.g., similar
concentrations of analytes) in determining similarity between samples in the SDG. The
reviewer may determine that only some of the samples in the SDG are similar to the
duplicate sample, and that only these samples should be qualified. Or, the reviewer may
determine that no samples are sufficiently similar to the sample used for the duplicate,
and thus only the field sample used to prepare the duplicate sample should be qualified.
If the appropriate number of duplicate samples were not analyzed for each matrix using the
correct frequency, use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the laboratory. Note the
situation in the Data Review Narrative, and for Contract Laboratory Program Project Officer
(CLP PO) action.
If the results from a duplicate analysis for a particular analyte fall outside the appropriate control
limits, qualify sample results that are > MDL as estimated (J) and non-detects as estimated (UJ).
If a field blank or PE sample was used for the duplicate sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked and
professional judgment exercised by the data reviewer when evaluating the data.
Note the potential effects on the data due to out-of-control duplicate sample results in the Data
Review Narrative.

Table 17. Duplicate Sample Actions for ICP-MS Analysis
Duplicate Sample Results
Both original sample and duplicate sample >
5x the CRQL and RPD> 20%*
Original sample or duplicate sample < 5x the
CRQL (including non-detects) and absolute
difference between sample and duplicate >
CRQL*
Action for Samples
Qualify those results that are > MDL that professional
judgment determines to be affected as estimated (J)
and non-detects as estimated (UJ)
Qualify those results that are > MDL that professional
judgment determines to be affected as estimated (J)
and non-detects as estimated (UJ)
The above control limits are method requirements for duplicate samples, regardless of the sample
matrix type. However, it should be noted that laboratory variability arising from the sub-sampling of
non-homogenous soil samples is a common occurrence. Therefore, for technical review purposes
only, Regional policy or project Data Quality Objectives (DQOs) may allow the use of less
restrictive criteria (e.g., 35% RPD, 2xthe CRQL) to be assessed against duplicate soil samples.
January 2010
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Inorganic Data Review ICP-MS

Spike Sample Analysis
A. Review Items:
Cover Page, Form V-IN (Parts A & B), Form XII-IN, instrument printouts, and raw data.

B. Objective:
The spike sample analysis is designed to provide information about the effect of each sample matrix
on the sample preparation procedures and the measurement methodology. Non-homogenous samples
can impact the apparent method recovery. However, aqueous/water samples are generally
homogenous and most soil/sediment samples are homogenous within a factor of two or three. If the
spike is added to the sample before the digestion (e.g., prior to the addition of other reagents), it is
referred to as a spiked sample, pre-digestion spike, or Matrix Spike. If the spike is added to the
sample after the completion of the digestion procedures, it is referred to as a post-digestion spike, or
analytical spike.

C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
spiked sample analysis.
2. At least one spiked sample (pre-digestion) shall be prepared and analyzed from each group of
samples with a similar matrix type (e.g., water or soil), or for each Sample Delivery Group
(SDG).
3. When the matrix spike recovery falls outside of the control limits and the sample result is < four
times (4x) the spike added, a post-digestion spike shall be performed for those analytes that do
not meet the specified criteria. An aliquot of the remaining unspiked sample shall be spiked at 2x
the indigenous level or 2x the Contract Required Quantitation Limit (CRQL), whichever is
greater.
4. The spike Percent Recovery (%R) shall be within the established acceptance limits. However,
spike recovery limits do not apply when the sample concentration is > 4x the spike added. In
such an event, the data shall be reported unflagged, even if the %R does not meet the acceptance
criteria.
5. If the spiked sample analysis was performed on the same sample that was chosen for the duplicate
sample analysis, spike calculations shall be performed using the results of the sample designated
as the "original sample". The average of the duplicate results cannot be used for the purpose of
determining %R.

NOTE: The final spike concentrations required for the various target analytes are presented in the
methods described in the Statement of Work (SOW).
D. Evaluation:
1. Verify using the Cover Page, Form VA-IN, Form XII-IN, and raw data that the appropriate
number of required spiked samples were prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
3. Evaluate Form VA-IN and the raw data to verify that all pre-digestion spiked sample results for
each required analyte fall within the established control limits. If not, verify that a post-digestion
spike was prepared and analyzed.
4. Recalculate using the raw data, one or more of the %R using the following equation, and verify
that the recalculated value agrees with the laboratory-reported values on Forms V (A & B)-IN:
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ICP-MS
Where,
SSR
SR
SA
% Recovery =
Spiked Sample Result
Sample Result
Spike Added
SSR - SR
SA
100
NOTE: When the sample concentration is < Method Detection Limit (MDL), use SR = 0 only for
the purposes of calculating the %R. The actual spiked sample results, sample results, and
%R (positive or negative) shall still be reported on Forms VA-IN and VB-IN.
E. Action:
NOTE: For a Matrix Spike that does not meet the technical criteria, apply the action to all
samples of the same matrix, if the reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make use of all available data, including: site and
sampling documentation (e.g., location and type of sample, descriptive data, soil
classification); field test data (e.g., pH, Eh, conductivity, chlorine); and laboratory data
for other parameters [e.g., Total Suspended Solids (TSSs), Total Dissolved Solids
(TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
anions], in determining similarity. The reviewer should also use the sample data (e.g.,
similar concentrations of analytes) in determining similarity between samples in the
SDG. The reviewer may determine that only some of the samples in the SDG are similar
to the Matrix Spike sample, and that only these samples should be qualified. Or, the
reviewer may determine that no samples are sufficiently similar to the sample used for
the Matrix Spike, and thus that only the field sample used to prepare the Matrix Spike
sample should be qualified.
1. If the appropriate number of Matrix Spike samples was not analyzed for each matrix using the
correct frequency, use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the laboratory. Note the
situation in the Data Review Narrative, and for CLP Project Officer (CLP PO) action.
2. If a field blank or PE sample was used for the spiked sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked and
professional judgment exercised by the data reviewer when evaluating the data.
3. If the Matrix Spike recovery does not meet the evaluation criteria and a required post-digestion
spike was not performed, note this for CLP PO action.
4. If the Matrix Spike %R is < 30%, verify that a post-digestion spike was analyzed if required. If
the post-digestion spike %R is < 75% or is not performed, qualify sample results that are > MDL
as estimated low (J-) and non-detects as unusable (R). If the post-digestion spike %R is > 75%,
qualify sample results that are > MDL as estimated (J) and non-detects as estimated (UJ).
5. If the Matrix Spike %R is 30-74% and the sample results are > MDL, verify that a post-digestion
spike was analyzed, if required. If the %R for the post-digestion spike is also < 75% or is not
performed, qualify the affected data as estimated low (J-). If the %R for the post-digestion spike
is > 75%, qualify the affected data as estimated (J).
6. If the Matrix Spike %R falls within the range of 30-74% and the sample results are non-detects,
qualify the affected data as estimated (UJ).
7. If the Matrix Spike %R is > 125% and the reported sample results are non-detects, the sample
data should not be qualified.
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                                         ICP-MS
    8.  If the Matrix Spike %R is > 125% and the sample results are > MDL, verify that a post-digestion
       spike was analyzed, if required. If the %R for the post-digestion spike is also > 125% or is not
       performed, qualify the affected data as estimated high (J+). If the %R for the post-digestion spike
       is < 125%, qualify the affected data as estimated (J).
    9.  Note the potential  effects on the data due to out-of-control spiked sample results in the Data
       Review Narrative.

                      Table 18. Spike Sample Actions for ICP-MS Analysis
Spike Sample Results
Matrix Spike %R < 30%
Post-digestion spike %R< 75%
Matrix Spike %R < 30%
Post-digestion spike %R> 75%
Matrix Spike %R 30-74%
Post-digestion spike %R< 75%
Matrix Spike %R 30-74%
Post-digestion spike %R> 75%
Matrix Spike %R > 125%
Post-digestion spike %R> 125%
Matrix Spike %R > 125%
Post-digestion spike %R< 125%
Matrix Spike %R < 30%
No post-digestion spike performed
Matrix Spike %R 30-74%
No post-digestion spike performed
Matrix Spike %R > 125%
No post-digestion spike performed
Action for Samples
Qualify affected results that are > MDL as estimated low (J-)
and affected non-detects as unusable (R)
Qualify affected results that are > MDL as estimated (J) and
affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated low (J-)
and affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated (J)
affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated high (J+)
Qualify affected results that are > MDL as estimated (J)
Qualify affected results that are > MDL as estimated low (J-)
and affected non-detects as unusable (R)
Qualify affected results that are > MDL as estimated low (J-)
and affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated high (J+)
Non-detects are not qualified
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Inorganic Data Review ICP-MS

ICP Serial Dilution
A. Review Items:
Form I-IN, Form VIII-IN, instrument printouts, and raw data.

B. Objective:
The serial dilution of samples quantitated by Inductively Coupled Plasma-Mass Spectrometry (ICP-
MS) determines whether or not significant physical or chemical interferences exist due to sample
matrix.

C. Criteria:
1. An ICP Serial Dilution analysis shall be performed on a sample from each group of samples with
a similar matrix type (e.g., water or soil) or for each Sample Delivery Group (SDG), whichever is
more frequent.
2. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for the
ICP serial dilution analysis.
3. If the analyte concentration is sufficiently high [concentration in the original sample is > 50 times
(5 Ox) the Method Detection Limit (MDL)], the Percent Difference (%D) between the original
determination and the serial dilution analysis (a five-fold dilution) after correction shall be less
than 10.

NOTE: The above criteria are method requirements for serial dilution samples, regardless of the
sample matrix type. However, for technical review purposes only, Regional policy or
project Data Quality Objectives (DQOs) may allow the use of less restrictive criteria
(e.g., %D < 15) to be assessed against serial dilution soil samples.
D. Evaluation:
1. Verify that a field blank or PE sample was not used for the serial dilution analysis.
2. Check the raw data and recalculate the %D using the following equation. Verify that the serial
dilution analysis results, and the calculated %D results agree with the values reported by the
laboratory on Form VIII-IN:
I - S
% Difference =
x 100
I
Where,
I = Initial Sample Result
S = Serial Dilution Result

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to the serial dilution sample, and that only these samples should be qualified. Or, the
reviewer may determine that no samples are sufficiently similar to the sample used for
serial dilution, and thus only the field sample used to prepare the serial dilution sample
should be qualified.
If the required %D criteria are not met, qualify all affected results that are > MDL as
estimated (J) and all affected non-detects as estimated (UJ).
If evidence of positive or negative interference is found, use professional judgment to qualify the
associated sample data. Note the potential effects on the reported data in the Data Review
Narrative.
It should be noted for CLP Project Officer (CLP PO) action and in the Data Review Narrative if a
field blank or PE sample was used for the serial dilution analysis.

Table 19. Serial Dilution Actions for ICP-MS Analysis
Serial Dilution Result
Sample concentration > 5 Ox MDL and
%D > 10*
Interferences present
Action for Samples
Qualify affected results that are > MDL as estimated (J)
Qualify affected non-detects as estimated (UJ)
Use professional judgment
* The above criteria are method requirements for serial dilution samples, regardless of the sample
matrix type. However, for technical review purposes only, Regional policy or project Data
Quality Objectives (DQOs) may allow the use of less restrictive criteria (e.g., %D < 15) to be
assessed against serial dilution soil samples.
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Inorganic Data Review ICP-MS

ICP-MS Internal Standards
A. Review Items:
Form XIII-IN, Form XV-IN, Form XVII-IN, instrument printouts, and raw data.

B. Objective:
The analysis of Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) internal standards
determines the existence and magnitude of instrument drift and physical interferences. The criteria
for evaluation of internal standard results apply to all analytical and Quality Control (QC) samples
analyzed during the run, beginning with the calibration.

C. Criteria:
1. All samples analyzed during a run, with the exception of the ICP-MS tune, shall contain internal
standards. A minimum of five internal standards from the following list shall be added to each
sample: Li (the Li6 isotope); Sc; Y; Rh; Tb; Ho; Lu; and Bi. If the laboratory uses lithium as an
internal standard, the laboratory shall use an Li6-enriched standard. The laboratory shall monitor
the same internal standards throughout the entire analytical run and shall assign each analyte to at
least one internal standard.
2. The intensity of the internal standard response in a sample is monitored and compared to the
intensity of the response for that internal standard in the calibration blank. The Percent Relative
Intensity (%RI) in the sample shall fall within 60-125% of the response in the calibration blank.
3. If the %RI of the response in the sample falls outside of these limits, the laboratory shall
reanalyze the original sample at a two-fold dilution with internal standard added.
D. Evaluation:
1. Verify using Forms XV-IN, XVII-IN, and the raw data that a minimum of five internal standards
from the specified list were used for the analysis, that the same internal standards were monitored
for the entire run, and that each analyte was associated to at least one internal standard.
2. Verify using Form XV-IN and the raw data that these internal standards were added to each
sample in the run, including calibrations, samples, and QC samples (except tune).
3. Verify using Form XV-IN that the %RI between an internal standard in a sample and the internal
standard in the calibration blank was reported for each sample.
4. Verify using Form XIII-IN, Form XV-IN, and the raw data that if the %RI for a sample was
outside the limits (60-125%), the sample was reanalyzed of a 2x dilution with internal standard
added.
E. Action:
NOTE: Apply the action to the affected analytes for each sample that does not meet the internal
standard criteria.
1. If no internal standards were analyzed with the run, the sample data should be qualified as
unusable (R). Record this in the Data Review Narrative and note for CLP Project Officer (CLP
PO) action.
2. If less than five of the required internal standards were analyzed with the run, or a target
analyte(s) is (are) not associated to an internal standard, the sample data, or analyte data not
associated to an internal standard should be qualified as unusable (R). Record this in the Data
Review Narrative and note for CLP PO action.
3. If the %RIs for all internal standards in a sample is within the 60-125% limit, the sample data
should not be qualified.
4. If the %RI for an internal standard in a sample is not within the 60-125% limit, qualify the data
for those analytes associated with the internal standard(s) outside the limit as follows:
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Inorganic Data Review
                                         ICP-MS
           If the sample was reanalyzed at a two-fold dilution with internal standard %RI within the
           limits, report the result of the diluted analysis without qualification. If the %RI of the diluted
           analysis was not within the 60-125% limit, report the results of the original undiluted
           analyses and qualify the data for all analytes that are > Method Detection Limit (MDL) in the
           sample associated with the internal standard as estimated (J), and non-detected analytes
           associated with the internal standard as estimated (UJ).
           If the sample was not reanalyzed at a two-fold dilution, the reviewer should use professional
           judgment to determine the reliability of the data. The reviewer may determine that the results
           are estimated (J) or unusable (R).

                    Table 20. Internal Standard Actions for ICP-MS Analysis
Internal Standard Results
No internal standards
< 5 of the required internal standards
Target analyte not associated with
internal standard
%RI < 60% or > 125%, and original
sample reanalyzed at 2-fold dilution
Original sample not reanalyzed at 2-
fold dilution
Action for Samples
Qualify all results as unusable (R)
Qualify all analyte results not as unusable (R)
Qualify all analyte results not associated with internal standard
as unusable (R)
If %RI of diluted sample analysis 60-125%, do not qualify the
data
If the %RI of the diluted sample analysis is outside the 60-
125% limit, qualify results that are > MDL as estimated (J)
and qualify non-detects as estimated (UJ)
Use professional judgment
Qualify sample results as estimated (J) or unusable (R)
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                   Regional Quality Assurance (QA) and Quality Control (QC)
A.  Review Items:
    Form I-IN, instrument printouts, and raw data.

B.  Objective:
    Regional QA/QC samples refer to any QA and/or QC samples initiated by the Region, including field
    duplicate samples, Performance Evaluation (PE) samples, blind spikes, and blind blanks.  The use of
    these QA/QC samples is highly recommended (e.g., the use of field duplicate samples can provide
    information on sampling precision and sample homogeneity).

C.  Criteria:
    Criteria are determined by each Region.
D.  Evaluation:
    Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data
    review. Each Region will handle the evaluation of PE samples on an individual basis. Compare
    results for PE samples to the acceptance  criteria for the specific PE samples if possible.
    Calculate the Relative Percent Difference (RPD) between field duplicates and provide this
    information in the Data Review Narrative.
E.  Action:
    Any action must be in accordance with Regional specifications and criteria for acceptable PE sample
    results. Note any unacceptable PE sample results for Contract Laboratory Program Project Officer
    (CLP PO) action.
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B. Objective:
The objective is to ensure that the reported sample quantitation results are accurate. It is appropriate
for the data reviewer to make professional judgments and express concerns, as well as to comment on
the validity of the overall data for a Case. This is particularly appropriate when there are several
Quality Control (QC) criteria that are outside of the specification parameters. The additive nature of
QC factors that fall outside of specification parameters is difficult to assess in an objective manner,
but the reviewer has a responsibility to inform the user of data quality and data limitations to assist
that user in avoiding inappropriate use of the data, while not precluding any consideration of the data
at all. If qualifiers other than those used in this document are necessary to describe or qualify the
data, it is necessary to thoroughly document/explain the additional qualifiers used. The data reviewer
would be greatly assisted in this endeavor if the acceptance or performance criteria were provided.
The Inorganic Review Summary (see Appendix B) and supplementary documentation must be
included with the review.
C. Criteria:
1. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
2. Reported analyte concentrations must be quantitated according to the appropriate analytical
method, as listed in the method.
D. Evaluation:
Examine the raw data to verify that the correct calculation of the sample results was reported by the
laboratory. Digestion logs, instrument printouts, etc., should be compared to the reported sample
results recorded on the appropriate Inorganic Summary Forms (Form I-IN through Form XV-IN).
1. Evaluate any technical problems not previously addressed.
2. Examine the raw data for any anomalies (e.g., baseline shifts, negative response, mass dependent
drift, omissions, illegibility, etc.).
3. Verify appropriate methods and volumes were used in preparing the samples for analysis. If
reduced volumes were used, verify that the laboratory had received Contract Laboratory Program
Project Officer (CLP PO) approval for the use of the reduced volume.
4. Verify that there are no transcription or reduction errors [e.g., dilutions, Percent Solids (%S),
sample weights, etc.] on one or more samples.
5. Verify that results fall within the calibrated range(s) of the Inductively Coupled Plasma (ICP)
instrument(s) (Form XI).
6. If appropriate information is available, the reviewer may assess the usability of the data to assist
the data user in avoiding inappropriate use of the data. Review all available information,
including the Quality Assurance Project Plan (QAPP), focusing specifically on the acceptance or
performance criteria, the Standard Operating Procedure(s) (SOPs), and communication with the
user concerning the intended use and desired quality of these data.
E. Action:
1. Use professional judgment to determine if there is any need to qualify data which were not
qualified based on the QC criteria previously discussed.
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Inorganic Data Review                                                                     ICP-MS

    2.  Write a brief Data Review Narrative to give the user an indication of the analytical limitations of
       the data. Note any discrepancies between the data and the SDG Narrative for CLP PO action. If
       sufficient information on the intended use and required quality of the data is available, the
       reviewer should include an assessment of the data usability within the given context.
    3.  If any discrepancies are found, the laboratory may be contacted by the Region's designated
       representative to obtain additional information for resolution.  If a discrepancy remains
       unresolved, the reviewer may determine that qualification of the data is warranted.
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                                   Calculations for ICP-MS
    Aqueous/Water Sample Concentration by Inductively Coupled Plasma-Mass Spectrometry
    (ICP-MS):
    The concentrations determined in the digestate are to be reported in units of (ig/L:

                                                      Vf
                               Concentration (ug/L) = C x	x DF

    Where,
        C      = Instrument value in |o,g/L (The average of all replicate integrations).
        Vf     = Final digestion volume (mL)
        V      = Initial Aliquot Amount (mL)
        DF     = Dilution Factor

    Soil/Sediment Sample Concentration by ICP-MS:
    The concentrations determined in the digestate are to be reported on the basis of the dry weight of the
    sample, in units of mg/kg:
                                                        Vf
                      Concentration (dry wt.)(mg/kg) = C x —— x DF /1000
                                                       WxS
    Where,
        C      = Instrument value in |o,g/L (The average of all replicate integrations).
        Vf     = Final digestion volume (mL)
        W     = Initial aliquot amount (g)
        S       = % Solids/100 (see Exhibit D - Introduction to Analytical Methods, Section 1.6)
        DF     = Dilution Factor

    Adjusted Method Detection Limit (MDL)/Adjusted Contract Required Quantitation Limit
    (CRQL) Calculation:
    To calculate the adjusted MDL or adjusted CRQL for aqueous/water samples, substitute the value of
    the MDL ((ig/L) or CRQL ((ig/L) into the "C" term in the equation above.
    Calculate the adjusted MDL or adjusted CRQL for soil/sediment samples as follows:
                                                        WM    Vf
                     Adjusted Concentration (mg/kg) = C x—— x—— xDF
                                                       WxS  VM
    Where,
        C      = MDL or CRQL (mg/kg)
        WM    = Minimum method required aliquot amount (g) (1 .OOg  or 0.50g)
        W     = Initial aliquot amount (g)
        VM     = Method required final sample digestion volume (mL)  (100 mL)
        Vf     = Final digestion volume (mL)
        S       = % Solids/100 (see Exhibit D - Introduction to Analytical Methods, Section 1.6)
        DF     = Dilution Factor
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                                MERCURY DATA REVIEW
The inorganic data requirements for mercury data review to be reviewed during validation are listed
below:
I.      Preservation and Holding Times	64
II.     Calibration	66
III.    Blanks	69
IV.    Duplicate Sample Analysis	72
V.     Spike Sample Analysis	74
VI.    Regional Quality Assurance (QA) and Quality Control (QC)	76
VII.   Overall Assessment	77
Calculations for Mercury	79
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                       An Example Analytical Sequence for Mercury
SO
S0.2
Sl.O
S2.0
S5.0
S10.0
ICV
ICB
CCV
CCB
samples
CCV
CCB
samples
CCV
CCB, etc.
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Inorganic Data Review Mercury

B. Objective:
The objective is to ascertain the validity of the analytical results based on the sample condition, and
the holding time of the sample from the date of collection to the date of analysis.
C. Criteria:
1. The technical holding time criteria for aqueous/water mercury samples is 28 days; preserved
(with nitric acid) to pH < 2. The addition of nitric acid to adjust the pH is only required for
aqueous/water samples.
2. The technical holding time criteria for soil/sediment mercury samples is 28 days, based on the
technical holding time criteria for aqueous/water samples.
3. Mercury samples shall be maintained at 4°C (±2°C) until preparation and analysis to allow for
re-preparation.
4. Samples and standards shall be analyzed with 48 hours of preparation.
D. Evaluation:
Technical holding times are established by comparing the sampling date(s) on the TR/COC
documentation with the dates of analysis on Form XIII-IN, and the raw data. Information contained
in the Complete SDG File (CSF) should also be considered in the determination of holding times.
Verify that the analysis dates on the Form XIIIs and the raw data are identical. Review the SDG
Narrative and raw data preparation logs to determine if samples were properly preserved. If there is
an indication that there were problems with the samples, the integrity of the samples may be
compromised and professional judgment should be used to evaluate the effect of the problem on the
sample results.
E. Action:
NOTE: Apply the action to each sample for which the preservation or holding time criteria was
not met.
1. If the pH of aqueous/water metals samples is > 2 at the time of sample receipt, determine if the
laboratory adjusted the pH to <2 at the time of sample receipt. If not, use professional judgment
to qualify the samples based on the pH of the sample and the chemistry of the metal(s) of interest.
Qualify results that are > Method Detection Limit (MDL) as estimated low (J-), and qualify non-
detects as unusable (R).
2. If technical holding times are exceeded, use professional judgment to determine the reliability of
the data based on the magnitude of the additional time compared to the technical requirement and
whether the samples were properly preserved. The expected bias would be low. Qualify results
that are > MDL as estimated low (J-), and qualify non-detects as unusable (R).
3. Due to limited information concerning holding times for soil/sediment samples, it is left to the
discretion of the data reviewer whether to apply aqueous/water holding time criteria to
soil/sediment samples. If they are applied, it must be clearly documented in the Data Review
Narrative.
4. When the holding times are exceeded, the reviewer should comment in the Data Review
Narrative on any possible consequences for the analytical results.
5. When holding times are grossly exceeded, note it for Contract Laboratory Program Project
Officer (CLP PO) action.

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Inorganic Data Review
                                       Mercury
    6.  When shipping or storage temperatures grossly exceed the requirements, the loss of volatile
       mercury compounds or metallic mercury is possible. The expected bias would be low. Use
       professional judgment to qualify the samples and note for CLP PO action.

                Table 21. Technical Holding Time Actions for Mercury Analysis
Preservation & Holding Time Results
Aqueous/water metals samples received with
pH > 2 and pH not adjusted
Samples not maintained at 4°C (±2°C)
Technical Holding time exceeded:
Aqueous/water Samples > 28 days
Technical Holding Time exceeded:
Soil/sediment Metals > 28 days
Action for Samples
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as unusable (R)
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Mercury
Calibration
A. Review Items:
Form II-IN (Part A), Form XI-IN, Form XIII-IN, Form XVI-IN, preparation logs, calibration standard
logs, instrument logs, instrument printouts, and raw data.

B. Objective:
Method requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable quantitative data for mercury. Initial Calibration
Verification (ICV) demonstrates that the instrument is capable of acceptable performance at the
beginning of the analytical run. Continuing Calibration Verification (CCV) demonstrates that the
initial calibration is still valid by checking the performance of the instrument on a continuing basis.

C. Criteria:
1. Initial Calibration
The instruments shall be successfully calibrated daily (or once every 24 hours), and each time the
instrument is set up. The calibration date and time shall be included in the raw data. The
calibration curve shall be prepared by the same method used to prepare the samples for analysis.
The curve shall be prepared with the samples that will be analyzed using this calibration curve.
a. Cold Vapor Mercury Analysis
1) A blank and at least five calibration standards shall be employed to establish the
analytical curve. At least one of the calibration standards shall be at or below the
Contract Required Quantitation Limit (CRQL). The calibration curve shall be fitted
using linear regression or weighted linear regression. The curve may be forced through
zero. The calibration curves for mercury shall possess a correlation coefficient of > 0.995
to ensure the linearity over the calibrated range. The percent differences calculated for
all of the non-zero standards must fall within ±30% of the true value of the standard. The
y-intercept of the curve must be less than the CRQL. All sample results shall be reported
from an analysis within the calibrated range.
2. Initial and Continuing Calibration Verification (ICV and CCV)
The acceptance criteria for the ICVs and CCVs are presented in Table 22. These standards shall
be prepared by the same method used to prepare the samples for analysis.

Table 22. Acceptance Criteria for ICVs and CCVs
Analytical
Method
Cold Vapor AA
Inorganic
Analyte
Mercury
ICV/CCV
Low Limit
(% of True Value)
85
ICV/CCV
High Limit
(% of True Value)
115
a.
Initial Calibration Verification (ICV)
1) Immediately after each Atomic Absorption (AA) system has been calibrated, the
accuracy of the initial calibration must be verified and documented for mercury by the
analysis of an ICV solution(s). If the ICV %R falls outside of the control limits, the
analysis should be terminated, the problem corrected, the instrument recalibrated, and all
affected samples reanalyzed.
2) If the ICV is not available from USEPA, or where a certified solution of the analyte is not
available from any source, analyses shall be conducted on an independent standard at a
concentration level other than that used for instrument calibration, but within the
calibrated range.
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b. Continuing Calibration Verification (CCV)
1) To ensure accuracy during the course of each analytical run, the CCV shall be analyzed
and reported.
2) The CCV standard shall be analyzed at a frequency of every hour during an analytical
run. The CCV standard shall also be analyzed at the beginning of the run, and again after
the last analytical sample.
3) The analyte concentration in the CCV standard shall be different than the concentration
used for the ICV, and shall be at the mid level of the calibration curve.
4) The same CCV standard solution shall be used throughout the analysis runs for a Sample
Delivery Group (SDG).
5) The CCV shall be analyzed in the same fashion as an actual sample. If the %R of the
CCV was outside of the control limits, the analysis should be terminated, the problem
corrected, the instrument recalibrated, and all analytical samples analyzed since the last
compliant CCV reanalyzed.
D. Evaluation:
1 . Verify that the instrument was calibrated daily (once every 24 hours) and each time the
instrument was set up, utilizing a blank and at least five calibration standards. Confirm that at
least one of the calibration standards was analyzed at or below the CRQL. Confirm that
calibration standards and samples were prepared at the same time.
2. Confirm that the measurements were within the documented working range of the calibration
standards.
3 . Verify that the ICV and CCV standards were analyzed for mercury at the proper frequency and at
the appropriate concentration. Verify that acceptable %R results were obtained.
4. Recalculate one or more of the ICV or CCV %R using the following equation and verify that the
recalculated value agrees with the laboratory-reported values on Form IIA-IN.
o/0R = (value) x 1QQ
True (value)
Where,
Found (value) = Concentration (in (ig/L) of mercury measured in the analysis of the
ICV or CCV solution
True (value) = Concentration (in (ig/L) of mercury in the ICV or CCV source

E. Action:
NOTES: For initial calibrations or ICVs that do not meet the technical criteria, apply the action to
all samples reported from the analytical run.
For CCVs that do not meet the technical criteria, apply the action to all samples analyzed
between a previous technically acceptable analysis of the QC sample and a subsequent
technically acceptable analysis of the QC sample in the analytical run.
1 . If the instrument was not calibrated daily and each time the instrument was set up, qualify the
data as unusable (R). If the instrument was not calibrated with at least the minimum number of
standards, or if the calibration curve does not include standards at required concentrations (e.g., a
blank, and at least one standard at or below the CRQL), or if the instrument was not calibrated
with standards prepared at the same time as the samples, use professional judgment to qualify
results that are > Method Detection Limit (MDL) as estimated (J) or unusable (R), and non-
detects as estimated (UJ) or unusable (R).
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                                        Mercury
    2.  If the correlation coefficient is < 0.995, percent differences are outside the ±30% limit, or the y-
       intercept is >CRQL, qualify sample results that are > MDL as estimated (J), and non-detects as
       estimated (UJ). Depending on the degree of the deviation from linearity, further qualification of
       the data may be required depending on the professional judgment of the reviewer [e.g., unusable
       data(R)].
    3.  If the ICV or CCV %R falls outside the acceptance windows, use professional judgment to
       qualify all associated data.  If possible, indicate the bias in the review. The following guidelines
       are recommended:
       a.  If the ICV or CCV %R is < 70%, qualify non-detects as unusable (R). Use professional
           judgment to qualify all results that are > MDL as estimated low (J-) or unusable (R).
       b.  If the ICV or CCV %R falls within the range of 70-84%, qualify sample results that are
           > MDL as estimated low (J-) and qualify non-detects as estimated (UJ).
       c.  If the ICV or CCV %R falls within the range of 116-130%, qualify sample results that are
           > MDL as estimated high (J+).
       d.  If the ICV or CCV %R falls within the range of 116-130%, non-detects should not be
           qualified.
       e.  If the ICV or CCV %R is > 130%, use professional judgment to qualify results that are
           > MDL as estimated high (J+) or unusable (R). Non-detects should not be qualified.
       f  If the %R is > 165%, qualify all results that are > MDL as unusable (R).
    4.  If the laboratory failed to provide adequate calibration information, the Region's designated
       representative should contact the laboratory and request the necessary information. If the
       information is not available, the reviewer must use professional judgment to assess the data.
    5.  Note the potential effects on the reported data due to exceeding the calibration criteria in the Data
       Review Narrative.
    6.  If calibration criteria are grossly exceeded, note this for CLP Project Officer (CLP PO) action.
    NOTE:    For truly critical samples, a further in-depth evaluation of the calibration curve may be
               warranted to determine if additional qualification is necessary.

                       Table 23. Calibration  Actions for Mercury Analysis
Calibration Result
Calibration not performed
Calibration incomplete
Correlation coefficient <0.995, %D
outside ±30%, y-intercept >CRQL
ICV/CCV %R < 70%
ICV/CCV %R 70-84%
ICV/CCV %R 1 16-130%
ICV/CCV %R> 130%
ICV/CCV %R> 165%
Action for Samples
Qualify all results as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated (J) or unusable (R)
Qualify non-detects as estimated (UJ) or unusable (R)
Qualify results that are > MDL as estimated (J)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated low (J-) or unusable
(R)
Qualify all non-detects as unusable (R)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated (J)
Qualify results that are > MDL as estimated high (J+) or unusable
(R)
Qualify results that are > MDL as unusable (R)
January 2010
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Blanks
A. Review Items:
Form I-IN, Form III-IN, Form XII-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, and raw data.

C. Criteria:
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed after the analytical standards, but not before
analysis of the Initial Calibration Verification (ICV) during the initial calibration of the
instrument (see Section II.C. 1). The ICB shall be prepared by the same method used to prepare
the samples for analysis.
3. A Continuing Calibration Blank (CCB) shall be analyzed immediately after every Continuing
Calibration Verification (CCV). The CCB shall be prepared by the same method used to prepare
the samples for analysis. The CCB shall be analyzed at a frequency of every hour during the run.
The CCB shall be analyzed at the beginning of the run, and again after the last CCV that was
analyzed after the last analytical sample of the run. The CCB result (absolute value) shall not
exceed the Contract Required Quantitation Limit (CRQL) for mercury.
4. At least one Preparation Blank shall be prepared and analyzed for each matrix, with every Sample
Delivery Group (SDG), or with each batch of samples digested, whichever is more frequent. The
Preparation Blank consists of reagent water processed through the appropriate sample preparation
and analysis procedure.
5. If the mercury concentration in the Preparation Blank is > CRQL, the lowest concentration of
mercury in the associated samples must be > 10 times (10x) the Preparation Blank concentration.
Otherwise, all samples associated with that Preparation Blank with a mercury concentration
< lOx the Preparation Blank concentration, and > CRQL, should be redigested and reanalyzed
(except for an identified field blank). The laboratory is not to correct the sample concentration
for the blank value.
6. If the concentration of the Preparation Blank for mercury is < (-CRQL), all samples reported <
lOx the CRQL (associated with that analyte in that blank), should be redigested and reanalyzed.
D. Evaluation:
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the proper
frequency and location during the run, and Preparation Blanks are prepared and analyzed as
appropriate for the SDG (e.g., total number of samples, various types of matrices present, number
of digestion batches, etc.).
2. Review the results reported on the Blank Summary (Form III-IN), as well as the raw data for all
blanks, and verify that the results are accurately reported.
3. Evaluate all of the associated blanks for the presence of mercury. Verify that if mercury was
present in a Preparation Blank or if a concentration was < (-CRQL), the affected samples were
redigested and reanalyzed. Verify that if mercury was present in an ICB or a CCB, the analysis
was terminated, the problem corrected, the instrument recalibrated, and the preceding 10
analytical samples or all analytical samples analyzed since the last compliant calibration blank
reanalyzed.

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E. Action:
NOTES: For ICBs that do not meet the technical criteria, apply the action to all samples reported
from the analytical run.
For CCBs that do not meet the technical criteria, apply the action to all samples analyzed
between a previous technically acceptable analysis of the CCB and a subsequent
technically acceptable analysis of the CCB in the analytical run.
For Preparation Blanks that do not meet the technical criteria, apply the action to all
samples prepared in the same preparation batch.
1. If the appropriate blanks are not analyzed with the correct frequency, the data reviewer should use
professional judgment to determine if the associated sample data should be qualified. The
reviewer may need to obtain additional information from the laboratory. The situation should
then be recorded in the Data Review Narrative, and noted for Contract Laboratory Program
Project Officer (CLP PO) action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the blank.
The reviewer should note that in instances where more than one blank is associated with a given
sample, qualification should be based upon a comparison with the associated blank having the
highest concentration of contaminant.
3. Some general "technical" review actions include:
a. Any blank (including Preparation Blanks) reported with a negative result, whose value is
< (-MDL) but > (-CRQL), should be carefully evaluated to determine its effect on the sample
data. The reviewer shall then use professional judgment to assess the data. For any blank
(including Preparation Blanks) reported with a negative result, whose value is < (-CRQL),
qualify results that are > CRQL as estimated low (J-) and non-detects as estimated (UJ).
b. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil/sediment sample results reported on Form I-IN will not
be on the same basis (units, dilution) as the calibration blank data reported on Form III-IN.
The reviewer may find it easier to work with the raw data.
4. Specific "method" actions include:
a. If the absolute value of an ICB or a CCB result is > CRQL, the analysis should be terminated.
If the analysis was not terminated and the affected samples are not reanalyzed, report non-
detects and results that are > MDL but < CRQL as CRQL-U. For results that are > CRQL but
< Blank Result, use professional judgment to qualify the data as unusable (R), or to report the
results at the level of the blank with a "U" qualifier. Use professional judgment to qualify
results that are > Blank Result. Note this situation for CLP PO action and record it in the
Data Review Narrative.
b. If the absolute value of the concentration of the Preparation Blank is < CRQL, report non-
detect and results that are > MDL but < CRQL as CRQL-U. Use professional judgment to
qualify results that are > CRQL.
c. If the mercury concentration in the Preparation Blank is > CRQL, the lowest concentration of
mercury in the associated samples must be lOx the Preparation Blank concentration.
Otherwise, all samples associated with that blank with concentrations < lOx the Preparation
Blank concentration and > CRQL should be redigested and reanalyzed. Raise the CRQL to
the concentration found in the Preparation Blank and report those samples that do not require
redigestion (that are > MDL but < CRQL) as CRQL-U. Note for CLP PO action and record
in the Data Review Narrative if the laboratory failed to redigest and reanalyze the affected
samples. The reviewer shall then use professional judgment to assess the data.
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                                      Mercury
                        Table 24. Blank Actions for Mercury Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
Preparation
Blank
Preparation
Blank
Preparation
Blank
Blank Result
Absolute value is
> MDL but <
CRQL
Absolute value is
>CRQL
< (-MDL), but
> (-CRQL)
< (-CRQL)
>CRQL
> MDL but <
CRQL
< (-CRQL)
Sample Result
Non-detect
> MDL but. < CRQL
>CRQL
> MDL but. < CRQL
> CRQL but < Blank Result
> Blank Result
> MDL, or non-detect
<1 Ox the CRQL
> MDL but < CRQL
> CRQL but < lOx the Blank
Result
> 1 Ox the Blank Result
Non-detect
> MDL but. < CRQL
>CRQL
<1 Ox the CRQL
Action for Samples
No action
Report CRQL value with a "U"
Use professional judgment
Report CRQL value with a "U"
Report at level of Blank Result
with a "U" or qualify data as
unusable (R)
Use professional judgment
Use professional judgment
Qualify results that are > CRQL
as estimated low (J-)
Qualify non-detects as estimated
(UJ)
Report CRQL value with a "U"
Qualify results as unusable (R)
or estimated high (J+)
No action
No action
Report CRQL with a "U"
Use professional judgment
Qualify results that are > CRQL
as estimated low (J-)
Qualify non-detects as estimated
(UJ)
January 2010
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Inorganic Data Review Mercury

Duplicate Sample Analysis
A. Review Items:
Cover Page, Form VI-IN, Form XII-IN, instrument printouts, and raw data.

C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
duplicate sample analysis.
2. At least one duplicate sample shall be prepared and analyzed from each group of samples of a
similar matrix type (e.g., water or soil) or for each Sample Delivery Group (SDG). Duplicates
cannot be averaged for reporting on Form I-IN. Additional duplicate sample analyses may be
required by USEPA Regional request. Alternately, the Region may require that a specific sample
be used for the duplicate sample analysis.
3. A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original and
duplicate sample values > five times (5x) the Contract Required Quantitation Limit (CRQL).
4. A control limit of the CRQL shall be used if either the sample or duplicate value is < 5x the
CRQL. The absolute value of the control limit (CRQL) shall be entered in the "Control Limit"
column on Form VI-IN. If both samples are non-detects, the RPD is not calculated for Form VI-
IN.
NOTE: The above control limits are method requirements for duplicate samples, regardless of
the sample matrix type. However, it should be noted that laboratory variability arising
from the sub-sampling of non-homogenous soil samples is a common occurrence.
Therefore, for technical review purposes only, Regional policy or project Data Quality
Objectives (DQOs) may allow the use of less restrictive criteria (e.g., 35% RPD, 2x the
CRQL) to be assessed against duplicate soil samples.
D. Evaluation:
1. Verify from the Cover Page, Form XII-IN, and the raw data that the appropriate number of
required duplicate samples were prepared and analyzed for the SDG.
2. Evaluate Form VI-IN and the raw data to verify that all mercury duplicate results for each method
fall within the established control limits.
3. Verify that a field blank or PE sample was not used for duplicate analysis.
4. Check the raw data and recalculate one or more of the RPD values using the following equation
to verify that the results were correctly reported on Form VI-IN:
S-D
RPD
(S + D)/2
Where,
RPD = Relative Percent Difference
S = Sample Result (original)
D = Duplicate Result
100
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                                                                                Mercury
E.  Action:
    NOTE:
       For a duplicate sample analysis that does not meet the technical criteria, apply the action
       to all samples of the same matrix, if the reviewer considers the samples sufficiently
       similar. The reviewer will need to exercise professional judgment in determining sample
       similarity.  The reviewer should make use of all available data, including: site and
       sampling documentation (e.g., location and type of sample, descriptive data, soil
       classification); field test data (e.g., pH, Eh, conductivity, chlorine); and laboratory data
       for other parameters [e.g., Total Suspended Solids (TSSs), Total Dissolved Solids
       (TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
       anions], in determining similarity. The reviewer should also use the sample data (e.g.,
       similar concentrations of analytes) in determining similarity between samples in the
       SDG.  The reviewer may determine that only some of the samples in the  SDG are similar
       to the duplicate sample, and that only these samples should be qualified.  Or, the reviewer
       may determine that no samples are sufficiently similar to the sample used for the
       duplicate, and thus that only the field sample used to prepare the duplicate sample should
       be qualified.
If the appropriate number of duplicate samples was not analyzed for each matrix  using the correct
frequency, use professional judgment to determine if the associated sample data should be
qualified.  The reviewer may need to obtain additional information from the laboratory. Note the
situation in the Data Review Narrative,  and for Contract Laboratory Program Project Officer
(CLP PO) action.
If the results from a duplicate analysis for mercury fall outside  the appropriate control limits,
qualify sample results that are > Method Detection Limit (MDL) as estimated (J) and non-detects
as estimated (UJ).
If a field blank or PE sample was used for the  duplicate sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked and
professional judgment exercised by the  data reviewer when evaluating the data.
Note the potential effects on the data due to out-of-control duplicate sample results in the Data
Review Narrative.

             Table 25. Duplicate Sample Actions for Mercury Analysis
Duplicate Sample Results
Both original sample and duplicate sample > 5x
the CRQL and RPD> 20%*
Original sample or duplicate sample < 5x the
CRQL (including non-detects) and absolute
difference between sample and duplicate >
CRQL*
Action for Samples
Qualify those results that are > MDL that
professional judgment determines to be affected as
estimated (J) and non-detects as estimated (UJ)
Qualify those results that are > MDL that
professional judgment determines to be affected as
estimated (J) and non-detects as estimated (UJ)
     The above control limits are method requirements for duplicate samples, regardless of the sample
     matrix type. However, it should be noted that laboratory variability arising from the sub-sampling of
     non-homogenous soil samples is a common occurrence. Therefore, for technical review purposes
     only, Regional policy or project Data Quality Objectives (DQOs) may allow the use of less
     restrictive criteria (e.g., 35% RPD, 2xthe CRQL) to be assessed against duplicate soil samples.
January 2010
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Inorganic Data Review Mercury

Spike Sample Analysis
A. Review Items:
Cover Page, Form V-IN (Parts A & B), Form XII-IN, instrument printouts, and raw data.

C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
spiked sample analysis.
2. At least one spiked sample (pre-digestion) shall be prepared and analyzed from each group of
samples with a similar matrix type (e.g., water or soil), or for each Sample Delivery Group
(SDG).
3. The spike Percent Recovery (%R) shall be within the established acceptance limits. However,
spike recovery limits do not apply when the sample concentration is > four times (4x) the spike
added. In such an event, the data shall be reported unflagged, even if the %R does not meet the
acceptance criteria.
4. If the spiked sample analysis was performed on the same sample that was chosen for the duplicate
sample analysis, spike calculations shall be performed using the results of the sample designated
as the "original sample". The average of the duplicate results cannot be used for the purpose of
determining %R.
NOTE: The final spike concentrations required for mercury are presented in the method
described in the Statement of Work (SOW).
D. Evaluation:
1. Verify using the Cover Page, Form VA-IN, Form XII-IN, and raw data that the appropriate
number of required spiked samples were prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
3. Evaluate Form VA-IN and the raw data to verify that all Matrix Spike sample results for mercury
fall within the established control limits.
4. Recalculate using the raw data, one or more of the %R using the following equation, and verify
that the recalculated value agrees with the laboratory-reported values on Forms V (A & B)-IN:

%Recovery = SSR " SR x 100
SA
Where,
SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added

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Inorganic Data Review
Mercury
E. Action:
NOTE:
3.
For a Matrix Spike that does not meet the technical criteria, apply the action to all
samples of the same matrix, if the reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make use of all available data, including: site and
sampling documentation (e.g., location and type of sample, descriptive data, soil
classification); field test data (e.g., pH, Eh, conductivity, chlorine); and laboratory data
for other parameters [e.g., Total Suspended Solids (TSSs), Total Dissolved Solids
(TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
anions], in determining similarity. The reviewer should also use the sample data (e.g.,
similar concentrations of analytes) in determining similarity between samples in the
SDG. The reviewer may determine that only some of the samples in the SDG are similar
to the Matrix Spike sample, and that only these samples should be qualified. Or, the
reviewer may determine that no samples are sufficiently similar to the sample used for
the Matrix Spike, and thus that only the field sample used to prepare the Matrix Spike
sample should be qualified.
If the appropriate number of Matrix Spike samples was not analyzed for each matrix using the
correct frequency, use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the laboratory. Note the
situation in the Data Review Narrative, and for CLP Project Officer (CLP PO) action.
If a field blank or PE sample was used for the spiked sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked and
professional judgment exercised by the data reviewer when evaluating the data.
If the Matrix Spike %R is < 30%, qualify affected results that are > MDL as estimated low (J-).
Qualify affected non-detects as unusable (R).
If the Matrix Spike %R falls within the range of 30-74% and the sample results are > MDL,
qualify the affected data as estimated low (J-).
If the Matrix Spike %R falls within the range of 30-74% and the sample results are non-detects,
qualify the affected data as estimated (UJ).
If the Matrix Spike %R is > 125% and the reported sample results are non-detects, the sample
data should not be qualified.
If the Matrix Spike %R is > 125% and the sample results are > MDL, qualify the affected data as
estimated high (J+).
Note the potential effects on the data due to out-of-control spiked sample results in the Data
Review Narrative.

Table 26. Spike Sample Actions for Mercury Analysis
Spike Sample Results
Matrix Spike %R < 30%
Matrix Spike %R 30-74%
Matrix Spike %R > 125%
Action for Samples
Qualify affected results that are > MDL as estimated low (J-) and
affected non-detects as unusable (R)
Qualify affected results that are > MDL as estimated low (J-) and
affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated high (J+)
Non-detects are not qualified
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                   Regional Quality Assurance (OA) and Quality Control (OC)
A.  Review Items:
    Form I-IN, instrument printouts, and raw data.

B.  Objective:
    Regional QA/QC samples refer to any QA and/or QC sample initiated by the Region, including field
    duplicates, Performance Evaluation (PE) samples, blind spikes, and blind blanks. The use of these
    QA/QC samples is highly recommended (e.g., the use of field duplicates can provide information on
    sampling precision and homogeneity).

C.  Criteria:
    Criteria are determined by the Region.
D.  Evaluation:
    Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data
    review. Each Region will handle the evaluation of PE samples on an individual basis. Compare
    results for PE samples with the acceptance criteria for the specific PE samples if possible.
    Calculate the Relative Percent Difference (RPD) between field duplicates and provide his information
    in the Data Review Narrative.
E.  Action:
    Any action must be in accordance with Regional specifications and criteria for acceptable PE sample
    results. Note any unacceptable PE sample results for Contract Laboratory Program Project Officer
    (CLP PO) action.
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Overall Assessment
A. Review Items:
Entire data package, data review results, preparation logs, calibration standard logs, instrument logs,
instrument printouts, and raw data (including any confirmation data).

C. Criteria:
1. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
2. Reported analyte concentrations must be quantitated according to the appropriate analytical
method, as listed in the method.
D. Evaluation:
Examine the raw data to verify that the correct calculation of the sample results was reported by the
laboratory. Digestion logs, instrument printouts, etc., should be compared to the reported sample
results recorded on the appropriate Inorganic Summary Forms (Form I-IN through Form XV-IN).
1. Evaluate any technical problems not previously addressed.
2. Examine the raw data for any anomalies (e.g., baseline shifts, negative absorbance, omissions,
illegibility, etc.).
3. Verify that the appropriate methods and amounts were used to prepare samples and standards for
analysis. If reduced volumes are used, verify that the laboratory had received Contract
Laboratory Program Project Officer (CLP PO) approval for the use of the reduced volume.
4. Verify that there are no transcription or reduction errors [e.g., dilutions, Percent Solids (%S),
sample weights, etc.] on one or more samples.
5. Verify that results fall within the calibrated range for mercury.
6. If appropriate information is available, the reviewer may assess the usability of the data to assist
the data user in avoiding inappropriate use of the data. Review all available information,
including the Quality Assurance Project Plan (QAPP), focusing specifically on the acceptance or
performance criteria, the Standard Operating Procedure(s) (SOPs), and communication with the
user concerning the intended use and desired quality of these data.
E. Action:
1. Use professional judgment to determine if there is any need to qualify data which are not
qualified based on the QC criteria previously discussed.
2. Write a brief Data Review Narrative to give the user an indication of the analytical limitations of
the data. Note any discrepancies between the data and the SDG Narrative for CLP PO action. If
sufficient information on the intended use and required quality of the data is available, the
reviewer should include an assessment of the data usability within the given context.

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    3.   If any discrepancies are found, the laboratory may be contacted by the Region's designated
        representative to obtain additional information for resolution.  If a discrepancy remains
        unresolved, the reviewer may determine that qualification of the data is warranted.
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                                  Calculations for Mercury
    Aqueous/Water Samples:

                               Hg Concentration (ug/L) = C x DF
       Where,
           C     =  Instrument value in |og/L from the calibration curve
           DF    =  Dilution Factor of the original sample

    Soil/Sediment Samples:
                         Hg Concentration (mg/kg) = C x ——- x DF x 0.1
                                                     W xS
       Where,
           C     =  Instrument value in |og/L from the calibration curve
           W    =  Initial aliquot amount (g)
           S     =  % Solids/100 (see Exhibit D - Introduction to Analytical Methods, Section 1.6).
           DF    =  Dilution Factor

    Adjusted Method Detection Limit (MDL)/Adjusted Contract Required Quantitation Limit
    (CRQL) Calculation:
       To calculate the adjusted MDL or adjusted CRQL for aqueous/water samples, multiply the value
       of the MDL ((ig/L) or CRQL ((ig/L) by the Dilution Factor (DF).  Calculate the adjusted MDL or
       adjusted CRQL for soil/sediment samples as follows:
                        Adjusted Concentration (mg/kg) = C x	™— x DF
                                                          WxS
       Where,
           C     =  MDL or CRQL (mg/kg)
           Wm   =  Method required minimum sample weight (g) (0.50 g)
           W    =  Initial aliquot amount (g)
           S     =  % Solids/100 (see Exhibit D - Introduction to Analytical Methods, Section 1.6).
           DF    =  Dilution Factor
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Inorganic Data Review                                                                 Cyanide

                                CYANIDE DATA REVIEW
The inorganic data requirements for cyanide data review to be reviewed during validation are listed
below:
I.      Preservation and Holding Times	82
II.     Calibration	84
III.    Blanks	87
IV.    Duplicate Sample Analysis	90
V.     Spike Sample Analysis	92
VI.    Regional Quality Assurance (QA) and Quality Control (QC)	95
VII.   Overall Assessment	96
Calculations for Cyanide	98
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Inorganic Data Review                                                            Cyanide


                      An Example Analytical Sequence for Cyanide
SO
S10
S50
S100
S200
S400
ICV
ICB
CCV
CCB
samples
CCV
CCB
samples
CCV
CCB, etc.
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Inorganic Data Review Cyanide

B. Objective:
The objective is to ascertain the validity of the analytical results based on the sample condition, and
the holding time of the sample from the date of collection to the date of analysis.
C. Criteria:
1. The technical holding time criteria for aqueous/water cyanide samples is 14 days; oxidizing
agents removed, then preserved (with sodium hydroxide) to pH > 12. The addition of sodium
hydroxide to adjust the pH is only required for aqueous/water samples.
2. The technical holding time criteria for soil/sediment cyanide samples is 14 days, based on the
technical holding time criteria for aqueous/water samples.
3. Samples shall be maintained at 4°C (±2°C) until preparation and analysis.
D. Evaluation:
Technical holding times are established by comparing the sampling date(s) on the TR/COC
documentation with the dates of analysis on Form XIII-IN, and the raw data. Information contained
in the Complete SDG File (CSF) should also be considered in the determination of holding times.
Verify that the analysis dates on the Form XIIIs and the raw data are identical. Review the SDG
Narrative and raw data preparation logs to determine if samples were properly preserved. If there is
an indication that there are problems with the samples, the integrity of the samples may be
compromised and professional judgment should be used to evaluate the effect of the problem on the
sample results. For aqueous/water cyanide samples, the reviewer should look for evidence that the
samples were tested for the presence of sulfides or oxidizing agents, and whether the appropriate
preservation steps were taken.
E. Action:
NOTE: Apply the action to each sample for which the preservation or holding time criteria were
not met.
1. If oxidizing agents are detected in aqueous/water cyanide samples at the time of sample
preparation, qualify results that are > Method Detection Limit (MDL) as estimated low (J-) and
non-detects as unusable (R). If sulfides are detected in aqueous/water cyanide samples at the time
of sample preparation and there is no evidence that the laboratory removed the sulfides (using
precipitation and filtration), qualify results that are > MDL as estimated (J) and non-detects as
unusable (R). If the pH of aqueous/water cyanide samples is < 12 at the time of sample receipt,
use professional judgment to qualify the samples based on the pH of the sample. Qualify results
that are > MDL as estimated low (J-) and qualify non-detects as unusable (R).
2. If technical holding times are exceeded, use professional judgment to determine the reliability of
the data based on the magnitude of the additional time compared to the technical requirement and
whether the samples are properly preserved. The expected bias would be low. Qualify results
that are > MDL as estimated low (J-) and non-detects as unusable (R).
3. Due to limited information concerning holding times for soil/sediment samples, it is left to the
discretion of the data reviewer whether to apply aqueous/water holding time criteria to
soil/sediment samples. If they are applied, it must be clearly documented in the Data Review
Narrative.
4. When the holding times are exceeded, the reviewer should comment in the Data Review
Narrative on any possible consequences for the analytical results.

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                                       Cyanide
    5.  When holding times are grossly exceeded, note it for Contract Laboratory Program Project
       Officer (CLP PO) action.

                 Table 27. Technical Holding Time Actions for Cyanide Analysis
Preservation & Holding Time Results
Aqueous/water cyanide samples received with
oxidizing agents present.
Aqueous/water cyanide samples received with
sulfides present, and sulfides are not removed
Aqueous/water cyanide samples received with
pH<12
Technical holding time exceeded:
Cyanide > 14 days
Action for Samples
Qualify results that are > MDL as estimated low
(J-)
Qualify non-detects as unusable (R)
Qualify results that are > MDL as estimated (J)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low
(J-)
Qualify non-detects as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated low
(J-)
Qualify non-detects as unusable (R)
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Cyanide
Calibration
A. Review Items:
Form II-IN (Part A), Form XI-IN, Form XIII-IN, Form XVI-IN, preparation logs, calibration standard
logs, instrument logs, instrument printouts, and raw data.

B. Objective:
Method requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable quantitative data for cyanide. Initial Calibration
Verification (ICV) demonstrates that the instrument is capable of acceptable performance at the
beginning of the analytical run. Continuing Calibration Verification (CCV) demonstrates that the
initial calibration is still valid by checking the performance of the instrument on a continuing basis.

C. Criteria:
1. Initial Calibration
The instruments shall be successfully calibrated daily (or once every 24 hours), and each time the
instrument is set up. The calibration date and time shall be included in the raw data.
a. A blank and at least five calibration standards shall be employed to establish the analytical
curve. At least one of the calibration standards shall be at or below the Contract Required
Quantitation Limit (CRQL). The calibration curve shall be fitted using linear regression or
weighted linear regression. The curve may be forced through zero. The calibration curve for
cyanide shall possess a correlation coefficient of > 0.995 to ensure the linearity over the
calibrated range. The percent differences calculated for all of the non-zero standards must be
within ±30% of the true value of the standard. The y-intercept of the curve must be less than
the CRQL.
All sample results shall be reported from an analysis within the calibrated range.
All standards shall be distilled.
b.
c.
2. Initial and Continuing Calibration Verification (ICV and CCV)
The acceptance criteria for the ICVs and CCVs are presented in Table 28:

Table 28. Acceptance Criteria for ICVs and CCVs
Analytical
Method
Colorimetric
Inorganic
Analyte
Cyanide
ICV/CCV
Low Limit
(% of True Value)
85
ICV/CCV
High Limit
(% of True Value)
115
a. Initial Calibration Verification (ICV)
1) Immediately after each cyanide colorimetric system has been calibrated, the accuracy of
the initial calibration must be verified and documented for cyanide by the analysis of an
ICV solution(s). If the ICV %R falls outside of the control limits, the analysis should be
terminated, the problem corrected, the instrument recalibrated, and all affected samples
reanalyzed.
2) If the ICV is not available from USEPA, or where a certified solution of the analyte is not
available from any source, analyses shall be conducted on an independent standard at a
concentration level other than that used for instrument calibration, but within the
calibrated range.
3) For cyanide analysis, the ICV standard solution shall be distilled.
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b. Continuing Calibration Verification (CCV)
1) To ensure accuracy during the course of each analytical run, the CCV shall be analyzed
and reported.
2) The CCV standard shall be analyzed at a frequency of every hour during an analytical
run. The CCV standard shall also be analyzed at the beginning of the run, and again after
the last analytical sample.
3) The analyte concentration in the CCV standard shall be different from the concentration
used for the ICV, and shall be at the mid level of the calibration curve.
4) The same CCV standard solution shall be used throughout the analysis runs for a Sample
Delivery Group (SDG). The CCV shall be distilled.
5) The CCV shall be processed and analyzed in the same fashion as an actual sample. If the
%R of the CCV was outside of the control limits, the analysis should be terminated, the
problem corrected, the instrument recalibrated, and all analytical samples analyzed since
the last compliant CCV reanalyzed.
D. Evaluation:
1 . Verify that the instrument was calibrated daily (once every 24 hours) and each time the
instrument was set up, utilizing a blank and at least five calibration standards. Confirm that at
least one of the calibration standards was analyzed at or below the CRQL.
2. Check the distillation log and verify that the calibration standards, the ICV and the CCVs were
distilled and analyzed.
3 . Verify that the ICV and CCV standards were analyzed for cyanide at the proper frequency and at
the appropriate concentration. Verify that acceptable %R results were obtained.
4. Recalculate one or more of the ICV or CCV %R using the following equation and verify that the
recalculated value agrees with the laboratory-reported values on Form IIA -IN.
o/0R = (value) x 1QQ
True (value)
Where,
Found (value) = Concentration (in (ig/L) of cyanide measured in the analysis of the ICV
or CCV solution
True (value) = Concentration (in (ig/L) of cyanide in the ICV or CCV source

E. Action:
NOTES: For initial calibrations or ICVs that do not meet the technical criteria, apply the action to
all samples reported from the analytical run.
For CCVs that do not meet the technical criteria, apply the action to all samples analyzed
between a previous technically acceptable analysis of the QC sample and a subsequent
technically acceptable analysis of the QC sample in the analytical run.
1 . If the instrument was not calibrated daily and each time the instrument was set up, qualify the
data as unusable (R). If the instrument was not calibrated with at least the minimum number of
standards, or if the calibration curve does not include standards at required concentrations (e.g., a
blank and a standard at or below the CRQL), use professional judgment to qualify results that are
> Method Detection Limit (MDL) as estimated (J) or unusable (R), and non-detects as estimated
(UJ) or unusable (R).
2. If the correlation coefficient is < 0.995, percent differences outside the ±30% limit, or y-intercept
>CRQL, qualify sample results that are > MDL as estimated (J), and non-detects as estimated
(UJ).
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                                        Cyanide
    3.  If the standards, the ICV, or the CCVs are not distilled for cyanide, qualify sample results that are
       > MDL as estimated (J).
    4.  If the ICV or CCV %R falls outside the acceptance windows, use professional judgment to
       qualify all associated data. If possible, indicate the bias in the review. The following guidelines
       are recommended:
       a.  If the ICV or CCV %R is < 70%, qualify non-detects as unusable (R). Use professional
           judgment to qualify all results that are > MDL as estimated low (J-) or unusable (R).
       b.  If the ICV or CCV %R falls within the range of 70-84%, qualify sample results that are >
           MDL as estimated low (J-), qualify non-detects as estimated (UJ).
       c.  If the ICV or CCV %R falls within the range of 116-130%, qualify sample results that are >
           MDL as estimated high (J+).
       d.  If the ICV or CCV %R is within the range of 116-130%, non-detects should not be qualified.
       e.  If the ICV or CCV %R is > 130%, use professional judgment to qualify results that are >
           MDL as estimated high (J+) or unusable (R).  Non-detects should not be qualified.
       f  If the %R is > 165%, qualify all results that are > MDL as unusable  (R).
    5.  If the laboratory failed to provide adequate calibration information, the Region's designated
       representative should contact the laboratory and request the necessary information. If the
       information is not available, the reviewer must use professional judgment to assess the data.
    6.  Note the potential effects on the reported data due to exceeding the calibration criteria in the Data
       Review Narrative.
    7.  If calibration criteria are grossly exceeded, note this for Contract Laboratory Program Project
       Officer (CLP PO) action.
    NOTE:    For truly critical samples, a further in-depth evaluation of the calibration curve may be
               warranted to determine if additional qualification is necessary.

                       Table 29. Calibration Actions for Cyanide Analysis
Calibration Result
Calibration not performed
Calibration incomplete
Correlation coefficient < 0.995; %D
outside ±30%, y-intercept >CRQL
Standards and QC not distilled
ICV/CCV%R<70%
ICV/CCV %R 70-84%
ICV/CCV %R 1 16-130%
ICV/CCV %R> 130%
ICV/CCV %R> 165%
Action for Samples
Qualify all results as unusable (R)
Use professional judgment
Qualify results that are > MDL as estimated (J) or unusable
(R)
Qualify non-detects as estimated (UJ) or unusable (R)
Qualify results that are > MDL as estimated (J)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated (J)
Qualify results that are > MDL as estimated low (J-) or
unusable (R)
Qualify all non-detects as unusable (R)
Qualify results that are > MDL as estimated low (J-)
Qualify non-detects as estimated (UJ)
Qualify results that are > MDL as estimated (J)
Qualify results that are > MDL as estimated high (J+) or
unusable (R)
Qualify results that are > MDL as unusable (R)
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Blanks
A. Review Items:
Form I-IN, Form III-IN, Form XII-IN, Form XIII-IN, preparation logs, calibration standard logs,
instrument logs, and raw data.

C. Criteria:
1. No contaminants should be found in the blank(s).
2. The Initial Calibration Blank (ICB) shall be analyzed after the analytical standards, but not before
analysis of the Initial Calibration Verification (ICV) during the initial calibration of the
instrument (see Section II.C.I).
3. A Continuing Calibration Blank (CCB) shall be analyzed immediately after every Continuing
Calibration Verification (CCV). The CCB shall be analyzed at a frequency of every hour during
the run. The CCB shall be analyzed at the beginning of the run, and again after the last CCV that
was analyzed after the last analytical sample of the run. The CCB result (absolute value) shall not
exceed the Contract Required Quantitation Limit (CRQL) of cyanide.
4. At least one Preparation Blank shall be prepared and analyzed for each matrix, with every Sample
Delivery Group (SDG), or with each batch of samples distilled, whichever is more frequent. The
Preparation Blank consists of reagent water processed through the appropriate sample preparation
and analysis procedure.
5. If the cyanide concentration in the Preparation Blank is > CRQL, the lowest concentration of
cyanide in the associated samples must be > 10 times (lOx) the Preparation Blank concentration.
Otherwise, all samples associated with that Preparation Blank with a cyanide concentration < lOx
the Preparation Blank concentration, and > CRQL, should be redistilled and reanalyzed cyanide
(except for an identified field blank). The laboratory is not to correct the sample concentration
for the blank value.
6. If the concentration of the Preparation Blank for cyanide is < (-CRQL), all samples reported <
lOx the CRQL (associated with that blank), should be redistilled and reanalyzed.
D. Evaluation:
1. Verify that an ICB was analyzed after the calibration, the CCB was analyzed at the proper
frequency and location during the run, and Preparation Blanks are prepared and analyzed as
appropriate for the SDG (e.g., total number of samples, various types of matrices present, number
of digestion batches, etc.).
2. Review the results reported on the Blank Summary (Form III-IN), as well as the raw data for all
blanks, and verify that the results were accurately reported.
3. Evaluate all of the associated blanks for the presence of cyanide. Verify that if cyanide was
present in a Preparation Blank or if a concentration was < (-CRQL), the affected samples were
redistilled and reanalyzed. Verify that if cyanide was present in an ICB or a CCB, the analysis
was terminated, the problem corrected, the instrument recalibrated, and the preceding 10
analytical samples or all analytical samples analyzed since the last compliant calibration blank
reanalyzed.
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E. Action:
NOTES: For ICBs that do not meet the technical criteria, apply the action to all samples reported
from the analytical run.
For CCBs that do not meet the technical criteria, apply the action to all samples analyzed
between a previous technically acceptable analysis of the CCB and a subsequent
technically acceptable analysis of the CCB in the analytical run.
For Preparation Blanks that do not meet the technical criteria, apply the action to all
samples prepared in the same preparation batch.
1. If the appropriate blanks are not analyzed with the correct frequency, the data reviewer should use
professional judgment to determine if the associated sample data should be qualified. The
reviewer may need to obtain additional information from the laboratory. The situation should
then be recorded in the Data Review Narrative, and noted for Contract Laboratory Program
Project Officer (CLP PO) action.
2. Action regarding unsuitable blank results depends on the circumstances and origin of the blank.
The reviewer should note that in instances where more than one blank is associated with a given
sample, qualification should be based upon a comparison with the associated blank having the
highest concentration of contaminant.
3. Some general "technical" review actions include:
a. Any blank (including Preparation Blanks) reported with a negative result, whose value is
< (-MDL) but > (-CRQL), should be carefully evaluated to determine its effect on the sample
data. The reviewer shall then use professional judgment to assess the data. For any blank
(including Preparation Blanks) reported with a negative result, whose value is < (-CRQL)
qualify results that are > CRQL as estimated low (J-) and non-detects as estimated (UJ).
b. The blank analyses may not involve the same weights, volumes, or dilution factors as the
associated samples. In particular, soil/sediment sample results reported on Form I-IN will not
be on the same basis (units, dilution) as the calibration blank data reported on Form III-IN.
The reviewer may find it easier to work with the raw data.
4. Specific "method" actions include:
a. If the absolute value of an ICB or a CCB result is > CRQL, the analysis should be terminated.
If the analysis was not terminated and the affected samples are not reanalyzed, report non-
detects and results that are > MDL but < CRQL as CRQL-U. For results that are > CRQL but
< Blank Result, use professional judgment to qualify the data as unusable (R), or report the
results at the level of the blank with a "U" qualifier. Use professional judgment to qualify
results that are > Blank Result. Note this situation for CLP PO action and record it in the
Data Review Narrative.
b. If the absolute value of the concentration of the Preparation Blank is < CRQL, no correction
of the sample results should be performed, report non-detects and results > MDL but < CRQL
as CRQL-U. Use professional judgment to qualify results that are > CRQL.
c. If the cyanide concentration in the Preparation Blank is > CRQL, the lowest concentration of
cyanide in the associated samples must be lOx the Preparation Blank concentration.
Otherwise, all samples associated with that blank with concentrations < lOx the Preparation
Blank concentration and > CRQL should be redistilled and reanalyzed. Raise the CRQL to
the concentration found in the Preparation Blank and report those samples that do not require
redistillation (that are > MDL but < CRQL) as CRQL-U. Note for CLP PO action and record
in the Data Review Narrative if the laboratory failed to redistill and reanalyze the affected
samples. The reviewer shall then use professional judgment to assess the data.
January 2010

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Inorganic Data Review
                                       Cyanide
                         Table 30. Blank Actions for Cyanide Analysis
Blank
Type
ICB/CCB
ICB/CCB
ICB/CCB
ICB/CCB
Preparation
Blank
Preparation
Blank
Preparation
Blank
Blank Result
Absolute value is
> MDL but <
CRQL
Absolute value is
>CRQL
< (-MDL), but
> (-CRQL)
< (-CRQL)
>CRQL
> MDL but <
CRQL
< (-CRQL)
Sample Result
Non-detect
> MDL but < CRQL
>CRQL
> MDL but < CRQL
> CRQL but < Blank Result
> Blank Result
> MDL, or non-detects
< 1 Ox the CRQL
> MDL but < CRQL
> CRQL but < lOx the Blank
Result
> 1 Ox the Blank Result
Non-detect
> MDL but < CRQL
>CRQL
< 1 Ox the CRQL
Action for Samples
No action
Report CRQL value with a "U"
Use professional judgment
Report CRQL value with a "U"
Report at level of Blank Result with
a "U" or qualify data as unusable
(R)
Use professional judgment
Use professional judgment
Qualify results that are > CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
Report CRQL value with a "U"
Qualify results as unusable (R) or
estimated high (J+)
No action
No action
Report CRQL value with a "U"
Use professional judgment
Qualify results that are > CRQL as
estimated low (J-)
Qualify non-detects as estimated
(UJ)
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Duplicate Sample Analysis
A. Review Items:
Cover Page, Form VI-IN, Form XII-IN, instrument printouts, and raw data.

C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
duplicate sample analysis.
2. At least one duplicate sample shall be prepared and analyzed from each group of samples of a
similar matrix type (e.g., water or soil) or for each Sample Delivery Group (SDG). Duplicates
cannot be averaged for reporting on Form I-IN. Additional duplicate sample analyses may be
required by USEPA Regional request. Alternately, the Region may require that a specific sample
be used for the duplicate sample analysis.
3. A control limit of 20% for the Relative Percent Difference (RPD) shall be used for original and
duplicate sample values > five times (5x) the Contract Required Quantitation Limit (CRQL).
4. A control limit of the CRQL shall be used if either the sample or duplicate value is < 5x the
CRQL. The absolute value of the control limit (CRQL) shall be entered in the "Control Limit"
column on Form VI-IN. If both samples are non-detects, the RPD is not calculated for Form VI-
IN.
NOTE: The above control limits are method requirements for duplicate samples, regardless of
the sample matrix type. However, it should be noted that laboratory variability arising
from the sub-sampling of non-homogenous soil samples is a common occurrence.
Therefore, for technical review purposes only, Regional policy or project Data Quality
Objectives (DQOs) may allow the use of less restrictive criteria (e.g., 35% RPD, 2xthe
CRQL) to be assessed against duplicate soil samples.
D. Evaluation:
1. Verify from the Cover Page, Form XII-IN, and the raw data that the appropriate number of
required duplicate samples were prepared and analyzed for the SDG.
2. Evaluate Form VI-IN and the raw data to verify that all cyanide duplicate results for each method
fall within the established control limits.
3. Verify that a field blank or PE sample was not used for duplicate analysis.
4. Check the raw data and recalculate one or more of the RPD values using the following equation
to verify that the results were correctly reported on Form VI-IN:
S-D
RPD =
(S + D)/2
Where,
RPD = Relative Percent Difference
S = Sample result (original)
D = Duplicate result
100
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E.  Action:
    NOTE:
       For a duplicate sample analysis that does not meet the technical criteria, apply the action
       to all samples of the same matrix, if the reviewer considers the samples sufficiently
       similar. The reviewer will need to exercise professional judgment in determining sample
       similarity.  The reviewer should make use of all available data, including: site and
       sampling documentation (e.g., location and type of sample, descriptive data, soil
       classification); field test data (e.g., pH, Eh, conductivity, chlorine); and laboratory data
       for other parameters [e.g., Total Suspended Solids (TSSs), Total Dissolved Solids
       (TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
       anions], in determining similarity.  The reviewer should also use the sample data (e.g.,
       similar concentrations of analytes) in determining similarity between samples in the
       SDG.  The reviewer may determine that only some of the samples in the  SDG are similar
       to the duplicate sample, and that only these samples should be qualified.  Or, the reviewer
       may determine that no samples are sufficiently similar to the sample used for the
       duplicate, and thus that only the field sample used to prepare the duplicate sample should
       be qualified.
If the appropriate number of duplicate samples was not analyzed for each matrix  using the correct
frequency, use professional judgment to determine if the associated sample data should be
qualified.  The reviewer may need to obtain additional information from the laboratory. Note the
situation in the Data Review Narrative,  and for Contract Laboratory Program Project Officer
(CLP PO) action.
If the results from a duplicate analysis for cyanide fall outside the appropriate control limits,
qualify sample results that are > Method Detection Limit (MDL) as estimated (J) and non-detects
as estimated (UJ).
If a field blank or PE sample was used for the duplicate sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked and
professional judgment exercised by the  data reviewer when evaluating the data.
Note the potential effects on the data due to out-of-control duplicate sample results in the Data
Review Narrative.

             Table 31. Duplicate Sample Actions for Cyanide Analysis
Duplicate Sample Results
Both original sample and duplicate sample > 5x
the CRQL and RPD> 20%*
Original sample or duplicate sample < 5x the
CRQL (including non-detects) and absolute
difference between sample and duplicate >
CRQL*
Action for Samples
Qualify those results that are > MDL that
professional judgment determines to be affected as
estimated (J) and non-detects as estimated (UJ)
Qualify those results that are > MDL that
professional judgment determines to be affected as
estimated (J) and non-detects as estimated (UJ)
     The above control limits are method requirements for duplicate samples, regardless of the sample
     matrix type. However, it should be noted that laboratory variability arising from the sub-sampling of
     non-homogenous soil samples is a common occurrence. Therefore, for technical review purposes
     only, Regional policy or project Data Quality Objectives (DQOs) may allow the use of less
     restrictive criteria (e.g., 35% RPD, 2xthe CRQL) to be assessed against duplicate soil samples.
January 2010
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Spike Sample Analysis
A. Review Items:
Cover Page, Form V-IN (Parts A & B), Form XII-IN, instrument printouts, and raw data.

B. Objective:
The spiked sample analysis is designed to provide information about the effect of each sample matrix
on the sample preparation procedures and the measurement methodology. Non-homogenous samples
can impact the apparent method recovery. However, aqueous/water samples are generally
homogenous and most soil/sediment samples are homogenous within a factor of two or three. If the
spike is added to the sample prior to any distillation steps (e.g., cyanide), it is referred to as a spiked
sample, pre-distillation spike, or Matrix Spike. If the spike is added to the sample after the
completion of the distillation procedures, it is referred to as a post-distillation spike, or analytical
spike.

C. Criteria:
1. Samples identified as field blanks or Performance Evaluation (PE) samples cannot be used for
spiked sample analysis.
2. At least one spiked sample (pre-distillation) shall be prepared and analyzed from each group of
samples with a similar matrix type (e.g., water or soil), or for each Sample Delivery Group
(SDG).
3. When the pre-distillation spike recovery falls outside of the control limits and the sample result is
< four times (4x) the spike added, a post-distillation spike shall be performed An aliquot of the
remaining unspiked sample shall be spiked at 2x the indigenous level or 2x the Contract Required
Quantitation Limit (CRQL), whichever is greater.
4. The spike Percent Recovery (%R) shall be within the established acceptance limits. However,
spike recovery limits do not apply when the sample concentration is.4x the spike added. In such
an event, the data shall be reported unflagged, even if the %R does not meet the acceptance
criteria.
5. If the spiked sample analysis was performed on the same sample that was chosen for the duplicate
sample analysis, spike calculations shall be performed using the results of the sample designated
as the "original sample". The average of the duplicate results cannot be used for the purpose of
determining %R.

NOTE: The final spike concentrations required for cyanide are presented in the method described
in the Statement of Work (SOW).
D. Evaluation:
1. Verify using the Cover Page, Form VA-IN, Form XII-IN, and raw data that the appropriate
number of required spiked samples were prepared and analyzed for the SDG.
2. Verify that a field blank or PE sample was not used for the spiked sample analysis.
3. Evaluate Form VA-IN and the raw data to verify that all pre-distillation spiked sample results fall
within the established control limits. If not, verify that a post-distillation spike was prepared and
analyzed.
4. Recalculate using the raw data, one or more of the %R using the following equation, and verify
that the recalculated value agrees with the laboratory-reported values on Forms V (A & B)-IN:

%Recovery = SSR ~ SR x 100
SA
Where,
SSR
SR
SA
January 2010

= Spiked Sample Result
= Sample Result
= Spike Added

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Inorganic Data Review Cyanide

NOTE: When the sample concentration is < Method Detection Limit (MDL), use SR = 0 only for
the purposes of calculating the %R. The actual spiked sample results, sample results, and
%R (positive or negative) shall still be reported on Form V (A & B)-IN.
E. Action:
NOTE: For a Matrix Spike that does not meet the technical criteria, apply the action to all
samples of the same matrix, if the reviewer considers the samples sufficiently similar.
The reviewer will need to exercise professional judgment in determining sample
similarity. The reviewer should make use of all available data, including: site and
sampling documentation (e.g., location and type of sample, descriptive data, soil
classification); field test data (e.g., pH, Eh, conductivity, chlorine); and laboratory data
for other parameters [e.g., Total Suspended Solids (TSSs), Total Dissolved Solids
(TDSs), Total Organic Carbon (TOC), alkalinity or buffering capacity, reactive sulfide,
anions], in determining similarity. The reviewer should also use the sample data (e.g.,
similar concentrations of analytes) in determining similarity between samples in the
SDG. The reviewer may determine that only some of the samples in the SDG are similar
to the Matrix Spike sample, and that only these samples should be qualified. Or, the
reviewer may determine that no samples are sufficiently similar to the sample used for
the Matrix Spike, and thus that only the field sample used to prepare the Matrix Spike
sample should be qualified.
1. If the appropriate number of Matrix Spike samples was not analyzed for each matrix using the
correct frequency, use professional judgment to determine if the associated sample data should be
qualified. The reviewer may need to obtain additional information from the laboratory. Note the
situation in the Data Review Narrative, and for CLP Project Officer (CLP PO) action.
2. If a field blank or PE sample was used for the spiked sample analysis, note this for CLP PO
action. All of the other Quality Control (QC) data must then be carefully checked and
professional judgment exercised by the data reviewer when evaluating the data.
3. If the Matrix Spike recovery does not meet the evaluation criteria and a required post-distillation
spike was not performed, note this for CLP PO action.
4. If the Matrix Spike %R is < 30%, verify that a post-distillation spike was analyzed if required. If
the post-distillation spike %R is < 75% or is not performed, qualify sample results that are >
MDL as estimated low (J-) and non-detects as unusable (R). If the post-distillation spike %R is >
75%, qualify sample results that are > MDL as estimated (J) and non-detects as estimated (UJ).
5. If the Matrix Spike %R falls within the range of 30-74% and the sample results are > MDL,
verify that a post-distillation spike was analyzed if required. If the %R for the post-distillation
spike is also < 75% or not performed, qualify the affected data as estimated low (J-). If the %R
for the post-distillation spike is > 75%, qualify the affected data as estimated (J).
6. If the Matrix Spike %R falls within the range of 30-74% and the sample results are non-detects,
qualify the affected data as estimated (UJ).
7. If the Matrix Spike %R is > 125% and the reported sample results are non-detects, the sample
data should not be qualified.
8. If the Matrix Spike %R is > 125% and the sample results are > MDL, verify that a post-
distillation spike was analyzed if required. If the %R for the post-distillation spike is also >
125% or is not performed, qualify the affected data as estimated high (J+). If the %R for the
post-distillation spike is < 125%, qualify the affected data as estimated (J).
9. Note the potential effects on the data due to out-of-control spiked sample results in the Data
Review Narrative.
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                                       Cyanide
                     Table 32.  Spike Sample Actions for Cyanide Analysis
Spike Sample Results Action for Samples
Matrix Spike %R < 30%
Post-distillation spike %R< 75%
Matrix Spike %R < 30%
Post-distillation spike %R > 75%
Matrix Spike %R 30-74%
Post-distillation spike %R < 75%
Matrix Spike %R 30-74%
Post-distillation spike %R > 75%
Matrix Spike %R > 125%
Post-distillation spike %R> 125%
Matrix Spike %R > 125%
Post-distillation spike %R < 125%
Matrix Spike %R < 30%
No post-distillation spike performed
Matrix Spike %R 30-74%
No post-distillation spike performed
Matrix Spike %R > 125%
No post-distillation spike performed
Qualify affected results that are > MDL as estimated low
(J-)
Qualify affected non-detects as unusable (R)
Qualify affected results that are > MDL as estimated (J)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated low
(J-)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated (J)
Qualify affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated high
(J+)
Qualify affected results that are > MDL as estimated (J)
Qualify affected results that are > MDL as estimated low
(J-) and affected non-detects as unusable (R)
Qualify affected results that are > MDL as estimated low
(J-) and affected non-detects as estimated (UJ)
Qualify affected results that are > MDL as estimated high
(J+)
Non-detects are not qualified
January 2010
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                   Regional Quality Assurance (OA) and Quality Control (OC)
A.  Review Items:
    Form I-IN, instrument printouts, and raw data.

B.  Objective:
    Regional QA/QC samples refer to any QA and/or QC sample initiated by the Region, including field
    duplicate samples, Performance Evaluation (PE) sample, blind spikes, and blind blanks. The use of
    these QA/QC sample sis highly recommended (e.g., the use of field duplicates can provide
    information on sampling precision and homogeneity).

C.  Criteria:
    Criteria are determined by each Region.
D.  Evaluation:
    Evaluation procedures must follow the Region's Standard Operating Procedure (SOP) for data
    review. Each Region will handle the evaluation of PE samples on an individual basis.  Compare
    results for PE samples to the acceptance criteria for the specific PE samples if possible.
    Calculate the Relative Percent Difference (RPD) between field duplicates and provide this
    information in the Data Review Narrative.
E.  Action:
    Any action must be in accordance with Regional specifications and criteria for acceptable PE sample
    results. Note any unacceptable PE sample results for Contract Laboratory Program Project Officer
    (CLP PO) action.
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C. Criteria:
1. Review all available materials to assess the overall quality of the data, keeping in mind the
additive nature of analytical problems.
2. Reported analyte concentrations must be quantitated according to the appropriate analytical
method, as listed in the method.
D. Evaluation:
Examine the raw data to verify that the correct calculation of the sample results was reported by the
laboratory. Distillation logs, instrument printouts, etc., should be compared to the reported sample
results recorded on the appropriate Inorganic Summary Forms (Form I-IN through Form XV-IN).
1. Evaluate any technical problems not previously addressed.
2. Examine the raw data for any anomalies (e.g., baseline shifts, negative absorbance, omissions,
illegibility, etc.).
3. Verify that the appropriate methods and amounts were used to prepare samples for analysis. If
reduced volumes were used, verify that the laboratory had received Contract Laboratory Program
Project Officer (CLP PO) approval for the use of the reduced volume.
4. Verify that there were no transcription or reduction errors [e.g., dilutions, Percent Solids (%S),
sample weights, etc.] on one or more samples.
5. Verify that results fall within the calibrated range for cyanide.
6. If appropriate information is available, the reviewer may assess the usability of the data to assist
the data user in avoiding inappropriate use of the data. Review all available information,
including the Quality Assurance Project Plan (QAPP), focusing specifically on the acceptance or
performance criteria, the Standard Operating Procedure(s) (SOPs), and communication with user
concerning the intended use and desired quality of these data.
E. Action:
1. Use professional judgment to determine if there is any need to qualify data which were not
qualified based on the QC criteria previously discussed.
2. Write a brief Data Review Narrative to give the user an indication of the analytical limitations of
the data. Note any discrepancies between the data and the SDG Narrative for CLP PO action. If
sufficient information on the intended use and required quality of the data is available, the
reviewer should include an assessment of the data usability within the given context.

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    3.   If any discrepancies are found, the laboratory may be contacted by the Region's designated
        representative to obtain additional information for resolution.  If a discrepancy remains
        unresolved, the reviewer may determine that qualification of the data is warranted.
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Inorganic Data Review	Cyanide

                                   Calculations for Cyanide
    Aqueous/Water Sample Concentration:
                                  Vf
    CN Concentration (ug/L) =  Cx— xDF

    Where,
       C      = Instrument response in |o,g/L CN from the calibration curve
       Vf     = Final prepared (absorbing solution) volume (mL)
       V      = Initial aliquot amount (mL)
       DF     = Dilution Factor

    Soil/Sediment Sample Concentration:

                                                     Vf
                    CN Concentration (mg/kg) =  C x —^- x (1/1000)  xDF
                                                   WxS
    Where,
       C      = Instrument response in |o,g/L CN from the calibration curve
       Vf     = Final prepared (absorbing solution) volume (mL)
       W     = Initial aliquot amount (g)
       S       = % Solids/100 (see Exhibit D - Introduction to Analytical Methods, Section 1.6)
       DF     = Dilution Factor

    Adjusted Method Detection Limit (MDL)/Adjusted Contract Required Quantitation Limit
    (CRQL) Calculation:
       To calculate the adjusted aqueous/water MDL or adjusted aqueous/water CRQL, follow the
       instructions in Exhibit D - Data Analysis and Calculations, Section 11.1.1.
       The adjusted soil/sediment MDL or adjusted soil/sediment CRQL for all methods shall be
       calculated as follows:
                      Adjusted Concentration (mg/kg)  = C x—— x  DF
                                                           WxS
    Where,
       C      = MDL or CRQL (mg/kg)
       WM    = Minimum method required aliquot amount (1.00 g for Midi or 0.50 g for Micro)
       W     = Initial aliquot amount (g)
       S       = % Solids/100 (see Exhibit D - Introduction to Analytical Methods, Section 1.6).
       DF     = Dilution Factor
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Inorganic Data Review                                                               Appendix A


                                 APPENDIX A: GLOSSARY
Analyte ~ The element of interest, ion, or parameter an analysis seeks to determine.
Analytical Services Branch (ASB) ~ Directs the Contract Laboratory Program (CLP) from within the
Office of Superfund Remediation and Technical Innovation (OSRTI) in the Office of Solid Waste and
Emergency Response (OSWER).
Analytical Sample ~ Any solution or media introduced into an instrument on which an analysis is
performed excluding instrument calibration, Initial Calibration Verification (ICV), Initial Calibration
Blank (ICB), Continuing Calibration Verification (CCV), and Continuing Calibration Blank (CCB). Note
that the following are all defined as analytical samples: undiluted and diluted samples (USEPA and non-
USEPA); Matrix Spike samples;  duplicate samples; serial dilution samples, analytical (post-
digestion/post-distillation) spike samples; Interference Check Samples (ICSs); Laboratory Control
Samples (LCSs); and Preparation Blanks.
Associated Samples ~ Any sample related to a particular Quality Control (QC) analysis.  For example,
for Initial Calibration Verification (ICV), all samples run under the same calibration curve. For
duplicates, all Sample Delivery Group  (SDG) samples digested/distilled of the same matrix.
Blank ~ A sample designed to assess specific sources of contamination. See individual definitions for
types of blanks.
Calibration ~ The establishment of an analytical curve based on the absorbance, emission intensity, or
other measured characteristic of known standards. The calibration standards are to be prepared using the
same type of reagents or concentration of acids as used in the sample preparation.
Calibration Blank ~ A blank solution containing all of the reagents in the same concentration as those
used in the analytical sample preparation. This blank is not subject to the preparation method.
Calibration Curve ~ A plot of instrument response versus concentration of standards.
Calibration Standards ~ A series of known  standard solutions used by the analyst for calibration of the
instrument (i.e., preparation of the analytical curve). The solutions may or may not be subjected to the
preparation method, but contain the same matrix (i.e., the same amount of reagents and/or preservatives)
as the sample preparations to be analyzed.
Case ~ A finite, usually predetermined number of samples collected over a given time period from a
particular site.  Case numbers are assigned by the Sample Management Office (SMO). A Case consists of
one or more Sample Delivery Groups (SDGs).
Continuing Calibration Blank (CCB) ~ A reagent water sample that is run 2 hours (ICP-AES, ICP-MS)
or every hour (Hg, CN) and designed to detect any carryover contamination.
Contract Compliance Screening (CCS) ~ A screening of electronic and hardcopy data deliverables for
completeness and compliance with the contract.  This screening is performed under USEPA direction by
the Contract Laboratory Program (CLP) Sample Management Office (SMO) contractor.
Continuing Calibration Verification  (CCV) ~ A single parameter or multi-parameter standard solution
prepared by the analyst and used to verify the stability of the instrument calibration with time, and the
instrument performance during the analysis of samples.  The CCV can be one of the  calibration standards.
However, all parameters being measured by the particular system must be represented in this standard and
the standard must have the same matrix (i.e., the same amount of reagents and/or preservatives) as the
samples.  The CCV should have a concentration in the middle of the calibration range and shall be run
every 2 hours (ICP-AES, ICP-MS) or every hour (Hg, CN).
Contract Laboratory Program (CLP) ~ Supports the  USEPA's Superfund effort by providing a range
of state-of-the-art chemical analytical services of known quality. This program is directed by the
Analytical Services Branch (ASB) of the Office of Superfund Remediation and Technical Innovation
(OSRTI) of USEPA.
Contract Laboratory Program Project Officer (CLP PO) ~ The Regional USEPA official responsible
for monitoring laboratory performance and/or requesting analytical data or services from a CLP
laboratory.

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Inorganic Data Review Appendix A

Contract Required Quantitation Limit (CRQL) ~ Minimum level of quantitation acceptable under the
contract Statement of Work (SOW).
Duplicate ~ A second aliquot of a sample that is treated the same as the original sample in order to
determine the precision of the method.
Field Blank ~ Any sample that is submitted from the field and identified as a blank. A field blank is
used to check for cross-contamination during sample collection, sample shipment, and in the laboratory.
A field blank includes trip blanks, rinsate blanks, bottle blanks, equipment blanks, preservative blanks,
decontamination blanks, etc.
Field Duplicate ~ A duplicate sample generated in the field, not in the laboratory.
Holding Time ~ The maximum amount of time samples may be held before they are processed.
Contractual ~ The maximum amount of time that the Contract Laboratory Program (CLP) laboratory
may hold the samples from the sample receipt date until analysis and still be in compliance with the terms
of the contract, as specified in the CLP Analytical Services Statement of Work (SOW). These times are
the same or less than technical holding times to allow for sample packaging and shipping.
Technical ~ The maximum amount of time that samples may be held from the collection date until
analysis.
Initial Calibration ~ Analysis of analytical standards for a series of different specified concentrations to
define the quantitative response, linearity, and dynamic range of the instrument to target analytes.
Initial Calibration Blank (ICB) ~ The first blank standard run to confirm the calibration curve.
Initial Calibration Verification (ICV) ~ Solution(s) prepared from stock standard solutions, metals, or
salts obtained from a source separate from that utilized to prepare the calibration standards. The ICV is
used to verify the concentration of the calibration standards and the adequacy of the instrument
calibration. The ICV should be traceable to National Institute of Standards and Technology (NIST) or
other certified standard sources when USEPA ICV solutions are not available.
Internal Standard ~ A non-target element added to a sample at a known concentration after preparation
but prior to analysis. Instrument responses to internal standards are monitored as a means of assessing
overall instrument performance.
Interference Check Sample (ICS) ~ Verifies the contract laboratory's ability to overcome interferences
typical of those found in samples.
Laboratory Control Sample (LCS) ~ A control sample spiked at known level(s). LCSs are processed
using the same sample preparation, reagents, and analytical methods employed for the USEPA samples
received.
Matrix ~ The predominant material of which the sample to be analyzed is composed. For the purposes
of this document, the matrices are aqueous/water, soil/sediment, wipe, and filter.
Matrix Spike ~ Introduction of a known concentration of analyte into a sample to provide information
about the effect of the sample matrix on the digestion and measurement methodology (also identified as a
pre-distillation/digestion spike).
Method Detection Limit (MDL) ~ The concentration of a target parameter that, when a sample is
processed through the complete method, produces a signal with 99 percent probability that it is different
from the blank. For 7 replicates of the sample, the mean value must be 3.14s above the blank, where "s"
is the standard deviation of the 7 replicates.
Narrative (SDG Narrative) ~ Portion of the data package which includes laboratory, contract, Case,
Sample Number identification, and descriptive documentation of any problems encountered in processing
the samples, along with corrective action taken and problem resolution.
Office of Solid Waste and Emergency Response (OSWER) - The USEPA office that provides policy,
guidance, and direction for the USEPA's solid waste and emergency response programs, including
Superfund.
Percent Difference (%D) ~ As used in this document and the Statement of Work (SOW), is used to
compare two values. The difference between the two values divided by one of the values.

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Performance Evaluation (PE) Sample ~ A sample of known composition provided by USEPA for
contractor analysis. Used by USEPA to evaluate Contractor performance.
Post Digestion Spike ~ The addition of a known amount of standard after digestion or distillation (also
identified as an analytical spike).
Preparation Blank ~ An analytical control that contains reagent water and reagents, which is carried
through the entire preparation and analytical procedure.
Relative Percent Difference (RPD) ~ As used in this document and the Statement of Work (SOW) to
compare two values, the RPD is based on the mean of the two values, and is reported as an absolute value
(i.e., always expressed as a positive number or zero).
Regional Sample Control Center Coordinator (RSCC) ~ In USEPA Regions, coordinates sampling
efforts and serves as the central point-of-contact for sampling questions and problems. Also assists  in
coordinating the level of Regional sampling activities to correspond with the monthly projected demand
for analytical services.
Relative Standard Deviation  (RSD) ~ As used in this document and the Statement of Work (SOW), the
mean divided by the standard deviation, expressed as a percentage.
Sample ~ A single, discrete portion of material to be analyzed, which is contained in single or multiple
containers and identified by a unique Sample Number.
Sample Delivery Group (SDG) ~ A unit within a sample Case that is used to identify a group of samples
for delivery. An SDG is defined by the following, whichever is most frequent:
    a.  Each 20 field samples  [excluding Performance Evaluation (PE) samples] within a Case;  or
    b.  Each 7 calendar day period (3 calendar day period for 7-day turnaround) during which field
       samples in  a Case are received (said period beginning with the receipt of the first sample in  the
       SDG).
    c.  Scheduled at the same  level  of deliverable.
In addition, all samples and/or sample fractions assigned to an SDG must be scheduled under the same
contractual turnaround time. Preliminary Results have no impact on defining the SDG.  Samples may  be
assigned to SDGs by matrix (i.e., all soil/sediment samples in one SDG, all aqueous/water samples in
another) at the discretion of the laboratory.
Sample Management Office (SMO) ~ A contractor-operated facility operated under the SMO contract,
awarded and administered by the USEPA.  Provides necessary management, operations, and
administrative  support to the Contract Laboratory Program (CLP).
Serial Dilution ~ The dilution of a sample by a factor of five. When corrected by the Dilution Factor
(DF), the diluted sample must agree  with the original undiluted sample within specified limits. Serial
dilution may reflect the influence of interferents [Inductively Coupled Plasma (ICP) only].
Statement of Work (SOW) ~ A document which specifies how laboratories analyze samples under a
particular Contract  Laboratory Program (CLP) analytical program.
Tune ~ Analysis of a solution  containing a range of isotope masses to establish Inductively Coupled
Plasma - Mass Spectrometry (ICP-MS) mass-scale accuracy, mass resolution, and precision prior to
calibration.
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Inorganic Data Review
                                                                        Appendix B
                                    APPENDIX B:
                       INORGANIC DATA REVIEW SUMMARY
CASE NO.
LABORATORY,

MOD. REF. NO.

SOW NO.	
REVIEWER NAME.

CLP PO: ACTION
                                      SITE
                                      NO. OF SAMPLES/MATRIX

                                      SDGNO.	

                                      REGION	
                                      COMPLETION DATE

                                      FYI	
REVIEW CRITERIA
1.  Preservation/Holding Time
2.
3.
                                ICP-AES
                                          METHOD/ANAL YTE
                                          ICP-MS      Mercury
Cyanide
Calibration
Blanks
4.  Interference Check Sample
5.  Laboratory Control Sample
6.  Duplicate Sample Analysis
7.  Spike Sample Analysis
8.  ICP Serial Dilution
9.  ICP-MS Tune Analysis
10. ICP-MS Internal Standards
11. Field Duplicates
12. Overall Assessment
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