INNOVATIVE APPROACHES TO DATA
VALIDATION
UNITED STATES ENVIRONMENTAL
PROTECTION AGENCY
REGION III
JUNE 1995
53 ^s9M^7 c
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, INNOVATIVE APPROACHES FOR
VALIDATION OF ORGANIC AND INORGANIC DATA-
STANDARD OPERATING PROCEDURES '
... JUNE 1995,
U.S. .ENVIRONMENTAL PROTECTION AGENCY .
REGION III
ANALYTICAL SERVICES AND QUALITY ASSURANCE BRANCH
201 "DEFENSE HIGHWAY, SUITE 200
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The procedures set forth herein are as They do not constitute
ralemaking by the Agency and may not be relied on to a or
procedural right1, enforceable by any other person. The
action that is at variance with the in this manual.
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INTROBUCllON
There are five levels of data validation within this manual approach. The levels consist of three
(3) organic review procedures (M-l, M~2, M-3) and two inorganic review procedures (IM-1,
, IM-2), (The terar "level8 is perhaps oiislrading because it impUes success
<' case with this or-any diiar-Jtfwd;fHpwซted to this document. The ."levels " *ป ladq^eadettt of
each other.) M-3 -iiiif IM*liBii^ described in the EPA'
National Functional Guidelines for Data Heview. Should the intended data use dictate review
by the protocols presented in the National Functional Guidelines for Data Review (IMป2 and M-
3), refer to the most recent version of Region HI Modifications to the National Functional
' Guidelines, . The remaining data review levels are described in detail in this document. The
- SOPs describing how to apply these levels to a dataปpackage are in Appendices A through D.
- AH probedozes xequire ftlilClJ* .<* GLJ? equivalent data .package, deliiverabldp,
' M general*, ofganic Levdl'M-1's emphasis is on iwiewkg poatiwe Atau "Itte prunaty
question asked is whether or not a compound is present. If it is, the next question is
whether the compound is potentially from field or laboratory-induced contamination. If the
. answer is negative, then the presence of the compound is considered confirmed, and the reported,
concentrations are considered usable for some predefined dab ma. If information regarding
data quality and usability is required, then the emphasis is shifted accordingly to in evaluation
of data quality pianaetefs, negatives, and detection Emits (Levd'ftf-2 ocAf-1). ff legally
defensible data are necessary, thai a Ml, CLP-equivalent data validation is performed (Level
M-3 or IM-2), There is a "definite focus at every step of the process. *Ms allows for a
differentiation in the levels of. data validation.
For guidance purposes, general data use categories and suggested levels of review are provided
in Table 1-3. However, it is important to note that the selected level of review win be
to the intended data use and specific project objectives.
Standard Operating Procedures
SOPs have been developed for Levels M-l, M-2, and IM-1 and are in the following sections
of this document
Voktiles (Appendix A)
, Semivoktilps (AppendkB)
Pesticides/PCB' (Appendix C)
Metals and Cyanide (Appendix D)
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' CONTENTS
: ,
Introduction
Glossary of Acronyms and Terms
Appendix (SOft) ,, . '^ ;',-.. . . . "."
A. Valldatloa of :VTo!afi!e.:Organic Anaijte Data (Levels Ml and M2)
A-l.
- 1. Pozpose^and'Aiipllcdnlity ..,..,,...,.,...,.,ป'.,....,ป.. 1
2. Quality CJoatei .Measures Cheeked .,,.......,.,.,..-....,,.,,. 1
i. ' '3. PttX5edu^i;*l>:',y^.::ซ^;ป- ...... *-. . . .-. w ....... .-. ........ .1
3".l -Xcti^'.LisVd'^qitifa^on .....-....,,.,,....,.,... . '.3
' '.- 3.2 'Bi^iioitioa'ofMBSS Spectra for Detwtel ,: .,-";,. ' , ,''
'"'';; bpujpouiwls ...'.........-.....-........'., . ...,-.. 6
/ .3.3 BiMuaBiiM of Chromatograms . . . . * .... .-. ,.,.,,..,.ป,. 1Q'
( 3.4 Bwtoatwa ^f >Seteotioii' Times ,.'.,......*......, '. . . . 14
, 3.5 'Bvalwticrt of Blanks ....... ....... .....-......".... 16
'3,6 Sunple Rfelerwnk ...'...............ซ....-..* ..... 17
Tsiblcs
Ml-VQA-1 QC ChccMist.for Lewi Ml CLP RAS Volatile Oiganks .-.^ ........ 2
'Ml-VOA-2 VolatilB^Oigamc Analytes and Action Lerds .........'...-..... 5.
Ml-VOA-3 VOAMass Spectral Evaluatioa Summary, ................... 11
A-2. Manual Levd M2 (for VOAs)
1. Purpose aid Applicability ............................... 1
2, Quality Control Measures Checked ...........'......-......... 3
3. Procedure ............................ ^ ........... .3
3.1 Action Level Notification .................;........?
3.2 TajMal Holding Times .............'............. 10
3.3 GC/MS Instalment Perfonnance Check 12
3.4 Initial Calibration ................................. 14
3.5 Contihuing Calibration ...................'........ 18
3.6 ..:.............. 20
3.7 System Monitoring Compounds (Surrogate
Spikes 25
3.8 Matrix Spike/Matrix Spike Duplicate .............'..... 28
- 3.9 Internal Standards .............................. 29'
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CONTENTS {Continueฎ
3.10 CRQLs ............................... 31
3.11 Tentatively Identified Compounds ...,..,.......,.'.,.. 32
, Tabtes
.M2-VOA-1 QC CteeUist for Level M2 CUP-MAS Yokffle Grganics ,,...'.'.*. .2
M2-VOA-2 VGA .QualifierSummary! ...............*..'.. ..-..';',;>,, . ; . .5,
M2-VOA-3 VOA'Siwopte and Matrix Quality Control Summary, vvl * .... 6
.M2-VGA4 ' VoWOIe'-Qipnic Analytw and Action Levds .....,, .,.,^,.ป_jj. ... 9
M2-VOA-5 CJusJffiiitloii erf VoibtilB Analytes Baปd on Tedtoii^ JixM^wH* t , 11
.M2-VQA-6 QuaMficatieoM Volatile Analytes Basal CM System Momtariiig''//'
Recoveries ...................... ."*.- ^".'';. i". . . . 27
B. ~~ Validation of SejiiIvoIatlEe Dat3 {I^veb Ml'and AH)
B-l. Mimual Level Ml (fbr SVOAs) ' -
1. Purpose and .....
2. .Quality'ConteDl'Maisino Cheeked
3:-' Procedure '.;.;.,.'.-.'.'.,..'.,
Ml-SVOA-1
Ml-SVQA-2'
Ml-SVOA-3
3.1
3.2
Acticni' Levd'Notification '........'................... 3
Evaluation of Mass Spectra for Detected
- Compottnds ..........:...................... 5
Evaliiatiai of Chromatograms . *; ,;^^ ..... 9.
EvaluatiQii of Retention Times ,...-,...,....,. ."......... 15
Evaluation of Blanks .,,.,,.,'. 16
Sample Paperwork .............................. 17
Tables
QC ChecMist for Ijevel Ml 2
Semivolatile Qiiganic Analytes and. Action Levels, ...,...,,,...,, 4
Man Spectral Evaluation Summary 1Q
3.3
3.4
3.5
3.6
B-2. Manual Levd M2 (for SVOAs)
1. Purpose and Aj^pHcability . ......',.........'.......' 1
2. Quality Control Measures Cheeked ........................... 3
3. Procedures ........................................ .3
3.1 Action Levd Notification .......................... 9
3.2 Technical Holding Times .......................... 11
3.3 GC/MS Instrument Performance Check 13
3.4 Initial Calibration 16
3,5 Continuing Calibration ............................. 20
3.6 ..................................... 22
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CONTENTS
Rtge-
1 3.7. '. .......... T. . . . _. ............... 28
3.8 Mtek"Spibe/&torป Spite Duplicate -..;..... 32
' 3.9 -.-...:....... ....;....,'... 34
3.11 CompoiicIS' ....... ^$ฃjฃvvY.--.;.'. 37
'"'.' 7^|fe^si:*4^'l,i'"V / ' TaWes
M2-SVOA4 . . .... ...... .>:^ff|
M2-SVOA-3 SฅQA ad'Mattk - - ^'
M2-SVOA-4 'Lards ........"..,; .."J&*"'
' R
.'-v^'iSe
' C.
Validate of Bate (levels Ml and M2) ,
1. Puipose and Apicalillity-
... r .-..'... ,,'.-:"-5rฃi?ซ^;:.:':, .....',.. 1
'"'^'"'^s'-v*'. .l"
2.
3. Pfooedote
' 3.1
,33" Eฅaliiatiottof Retotion.Times' , . . I . , .. .Vป'-;*1VKV. ...... .5
3.3 Evaluation of Chroamtograms ..-.. .-. ; , .. i-,"v-C>. ....... .7
3.4 Bvalttatioa of Htoto .................. *......... 14
3.5' Sample Paperwork' ....'..................,...;.'.... 19"
Tables
Ml-PEST-1 Checklst for Level Ml PEST/PCB '. . .2
Ml-PEST-2 PEST/PCB Action Levels. ........... .............. 4
Ml-PBST-3 Time for Windows ................ 8
Ml-PEST-4 PEST/PCB Retention Time for Evaluation Summary. ............ .9
C-2. Manual Level M2 (for Pesticides/PCBs)
1. Purpose and Appicability ............................... I
2. Quality Control Measures Checked .......................... 3
3, Procedures ............ ป............................ .3
3.1 Action Leyd Notification .......................... 7
3.2 Technical Holding Times ........................... 9
3.3 GC/ECD Instrument Performance Check ................ 11
3.4 Initial Calibration ............................... 16
3.5 Continuing Calibration ..,.;..... 18
3.6 .....................................21
3.7 Surrogate Spikes 25
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CGMปfT5 (Continued!)
Page
_ 3.S 'Mftfri* Duplicate ................... 27
' 3.9 -Pesticide Qearap Checks ............;..........'... 28
3.10 CRQLE ....;......................... 30
'
M2-PEST-1
M2-PEST-2
M2-PEST-3
SI
Attachment to Appendix C-2
c ( , . ^ " =* A - V1- . r .
D.-
.Ijte Data (I.evd MI)
:2.3
'2,4
2.5
2.6
' ' ' 2.7
2.8
2.9
2.10
2.11
2.12
2.13
2.14
2.15
1M-WNORG-QC.
ttf-l-JNQRG-AL
M-1-INORG-HT.
IM-1-MORG-CAL.
EM-1-INORG-SPK.
IM-1-INORG-QL.
IM-l-MORG-fflDA
.. .i. .......-, ,.C. ..,-.- 2
,...'...,,...,;;/..'..,...-.. .2
.........'....'.*-'*." .1.. 7 .'...-.. 4
Notification . *.. .'..,ป.... t. .-."....".'.. ,.. .6
HoldingISuei,'...........'.........,.,,....... .8
Caltoti.cป .-,''.'. ,.,.,.,...',......'.... ..-o,-,,,......9
!. ............................... r."....... 13
ICTtotetferacc Sample (ICS) ...........'....... 14 _
Laboratory Control (LCS) .......'.,...../..... 16'
Diqilirate Sampte Analysis ......" 17
Mabix Spite Analysis ...................... 18
Fttnrace Atomic. Absorption QC ..................... 20
ICP Dlution 21
Field Dinettes . . ................. ._ 22
Rqxffting Limit. Verification ........................ 23
Sample Paperwork *............................. 24
Tables
QC Checklist for Level Ml-CLP HAS TAL Inofganics 3
Tarfet Analyte Lis* Mrtds aad Action Lewis 7
Holding Time Summary ............................... (back)
CaMbtatioit Smansaiy (back)
Stannary of Spike Reccwery/Dupiicate'Tttecision ................ (back)
Summary of Dito Qu*Hfieซ .............................. (back)
Inorganic 'Regional Date Assessment ................. (back)
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Glossary of
Acronyms-
AA
,AOB
APO ". - '
'BPB . ;
,BNA ' ' '
CAM)
CCB ' .
CCS
CCV,
CP'
CtP'
CRDL
'
CSF
cv ' .
DAS
DFIPP
DPO
DQOs
DV
BCD
EICP
EMSL-LV
EPA
GC
GC/EC
GC/MS
GPC
HAZRAP
ICB
ICP
ICS
icv
IDL
IRDA
IS
LCS
_ ., 1
recovery -of of ', < J, _, .^, -. . v \ .
atDnuc ab*orptiDii-.,.-.. ' ivsv","" < '".; ^.so- -U,ASซC.I-!--*- - ', - "
:v: \v /
:..
SBC3 |
CoeffidซtofVantfioii
ft . ' " ' > * - . , " , ' V .A- ( I" ' .
delivery of laalytiai 'scsrvias . . , -'.". ',/-""-%~~rr
DecafliiorofcriptiaaylpliospMiie (semivolatie
deputy project officer
data quality objectives
data validation
electron-capture detector .
ion current profile
Enviionmentel Monitoring Suppoif Laboratory- las Vegas
United Environmental Protection Agency
gas chromatograpliy
gas chromatography/electron capture
gas chromatography/inass
gel Permeation Chromatography
Hazardous Waste Remedial Actions Program
initial calibration blank
inductively coupled plasma
interface check sample
initial calibration 'verification
instrument detection limits
Inorganic Regional Data Assessment
internal
library control sample *
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MCL
ml
"
m/z
MfflSA
mm
OABS,
,.
maximum cofltaminaticHi Emit
Method of Addition.
the of (m) to of by GC/MS
Naval and Support Activity
Institute of
'HAS-
-MC
KPD
KRF
RRT
ESD
RT
SAS
SDG
SMC
SMO
SOP
SOW
SVGA
TAL
TCL
TIC
THPH
TPO
VOA
* -ป : > W<*pฐt*ซปsii35*siซ **"- 'n-.'ซi
;.-
'
.
relative
retention time
special analytical
ddivay -groi^
monitoring
procedure
of work
semivolatile
list
compound list
tentatively compound
total petroleum hydrocarboiis
technical projซ;t officer
volatile organic anatytes
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Associated Any to a QC 'analysis,
For '
* - For ICV, all run under the
. calibration curve,
ป For RPD, aH SDO
distilled of the same matrix, ,
> '*'"'' f "*"
Curve ' , - : - .' A plot of of standards.
' ' ' ''- ^/:''vAfiiiI%^
a time^ipttlal fpr'-a|wticttkr site.
^
A Caป of one -of
GfOU$(s).-
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' . , . ..'. Appendix &; . ". r: :
VaUdation of.Volatile. Organic Anafyte Data
* Sobapgendlx'-A-i covers 3Lefel Ml ' .: -.
* SubapfMindix A-2 covers Le?dl M2
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no,: Ml-VGA
Revision: 1
1 of 18"
Appendix A*l
of
.. . ..Manual: Level-Ml /'- . ..''.
4^.^'fx^w" ^;< - ' -'''^f^^^^^^^f. " ''' ''" ".
,., . .
'vl.'\' This ias!tewtiiMis'^;naMiBly vafidite^^yotolile
';-. ' XVOA) tie nปlii"ifflwwi&re -at'-JLevdi Ml;"'
" b ' " >< ** ** B *^ ** ซ "" * Jt n,* t ^* * t ^ "fcซfc _^l>'t* s*V V B = '- ,
.'is laboratory
:;^.,.r^ซ;^,,:'-;^^^^^^^,i^-ccm^^^^ Q^ sow_
aBPL'S*^ ."S/i-f . f
-------
No.; Ml-VOA
ReYlsion; 1
2 of 1ft ^
* Table Ml-VOA-1
mi
'.' .-.. >:,~' '.-.
Action Levei^NotJ:
g -; ::':-:'
Staff
(161, MD)
Internal Standard Ares
field Blank
Manual
IVI2
:.-; .-ป,ป,
.X
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Procedure no.: MI-VGA"
Revision: 1
Date:
Page 3 of 18-
RepOTting requirements for Level Mi are:
ป Hand annotate .tiie Form. Psf including
Date validation cpjafifiefS
- ' Ifatifieation number
Sampling location ฐ
r(' i.e. , Ml . -
associated mtii analysis'- - / ' -'''
iP ", ' r ^ " . * " ' * -'
. -toclude ^*'ฃpnomi$ 'attachments ' ..-.-
" Xisf oฃ data validation qualifiers . - :- ""-.
" ' Support documentation inekiding forms that support assigaiug date
-,, cnialifien "- "''',-"" - . ,.-"-, ' -. :_- .
- Chain 'of =eistody form' ;- :\- ;
3.1 'Artiฉn Level Notifiiation/- ' - - ;..-".'*- \
* ' " - *" , "
The purpose behind action level notification is 'to mate the EPA Remedial Project Officer
' (RPM) or^tiie, Site Btojed Officer (SPO) aware of flic risk at the
site, fa with''tt|e'l^on;I!tt Harafdora Waste DivMon pฉHcyป the -EPA RPM
or SPO must be promptly notified of any contaminant exceeding the established action level
SPM :or_ SPQt Validation of the rest
of the data may thai be completed normally,
3.-1.1 Acceptance Criteria,
EPA's Office of Solid Waste and Emergency Response has established - 10-day health
'adwsory limits or the action for several "organic compounds and elements of special
health risk concern on the Safe Drinking Water Act, The volatile organic
compounds 'and their 10-day heaMi advisory limits are listed in Table Ml-VOA-2. The
criteria for action level notification are as follows:
The contaminant' concentration must be equal to or above the established 10-
day- health advisory limits.
* Data for contaminants exceeding the action levels mast be validated as a top
priority.
The following1 _ EPA personnel must be notified of the action level
exceedances;
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EPAlPMorSPO .
EPA Section CMefs: ' -
- -Site (SI)
'EPA
Procedure not: Mi-VGA
Revision: 1
4 of 18
' '- , JOA '' ;
\ ' , < ,
Hie data validation should be completed per normal procedures.
instructions from the Hazardous Waste 'DtvSsion -should be
followed,
Records should be ksept of the data review, action -level notification and any
folow-up instructions and actions.
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Procedure no.: MI-VGA
Revision: 1
Page 5 of 18-
" M1-Y0A-2
VGLATttJE AND
Compound
Action
Compound
Action
Lerd*
,Qnfaoa .
1,000
' cis-4 ,
'1,000
traas-1,2-
Diditewethyleiie
1,2-Didioropropne14^1,"^
Methyletliyl
(HER,
.ป -
5.7^00-
Tdiaw
Yinyl chloride
Xyfcnes
'7,800-
*AJ1 units are tig/L
3.1,2 Review
All data required to perform the complete Level Ml validation, as in the following
sections, are necessary for outlying out action level notification. The location of the
and their retrieval procedures are also discussed below.
3.1.3 Procedure
The evaluation preceding action level notification will primarily consist of
comparing the results on Form Fs with the levels in Table MI-VOA-2.
Following the identification of the contaminants the action levels,
validation should be performed using the criteria, and in the
appropriate sections bdow.
3.1.4
The action resulting from date ฅaMdation will be the notification of
to the to Section 3.1,1.
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Procedure no.: Ml-VOA
Revision: I
Date:
1 6 of 18
3.1.5 Meporting
Copies of Form I's can be used to highlight die contaminants above the action levels. The
findings of the focused validation can be summarized in a memorandum, and Hie data
qualifiers resulting from focused validation may be written on the Form I's. The
up forms should be clarified that they represent validation of only the contaminants
elir.aiil;tot:.all date. .'.' , " \ ' "-lซ;-.ซv " .
I The primary QC indicator Checked in Lewd Ml is the mass spectra for' die detected
conpoitina's. TMs"ind!cstaf*;^OTiis''to frraluatiiig a coinpoiniFs pooaซป'by*BBidMng its
mass spectrum with a stknd^!<&bwn) mass spectrum for the compoufld;.'':'N0" assessment
is made of the reportel. quantity of. the comporod or' -any. quantitative quality control'
indicators that could lead some'uiicertainty, to the reported value.
J.2.1
-The acoe|>tance criteria-IGnr ;ipป-;'Spediil mateMng we ;gwa/ln-ttie;;CIJ' -FiairticHffll
Guidelines and axe as'fbllpws:^ Vi'-^'' .. .' .-.,': '''"'/. '
* \ v ., ^
* All .-ions pnaeai'.in .the standard (known) ^^pcctaini at^a relative i
, greater ten 10 percent must be present in the sample
* Hie relative intensities of the quailymg ions (those above 10 percent relative
intensity), must be within +/-20 percent between the standard and
1 spectra, for example, an Ion with a relative abundance of 50 percent in Ac
. -standard _speetrum must be present between a relative abundance of 30 and
70 percent in the sample spectrum).
* Ions present in the sample above 10 percent relative abundance must be
accounted few. '
3,2.2 Review Items
Form I's for each field sample, field blanks,.and laboratory blanks included in a Sample
Delivery Group (SDG) are necessary to compile a Est of Ae detected compounds. Mass
spate are then necessary for of the detected compounds in a sample. The required
mass spectra include both the sample spectra as well as the standard spectra.
With respect to the blanks, it may be beneficial to evaluate the blanks before the sample
mass spectra are evaluated. If a compound is found to be a common contaminant, i.e., it
is- present in any one of the blanks and also in the sample, the concentration in the sample
should be evaluated with respect to the highest blank contemination using the 5 (or 10}
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Procedure no.; MI-VGA
: ' Revision: 1
. . Page 7 of 18'
times criteria before proceeding with the evaluations. Hie effort
required for the sample mass spectral evaluation- may be significantly reduced by
: performing the blank evaluation first -Hie mass spectra for the blanks; however, should be
evaluated to ensure that the contaminants were identified properly, '
All sample Form Fs are generally located together in front of the package. * Copies of
the Form Fs can , also be found in the by sample;
Le.f the Form I and its substantiating raw data for a sample are placed together. , The raw
-.data- indude^qi^^ in that
sample are. A stendaM (knowii) mass spectrum, and two sample mass spectra (one
unaltered and another background-subtracted) are generally provided. "The presentation of
the mass speOra differs for different instnimen^ manufacturers, tat information
for evaluating mass spectra Is .always provided in 'some form.' Hands-on with
different brandsi-rtfiki3^'^^^rometeป;;':altliซii^i",not essential,-; -'Cair be; in .
" tntetprcting the i
' '
'Copies -should be nade,_-ฉf;,te';,;l^i Psf .preferably from the summary data if
_ included. Otherwise, the forms can be pulled out from the raw data package. AM.
* should then "be highlighted with a marker or other convenient means. The, raw
should thai' 'be tagged -':'^;:;ev^: sample for evaluating- 'the -mass' spectra 'and the
chromatograms (recortstracted iohciurent profiles). ' ;
'3,2.1 Evaluation of Mass S^ectm : " *^-
Compare the highlighted Form Fs -with the raw data, . Verify that sample
results are present for all of the samples listed on the ehain-of-eustody form. Verify that
raw data are provided for every ample, and a Form I for every sample represented
by raw data. Verify on a sample-by-sample basis that spectra are provided for every
detected (highMghfced) comporal reported on the Form I*s. A verification should
then be.|erfomied that all target compounds for which mass spectra are provided are also
reported as detected on Form I's.
Mass spectral comparison routines based .on the evaluation criteria presented earlier
(presence of major ions and their relative intensifies) are built into the instrument software;
therefore, performed automatically, A listing of ions and their relative is not
produced; rather a score based on the extent of the fit of all criteria is produced. He
score is on a basis of 100 or 1000 for a perfect match of the presence of major ions
and their relative abundances. The score is printed on the quantitatioa report as a "q"
value. A upward of 60 percent of the maximum (upward of 60 or 6GG) is generally
considered acceptable for positive identification for a compound.
Visual comparison of a mass spectrum involves looking for the ion (the mass fragment
with the highest intensity), the parent ion (mass fragment equal to the molecular weight of
the compound) and other characteristic ions representing removal of one or more functional
-------
, , ' Procedure no.: Ml-VOA
- , Revision; 1
' . , Page 8 of 18
groups (such as -CH3f -CH2-ป -dป -OHf or a combination thereof) from the ton, the
Ion or other ions. Tfe removal of functional groups is often ^successive and
a fingerprint for a type of compound; i.e., straight-chain hydrocarbons produce a
characteristic envelope of .mass fragments by 14 units. Similarly, aromatic
compounds produce a peculiar fingerprint The base ion the
; fragment; therefore, it is always present However, a ion often is and may
not exist at all or may at a low, abundance or relative intensity. ':., ry.'. 1 , ..., . ~
"-. ,;-';' ';--v-V-"'';.- . , '.... ,,-';-: "''--: ;' -r";>i'^^yK.W?i-:*-.f ,
Compare the standard (known)mass spectrum with fee- sample
spectrum for the preface of the base; parent and other characteristic;, ions. Although
background-subtracted and unaltered spectra are generally provided, the former type
of spectra are much cleaner looking due to the subtraction of column bleed or other broad-
based interferences; therefore, better suited for comparison. Generallyy&e,.presence of
major ions and overall matching of the fingerprint-pattern between rthe^staDdard and the
sample spectra can be satisfactory. The comparison is rather: ^bjective^ and
a" '
Interference still may be present in a background-subtracted mass .spectrum due to co~.
etutmg compounds ( as compared to column bleed or broad-ba^d interferences), Unless *
the interfering compound is an isomer or an of the compound in question, the
fingerprint produced by the target compound and the interfering compounds can be quite
different. Inseparable isomers reflect a limitation of the gas chromatography without any
recourse, Such isomers axe reported as "total", for example, (combination of
ortfto-, taste- and pajta-xyloaes). Analogous compounds generally have different retention
times; therefore, may not be. of much concern, Thus, eo-etutittg eปmpouods do not
any problems to evaluating the spectra. . '
Seldom does a CLP laboratory incorrectly interpret a mass spectrum, but there is a
subjective element to. mass speettal mterpretation. While working within the CLP
guidelines, the laboratories do have their own reporting practices at' the limit of the
instrument's sensitivity. Most of the mass spectral identification problems occur the
limit of detection where the differences in the relative intensities are not easily discernible.
Special attention should be paid in evaluating mass spectra for compounds at low
concentrations. In addition, oxygenated compounds such, as acetone and 2-butanone
produce poor mass spectra. For such compounds, the standard spectrum may show the
presence of the parent ion,_ but the same may not be true of the sample spectrum.
'Professional judgment should be exercised in evaluating- such spectra.
Rearrangements and other side-reactions often occur inside a mass spectrometer. These
phenomena produce mass fragments that are not easily accountable from the staictore of
the parent compound.
-------
Procedore no.j- Ml-VOA
Revision: I
06/30/1995
9 of 18
Aclwn
"M the event the spectrum of a detected compound 'dew. not at all resemble the
, standard spectrum or has extremely poor matching, the 'compound should .be considered
undetected. In this the detected value should be changed to the CRDL for that ample
'and flagged as undetected, "if.".. jgjQfTB: This is -In, 'content to the B?A
Functional Guidelines which 'fecommsid rejection of data, R is felt that an outright
rejection of data is not justified. If the mass spectrum produced at a "target compound's
mt^^oa-^m& do^ n^m^^'th&'StmAsu^-s^&triim, a conclusion can be drawn that the
target compound is not present and the mass spectrum may be due to something else. In
such a the target compound should be considered as undetected and should mot be
rejected./ Mate are- that" Jte>jlittiet compound -in <|iiesticn.;daef--piodDW:ii-good
spectrum by inspecting the standard mass spectrum from the cah'bration and the fit score on
the quantitatioa report for.sthe^daily /or .continuing calibradon,^ Data ; for undetected
compounds ace usable for 'maiyjpurposes such as risk assessment; therefore, rejection of
data* is' not' beneficM to atproj^*':-The conflict of irapmper characterization should be
brought li^aMi^^ .':-, ,/
.If Is 'some evMmce-ฉ!' teimnpoand's (as deton^M,|iy,visBil matching of
the tee ion, parent ion and fingerprint pattern despite a poor fit score), the compound
should be considered tentatively identified. The reported value should not be altered In this
case; however, a data qualifier code, *"W\ should be appended to the data point-to denote
tentative identification; . . -' . . - C_-- ' ,
In both of the above eases* evaluation of additional information such as the retention time
and frequency of detection in other field samples is warranted. Previous site history is
an important evaluation; however, information essential to perform such an evaluation (in
contrast to 'validation*) may not be easily available to a date, validator. Nonetheless, it is
incumbent upon a date validator to mate appropriate recommendations to fee project
'manager or the remedM officer,
3.2.5 Reporting
The most convenient form of reporting the mass spectral evaluation is through a brief
memorandum to appropriate authorities. The highlighted Form Fs and the mass spectra in
question should be appended to the memorandum in support of tite conclusions. Also fill
out and attach the Mass Spectral Evaluation Form, as depicted in Table Ml-VOA-3, to the
report as a record of what was done. Record the date(s) of analyses. Field sample
numbers should be transcribed from the chain-of-custody in the Sample Identifier column.
Notations may be placed under the "MS" column for each sample to describe the mass
spectral evaluation. The following notations are suggested:
* X Acceptable miss spectrum,
-------
Procedure no.; Ml-VOA
Revision: 1
Bate; 06/30/1995
10 of 18
N Tentative identification. Partial proof of "a compound's but all
identification criteria not met. . .
U No mass spectral match. Using professional judgment, the compound is
considered undetected. ,. . ,, ' " '
" , ' " " \ , ~
' " 'f.' ' ซ " '" ' . - y "
RMo mass spectral match. Using professional judgment, the compound
'
3*3
-The purpose behind evaluating the chromatograms is to get an idea regarding potential
negatives, and- analytical errors. Checking for positive data as described under
spectral evaluation does not off er any insight intoxiata that, are not rqjortoi (i.e. j reported '
. at nondetects). - JUboralo%^rpr or gross interference from other compounds could be the
reasons for en^n&smT^^^ng. Tb& gas chromatograms or the reconstructed. ion current
' (RIG) profiles are the primary tools used for the false negative evaluation under Level Ml.
,
Thegte aw no'EPA-^ttMisbttt critocia for, evaliiaiBg ctoonatogwiis'-for negatives.
The criteria used for evaluating cftromatograms are based on good laboratory and scientific
practices, and these ate not tod and fast requirements. Hie suggested evaluation criteria
are:" .''-
* There should not be any significant peaks in the chromatograms that are not
accounted for as TCLs or TICs. Significant peaks ate those with a
minimum peak height of 10 percent of the closest internal standard,
The chromttogfams should ideally have base-Hue resolution between
adjacent peaks. Also, there should not be broad (unresolved) envelopes in
the chromatograms.
There should not be abrupt shifts in the baseline.
* There should not be peak tailing or sharp rise in the peak fronts.
-------
* Case No.:
. SDGNo.f
Data Reviewer:
Site:
Procedure No,: Ml-VQA
Revision; I
Date: 06/30/1995
Page 11'of 18
' Table Ml-VQA-3"
YGA EVALUATION SUMMARY'
, - Bates Analyzed;
* , *
>
SuB^^fg^f^n.
I
5r . ' .. -
a, - ,--
< - ' - -
fi l :..,-- ..ฃ
i ".--..- : :"-"
i ' " -. ' _'- .-. '''
.9-. . ; "'-' -V ; *-";*ป>'-
10'. ' "" ''- ''.-."',-, -i,
- V
OifonudiiM,- - ifi
Bcorootacaanc -
Vsnyi CJUorids (*)
Ofewitaw -
McJhytene Calends
AMIm -.' ' '
CaAoa Disal6de , " ~:
1.1-DfciilMMtfMi* - (*)
l,l-Dk&kucMlune (f)
1 ,2-E*jcliIo roeshe ne (told)
Chloroform
O
1,2-DfehkMotihiiie
i-BuUnone
1,1,1 -TrieU omethMe
Csrbon TeUachioridc
Bromodich!oromฃthane
l,24ปehlQR>propuซ {*)
eit-1 ,3-D!cMoropropene
Triehlotoethene
Dibrornochloromethane
I , i ,2-Trichtoroeihmc
Benzene
AR
tnns-1 ,3-DichIorspropene
BfOfnoform (f)
4-Mrthyl-2-Penunone
2-Hexซnone _
Teltachtoioelhen*
1,1,2,2-Tetnehloroclliine (*)
Toluene i
*){AR)
Chlotobenzene (#}(AR)
Elhylbcnzcne i
Styrene
Xyknes (tote!)
*>(AR)
(AR)
(AR)
t- - - - -
-*- --- - --
* -- - ^ - -
*-.- - -.-.
t -',-.. .' . : , .- *-+--. -.'-i*y. .sSft::: ?>. -.-
-T-- -. ,' " ' " " : -; ./: - - -: --; -, ',
'i, '-;.--.' ซ . .--. -. {:;- f
.%'" ::>, -ป"...- ,- i . - . -.. . ----,/.:'.'':-:'.,.-
m:^j^^:". . .-:.--. -t..> TV-. ;.-; -
* !'
MS
ET^
;: - jjv.^-
MS
,'":>
't
ปf
V'ป
". -!"
. .*
^c
. \
. '
.
T^'^
MS
-&i
'db
--*.
-,-,ป
*
RT
%-ฃ
"""; '-
---,.;.
-
'
i^4^'-
MS
*v.ป
- -.'-(
r -
'.
JEf
'.**''
ซ -
'I-*. :
MS
W
-. :
<- ..
MS
ซf'
'
\ป'-:
MS
" , ,
RT
' * *
'.,-
-
i
-/KS.V-'
MS
-, .*;
' ';,*,
, -_;..
">
.v.
. ~~
.-
-
,kr
v-;
-'-,.-
.-. >
'- 'v.
--i
"~- ,-
..
y 9' ' '
MS
;;'*'.
ป;..,;
>.,
J, .
1
t
Kf
\'<
"_r "
''ป
MS
- -
ET
-------
Procedure no.: Mi-VOA
Revision: 1
06/30/1995"
12 of 18
3.3.2 Review Items
Qiromatograms, or the MC, profiles far each sample are necessary for the evaluation. The
WC profiles 4ean be found in the front of the' raw data for _ sample.' -The
quantitation report for each sample Is also necessary to retrieve dither the retention times or,
information regarding <$oui numbers to compare with the peaks on the chromatograms.
-.3.3.3..
. . .
VisuaUy;ta3pect.t^.c^ that appear" to be'at;linsfcl6-pefceat in
height of the nearest internal standard, ' Compart that the scan number dr the retention time
that iqppeaxs CM (jbe'^ods'of ^IJUC profile with feat listed on ttHป;quahtitation report far
'the TQLs or' the'-lbtwyvsai^'-iw^ for the-TICs/ Mite '
ate accounted -ibr. -.- ป-'&fti&*,r.-' .. , . '/
.
Also obซave theMC.ptott=ttf"Iw*:-i!eปlBtion be(weeasa4Jai^.pefliiEi.>*vPoor peak-to^"
peak resolution Is indicative of degrading performance of the gas chromatographic column.
The -values obtained froni-,a3^padirig 'system "are" prone to be inamuate. Obviously \
certain isomerie or homologous compounds are difficult to separate. % But generally, there -
should'-femt lซt 90 perc^ " ,.."
"' ' ',' :;V ,. -.' ' . '' '
\ ' , :
. .Inspect Ae WC profile for broad, uniesohred mvdqpes. These axe geaearally indicative of
outside' mterference firom' .a of homologous compounds" such a^stralght-chaih
hydroaAons. Especially, ijbie intexference with the internal standaxds-and surrogates
under the envelope using the area counts. The standard values that are for from
the expected values may be indicative of potential problems with the TCL delation or
quantification.
Inspect the RIC' profile for abrupt shifts in the baseline. Such shifts are indicative of
problems with instalment sensitivity or leakage in the system. The counts obtained
from shifted baseline are inaccurate, or even the detection of a TCL at low concentration
may be missed. .
. Rapid peak rising or peak tailing indicate problems with the gas chromatogrpphic column,
such as depleted stationaiy phase on the column, decomposition of the stationary phase or
creation of active sites. Again, a visual inspection of the RIC' profile will yield information
on the shape of the peak.
3.3.4 Action
Professional discretion must be used when evaluating and qualifying data based on the
chromatographic evaluations. An experienced chemist can generally infer the magnitude
and the frequency of the problem from the RIC profile. If the problem appears to be
-------
Procedure no.: MI-VGA
, Revision; 1
Date 06/30/1995
Page 13 of IS
systematic,* thai .it. should be brought to the laboratories attention and resolved.
Intermittent problems nay or may not require any action. The- foicrraig jpudeines are
suggested when acting on RIC profile observations: ' ' .
* Any unaccounted TCL peak with area equivalent 'to or greater than the
lowest 'reportabie fiinit for the sample mist be bitMight.-.tp''tfae -laboratory's
" ' attention and resolved. ; Any unaccounted n6n-TCIM^|^pG) peak with an
'ana ^poal"*'|&;-d^"^i3rator" than"'. 10 percent MM^dฃ-tJi^^^^^%ite^il standard
must also he r&solved wi^ ^ percent
oM protocols.
cannot be r^^v^Sl^fe'flabNaaalory, tfie
and brought to^AซJ^ปtaoi:;Qf ,tfce CLP-
TPO; .'t&^Maatt litosiit- The data' for IlECs- nay .be
" omtadtt^'toK^l^uaiSl.the proHems "ace "'
' H! a',podk'-Jwdltttซ problem is evident for
^steradfc:'il.e./^ปoซat'in aU caibiation,
samples and mcreasmg as tie ran progresses), additioni;;QC^measures such.
as ittie^wntiflnii^^ailibmfioii'per^ and
' '/sMiiqgate'istaiid^
eyaluated to' determine if the peak resolution problem could affect detection
^ or quantification. If determined so, the positive-data may be qualified as
estimated, :"J," Negatwe date may also be.qnaOfied w;ซtiaiatedป **UJ** If
the ability to detect at low concentrations is also -"deemed faTbe jeopardized
by poor resolution of adjacent peaks.
* Broad envelopes of homologous compounds could interfere with
quantification "or even detection. If the toterferenee is evident -from the
recoveries of the internal and surrogate in the vicinity of the
envelope, 'associated compounds may also be with., Using
professional discretion, the positive and nqgafive date may be considered as
estimated, "J" and **UJ*% respectively. If the project'objectives cannot be
met with fee estimated data, alternative sample preparation and cleanup
procedures may need to be developed and specified. The recommended
solution should be brought to the attention of the MPM, the SM and the
TPO.
, Discrete shifts in the baseline in the middle of a run are indicative of
intermittent problems. If the shift is due to or change in the system
pressure, the positive as well as negative date may be considered estimated
(*T* and C*UJ," respectively). The problem could also be due to
fluctuation in the instrument electronics which may to drastic changes in
the sensitivity of the instrument to detect the compounds. As a' note,
professional judgment should be exercised in determining the severity of the
-------
'' , ' < Procedure no.: Ml-YGA
Revision: 1
Page 14 of IS
problem. For example, the magnitude of a drop in .fee baseline below the
zero Une may-not be estimated and could be very significant On the other
bandr' a drop that yields a baseline still above zero can be put in a
perspective with the original baseline and a of the entire
RIC profile. *"",.. ' ;
* The problems with peak symmetry are indicative of degradation, and
shoidd ;b|fefo^^ to the attention of the laboratory for a corrective action.
.i^ould. be used when and if qualifying any data due to
i^lli^te; > First the problem should be defined in terms of
hout the chromatogram and ate from sample to sample.
-shapes and counts for the internal anil surrogate
to see if the problem could have
:and/or quantification. -, Data qualification may. be
counts are acceptable. ' , .
3.3.5-
,..
The-Mass, Spte*dl-iBra|^^w^ni;CM>le Ml-VOA-3) 'presented earlier'may be used- to"
note, any 'brief otimnieii^litt'i^^^oniMo^pMc evaluations.' The comments may be noted
each sample'identifiet.v For more descriptive comments, a separate may be
used. ' - '-'. >'*:' HX ; - .'- '
"i/--.- v
3.4 EvaSiiation of Retention Times
WMle not unequivocal in identifying a compound, the retention times are quite helpful in
con&fming the presence of'a detected compound. Matching of spectrum and
retention time of sample with those of a standard yields Hghef credibility and confidence
level to the-detection in the sample. On the other hand, not matching the retention time
may or may not invalidate 'the detection. If a mass spectral match is made beyond any
doubt, poor matching of the retention time may not have adverse impact on the detection.
If mass spectral matching is unacceptable or only partial, and the times do not
match, then a strong doubt can be cast on a compound's presence.
3.4.1 Acceptance Criteria
The criteria for retention times are specified in the EPA's functional guidelines as follows:
The relative retention times (KRTs) must be within Hh'/-Q.06 RRT units of
the appicable internal standard RRT,
-------
Procedure IKK: Ml-VOA
Revision: 1
Date; 06/30/1995
Page 15 of 18-
3.4.2 Review Items
Qutntitation reports for'the'ample and continuing calibration are required for the
evaluation. These are located in the raw data for samples and standards.- A copy of the
continuing calibration quantitation reports may be made or the reports pulled out from the
raw data, to facilitate a comparison with the sample quantitation reports.' -
3.43 Brottf , ,- ',.ฃ'\--:>.l'4*';"r
For the detected compounds,; determine the relative retention tme.fo*-Ae;tt>nqปinids by
dividing Aeir retention times 'with the'tetention time of their'associated infernal standard in
the samples as well as in fie applicable continuing (or initial) calibrations, lie sample
KRTs must fidl'in range 'afjttidud RRT'+/- .0.06.units. - V -' ,
*ป*,ซ s ป, , ,, (gk*" " "',' t ^J>*'1"< '^S*J8*tf*-' '"
3,4.4 Action -. " -;':"(""'\>;^T-; '. " "
Action for retention time evaluation requires professional discretion. Action taken must be
based on- other data such as mass spectra and not on retention times alone. The following
actions are suggested 'for several potential situations. ' :
* ^ Accxpteble matcMiig of the mass spectra and*'tht" feNo ซtion-
' ' suggested; _ ' . ''.;''.''.,'
f ' : .
ซ " Acceptable mateMng of the mass spectra, but poor .matcMng of the IRTs
No' action suggested, but the cause of retention shift may be
investigated. Check to see If similar discrepancies ne observed in other
parts of the chromatogram. Often high concentration of a compound will
cause shite in the retention times for other compounds in the neaAy dating
region, but m retention times in other areas may not be observed.
Shifts aH through the chromatogram may be indicative of an erratic system,
such as flow rate fluctuations,* poor temperature regulation, restriction or
leakage in the system. There are likely chances that the sample -rallies in
such conditions may be inaccurate. Positive data may be qualified as
estimated, "I/* if deemed essential. l
3.4.5 Reporting
The Ml-VOA-MS Form (Table Ml-VOA-3) presented earlier may be to record any
problems in the RRT matching. For the detected compounds In sample, the calculated
RRTs may be recorded under the '"RT" column. A data'qualifier cole may be added to
the values exceeding 0,06 RRT and requiring qualification, such as "O.I5J," for a
compound with a difference of 0.15 RRT units and where a professional judgment to
estimate the data is" exercised.
-------
no.: Mi-VOA
Revision; 1
16 of 18
3.5 Evaluation of Blanks
Laboratory blanks and field blanks have a profound impact on false (post,tives reported in'
samples; i.e., compounds reported as positive detects but not originating from the samples
themselves. Cross contaiiiflatiofl from the sampling equipment, incidental contamination
from the fidd oondi^ui^\or^ooatainination from the laboratory .equipment or. general
of Mbe positives in the sampfes.', "..-,.*
3,5. 1
... ; , , ,
Criteria for blank evaluation 'are specified in the EPA's functional guidelines. In addition,
Region in has some additional requirements modifying the guidance. The acceptance
criteria, for .blanks qgdyAeqiially '.to any- typฎ of blanks associated' with ..either sampling .or
analysis, such as trip blankss rinsate blanks, field-of bottle blanks, and laboratory method
blanks, ' While there are several criteria for evaluating the blanks, the only criterion
applicable to Level Ml is the comparison of the blank and concentrations. This
criterion is: " ' : -.;?(.' '''?..*' 4;i .'/'.
, , n i " .''"'' ฐ
;'-.!;-':,"*:>y-fe'' ;" ' '
For common contaminants, such as methylene chloride, and
2-bwtanonef ' tte .sample a>ncentotioB" must. be nummally 10 tines "the blank
concentration to be considered a positive detect. Other contaminants must -
be present in fee sapipte "tt or above 5 times the blank concentration. The ,
blank with the highest .concentration must be used (this is, if fee laboratory
blank has the highest conceatration of methylene chloride, and'the equipment
rinsate blank has the highest concentration of acetone, both of these blanks
must be used to qualify the respective contaminants), AM blanks should be
checked and the highest concentration of contaminants in any blank should
be used for data qualification.
3.5.2 Review Items . "
Data requirements and data retrieval procedures for blanks are the as those for the
field samples because the Hanks as well as field samples are validated similarly. Form 1's,
mass spectra, chromatograms, quantitation reports, etc., are essential for performing a
validation of the blanks first
3.5.3 Evaluation Procedure
Validate the blanks the same as the field samples, detailed validation procedures are
described above under appropriate sections. Use the .validated blank results for a
comparison with the sample results. Make certain that the samples and blanks are
evaluated on the same basis of sample weight or volume, dilution factors, moisture content,
etc. Use the 5 (or 10) times the highest blank concentrations for qualifying the sample
data.
-------
Procedure ao,: Mi-VGA
Revision: 1
Bate: CM/30/1995
Page 17 of m
3.5.4 Aetmn
If -the sample concentrations' do not meet the criteria of 5 (or 10) -times the blank
concentration, the sample should be undetected (or as not
detected substantially above te--tevels reported in the blanks); therefore,-flagged *'B" in
accordance with the legion m data validation guidelines. '',,-,_-
3,5,5
Form I*s may be use4 -fij:wrife'''tiie "Bir data qualifier'for the.ddte"nซv^i^ittg'the blank.
'Criteria,.
3,6 .Sample
. The purpose for evaluating the 'ample paperwork is to determine that the samples being'
validated are indeed the ones taken from the site, and have not been tampered with.
'Accurate sample identity is of paramount importance in substantiating'the sample data.
Without unequivocal sample identity and chain-of-custody procedures, the sample data may
not be defensible or.fflforoable., , * * ' ",... ' -/rr^^': :- ' ' "
Under the current'CIf-''contiaclsf the original paperwork (Le., the-purge ."iaciage or the
administrative record) is included in the data from the laboratory. It is
that 'the date validator is not privy to the original paperwork; therefoi^r-tiie "evaluation
criteria and procedures described below apply only to the documents that are generally
included in the date validation package. These documents are the chain-of-custody forms
and Region ffl Shipping Record.
3.6.1 Acceptance Criteria . .
Criteria for acceptability or authenticity of the sampling paperwork, document control and
chain-of-custody have been established by the* National Enforcement Investigations Center
(NEIC), in support of the CLP. Overall criteria are too numerous and subjective to be
'discussed here, but the criteria that apply to data validation are as follows;
* The chain-of-custody form should be properly and completely filled out
including the sampler signatures, date and time of sampling, sampling
identification, analyses requested, traffic numbers, tag numbers, etc. These
are minimally required to confirm the authenticity of the sample and its
data.
The chain-of-custody must be maintained at all times. The custody transfers
between different parties must fie signed and dated.
-------
Procedure no,: HI-VGA
Heroics: 1
18 of 18
3.6.2
A copy of the ctak-of-custody form to the identity of the In
addition, the HI is to the QC Hie
chains-custody and are in of die
3,4 3 ' ='" . . '
that . the chau^c Ac and a. _ time
and Hie laboratory of the.
most have the of.^labobuazy custodian. Any on tite form
outv^'.'i:ibtgle line.thrpngh the' entry. Verify aH
have' unique station identification, traffic numbers and tag
that the Region IH Shipping'.Record the cm the
ofcBStody. . i ' -.' - ''
' ' '"'' '
. . ...
action to be in qualifying the data, is highly on. the of the
'problem. Some to ptporwoiSc.Me practically in real An
should be to reconcile the by the
the papqrwork.; ' Occasionally, tite to (he
of-custody; however, fee ^fidd-'notAcxiks may amply _flie event.
BxAlems are also* inevitable in or fag and
numbers. _ Goieraly, are of to or
refute the problem,
3.6.5
Any discrepancies found in the paperwork most be immediately brought to the of
the EPA RPM or SPG. Clearly define the problems in, a memorandum to the responsible
parties. Attach marked of the chak-of-eustedy forms to the findings.
-------
Procedure No.: M2-VGA
Revision:, 1
Date; 06730/1995
Page 1 of 34:.
Appendk A-2 -
VaMdatlon of Volatie Organic Analyte Data
/... Manual Ltevcd M2 '
'" * ' " ifi" < * * 11 ' '
... "; "" .,.'"'...','v;.(.-.
,, " ft'v -.'7/' '^^^If^^^f'J'Si^:-^-i
.^ta ' ".\ ,.,- /i,.^^,/'"-'^'^?t4&^ซ^^|^**ii^/;,:v
Ttefproooliife' propdtt itep-bjNttep mstroctionir tbTtoaiHiailyAW^ -'
analyte-.CVOApdata using ^e'.mmiHl ianofalive date -wlidttipn'
This ffliprowA focuses tjp""flM! tucซ..ojf infi]inQ32UHi oontsuicfl on.the
of dMOTttografiir'a^ .The"_
modifications to Regions IH's'National Functional Guidelmes for ^^C^
. ,
The procedure is appHcable torthe VOA data obtained
Jftogoaa Sb^ement of -Work (O^^SOW). ;.HaM"copy cfatt
* roeofiซioiป ate "osoitial" 'in "ofidor,' tQ .cany 'out the pnxxdme. _
- -. . " ., '' ฐ ' . ^ "'*
. . . . .,
Data validated using this procedure are considered usable for the following types of
. proposes; however, the- data -. must on ' a ose-by-case ;baas . whe^ica- 'the
piปccdiiiปisTOtablefor'ffidr";totodeddMaiises. The suggested data uses1 at: : ' ;,
* Oversight, of 'activities led by other parties "-'. '..'
* Comparison to action levels'
* InitiEd site investigation ' ~"
*
* Contamination sources
* Nature and extent of contamination
ป Preliminary risk assessment
* Risk assessment with known -high levels of toxics
Feasibility study
Preliminary design
* Treatability study
* Initial cleanup verification
-------
No.:' M2-VOA
Revision No.: 1
2 of 34:
M2-VOA-1
M2
CLP MAS
-"
' Actioa Lewi
WlM-CaitatiM
Ccwtinaijig G&bMtion
Laboratory Blaak
Internal Standard Area
Field Blank
Sample Paperwork
Holding Time
Retention Time
Surrogate Recovery
Dilution Factor
Moisture Content
Mass Spectra
Chromatograms
Raw Data
iV.,' "
'
X
X
Manual
X
X
X
X'
X
.MS
X
X
X'
X
X
X
X
X
X
X
X
X
Combined
,1
X
X
X
X
X
x
x
X
X
'x
X
X
X
X
X
X
-------
Procedure No.: M2-VOA
I
Page3 of 34.
2, Quality Control
M2-VOA-1 Ae (QC) this date
vaMdatioa procedure. . " .
: . -
He following of the QC the
and data, of the QC in the
the QC
a
the QC and of the QC in
_
Hie are listed Wow:
3,1 '
3.2 TecMeall
*.-"'**.
3.3'
3.4 ;;:-
^3.5 . Contiimiiig (CCS)
3.6 ' '
3.7 System Monitoring Compounds (CCS)
3,8
3.9 Internal
3, 10 Reported Contract Required Quantitation Limits (CRQLs)
3.11 Tentatively Identified Compounds
Two forms have teen deฅel0ped to in the performance and documentation of
implementing Level M2, The first form, M2-VOA-QUAL, holding time,
calibrations, blanls, -surrogates, and standards. The form, M2-Y0A-SPK,
summarizes surrogate and matrix quality control checks. These forms are
in Table M2-VOA-2 and Mf -VGA-3, -
-------
Procedure No.:' M2-VOA
levMoa: I
4 of 34
Reporting- for Levd 1C are:
* Hand annotate the Form Fa, includrng
Data validation qualifiers
raunber
A.statemmttiml defines the levd of the review, ie.
T->Vfr3?3!7i* '.'.V - , . v .-'"
Majoฃ jfjoajunor probteDas-assoaalM with' the tnjulysB' v
" "" ปthat may hive
, .
i^^f^M%aiiiaticป q . , . -.,.,', ;>;'..;...,' ,
Support' doc:umentation .includi,ng forms that support
'
Samples affected by calibration should be on the *
''
. _
The data quaHfios m ttris are as fottows:
Codes Relation to . Idktaodtificatlon -(Confidoice concemkg ~dr of
compounds)
U ' ป Not detected. He associated number indicates
to be detected,
(NO CODE) = Confirmed 'identification.
B. = . Not detected" substantially above the levd reported in laboratory or
field blanks.
R = Unreliable result. Analyte may or may not be in the sample.
Supporting necessary to confirm result,
N = Tentative identification. Consider present. Special methods may be
needed to confirm its presence or in Mure sampling efforts.
-------
Case No.:
Fncedme No.: M2-ฅOA
SDGNo.:
Date Reviewer:
Site:
TsMeM3-VOA-2. VQA Qnali*r fcMiwy CCdftntiMi, NMn, Ufag Ita* Surrogates, Is&
Swnptes Analysed Within 12 Hours of
Tune? Yes No
lซ*mซซti ID-
TuaeOK? YM No
Biliiiii&^l MIftilic ffi0*
^
CoatpMMti , SPCC (#)
. . . cccw
tthmfflfi*Wft JdL
Chlotocthsoe
MlAftafCMisitt
JteffPPl
Oaffefti IMfllSdlii
]UIJS*hw*ซnป ***
I 1-BtttarfhiiM _ML
] ,2-I>ich)oixKAens ftotaD
CMiMotmn " f*}
HifrlXfAtapiAmA,
2-lhUMMMMI
! 4 ,1 -TrichloKKthatw
Ca*<ปT8ffปiAlpซMf
J3romodich!oromsthait<;
1 ZrWditamiKMMiis^ f*4
el*-i 3-DfcUซซปwoeaซ
ItidilaB^KW
Ditromochlorotneiisane
1 1-2-MfillaiwSHBf
Befnsซaป x AR
taunt-! 3-ปWซซปKwene
Brotwปfoiป (i)
.iJAdffl^fWtHMW-
.MtaaaoM
TetmuyซwAHs
I 1 2i-TB|ซ4AifoAin* rซ
Tolueae f*VAW
ttIซ*ftซBiie ' IfiCARl
BllvfcซlH!Wป " 'jCtfARi
StvmM CAP)
Xvlenes ("totan .(AS)
Sscuple Identifier:
i
2.
Ill
4r . .,,. ...... ., __ ..
f . . jrl . ..-,-,,
6. "
7 ,
,ft ,u nn, , -i, -, -,-,-,-
9. ' .
JO,
, .. Time:
' UWCA
MFB
litzvift
S2
"*
JS
S3
Blanks '
MaSh Tv4o
xfiwGwu Jli^p
.
-
ISTDs
JSI Kl
" i*
ซ . ' "
,
m
OoaSS^
c+'ป
1 J. **
. '
.1
s
f
i
i
s
*
2
1
S
1
3
Rqsorted ซs: RT fttSSi.K^U
TlCs Bqmited fa Blank(s):
-------
No.:,
SDG No,:.
Data Reviewer:
, Site:
Procatee No,: 1C-VGA
, Revision: 1
Page 6 of 34
VOA
I Mattfe Sfiks QaaBty Cfifflto>! SซB3OTUuy
Sample Identifier.
(Acceptance Range, XR):
1.
i. '...,..
-3.
4.
5. .,
.*..
1,
8.
ป.
10. -
11. " .
12.
13.
AqMonSMWteftmmiiM. %H
SI
1*410
"( ,
*;. *,
f
sz
ซM15
'- " ,
ซ "
S3 " '
7*414
Son Ssmp !c Recovery, % R
SI
84-138
\
82
sww .
S3
70-iai
>
Qusiifiers (+/-}
-
SI M
, S2 >ป
SPCCf)
CCCf)
Sjakซ Compoimd Aromatk (AR)
Mainhf SflrikB. BRr/jirffrv ซ,H
BMie ,
Aetoa!
MASris Sjato 3>sipScซte,
ltllKS8WI8*3f t %M
IMP
Aetaal
MSflMBD IhndUM, WTO
Raage
- AGtajJ
QoaKfim
!+/-)
AQUEOUS SAMPLES
I,l-Dichloroซtiienc (*)
TticUomdhMM
Bซn7,ens AR
TohMtw CXAR)
Chloroheruenc (ff)(AR|
61-14$
7'wao
7Wป
, 76-125
7S-130
ซM45
7M20
76-12?,
76-lJS
75-130
14
14
11
13
13
SOE.-SAMPL1S
Ifl-Diซhteปซfceซป f*J_
Trichlorocthcnc
Bcnzsus AR
TotaMW WAKL
ea*>ซfeซiซปoe (I){AR)
SM72
62-137
66-142
S9-139
60-m
59-172
62-137
66-141
5Wป
60-133
22
24
21
21
21
%
-------
No.; AC-VGA
Revision: 1
7 of 34.
Codes Related to Quantitattoii (Can be for tปth positive and
quantitetion limits):
J = Analyte value may not be or
K ' ซ AiMy* pett. Iqjoi^' value raif be UiiAibijli.''.' Actual value
...-"
^ 'St\f''*^f SMฃ' " ! .
" ""' ' ''"' '^ fjSsjjv 'p| . - ^ 'St\f''*f M' " .
AMyte fttssenC" value is
' " ' "'t:""
Oilier Codes
UJ = Not.'drtH^^^filaticttliiiiitinay be inao^pte of/la^ปcaซ.
Q * No analytical;.iesu!t .. " \ .-;'.'"^ >.'-'"''
1 * - from'iiatttrf / ', :,'
3.1 Leฅel . ^
Hie purpose action level notification is to tie EPA Project Officer
(1PM) or the Site Project Officer (SPO) of the risk at the
site. In accordance with the ffl Hazardous.Waste Division policy, the EPA RPM
or SPO must be promptly of any ftc
or the i(Way health aciviปry limit. IbejiajajEEO^
must be validated .as a top priority :^n
-------
Procedure Net.:
Revision: 1
8 of 34
Data for the lewis must be validated as a top
priority.
* 4
The foiowmg, EPA must be of the level
exceedances:
Cation (SI)
The remaining date vafidatioa should .be completed per procedures.
*
Any mstruetkwis from the Hazardous Waste Division' should be
followed.
Reconds should be kept of the review, action level notification and any
follow up and actions,.
-------
Procedure No.: M2-VOA
' Revision: 1
.'
' 'Age 9 of 34'
. M2- VO A-4 - " '
-CompouBil.
'.Action
c-"-
Benzene
.Gabon'
Cttorobenzeae
000
ปWW
ttans-1,2- 1 -.
DleUoroefhyleae
''
*
jf
BfliylbauEeae/
Metfaytethyi ''-.
"
,
7,500
Tetrtdhloroetliylwe
l,l,l-lticUart>ethane
Vinyl ,
Xyleaes
7,800
*All uoits are tig/1.
3,1.2 Review
All data required to' perform the complete Levd M2 validation, as in the folowifig
are for canying out level notification. He location of the
and their retrieval procedures arc also below,
3.1,3 ProceAtre
The evaluation preceding action level notification will primarily consist of
comparing the results on Form Fs with the action levels in Table M2-VOA-4.
Following the identification of the contaminants the action levels,
validation should be performed using the criteria, and in the
appropriate sections below.
3.2.4
The action resulting from data validation will be the of
to the identified above in Section 3.1.1.
-------
Procedure No.: AG-VOA
Revision: 1
06/30/1995
Page 10 of 34
3,1,5 Reporting . . '
Copies of Form Fs can be used to highlight the contaminants above the action levels. The
findings of-the' focused validation can be summarized in a memorandum, and -the data
qualifiers i^ulting, Iromvfocu^lralidation may be written on the Form J*ii, Hie marled
op forms should "be :-cla|fi^^^jthey: represent validatioa of only the contaminants
3.2 Teclinkal Ho!
The objective is to a
from time of oollectiojtt'-l
'TOM*
'
3.2,1
Technical requirements
matrices. T!ie holding, 1
oily wastes, 'and sludge): ai
'time will be applied to a
established and. available, the
ty of results based on the, holding time of the sample
ซ
ing times have only been established for' water
. (and other non-aqueous matrices such as soiiments,,
yimder investigation.' In -Region II1S a 14 day holding
' """*samples. When sol. holding time"criteria tie
.for qualifying scil' samples win be re-evaluated.
TTie holding time oiteria for water Camples, as stated in the current
(dean Water Act) .is as follows:" "
" Part 136
For non-aromatic, volatile compounds in cooled (@ 4ฐC) samples, the
maximum holding time is 14 days from sample collection.
1,
Maximum holdkg times for purgeable aromatic hydrocarbons in cooled (@ 4*C ฑ,
2*C), acid-preserved" ^>H 2 or Wow) water samples are 14 days from '
collection.
Water samples that have not been maintained at 4*C (ฑ 2ฐC) and/or preserved to a
pH of 2 or below should be analyzed witMn 7 days from sample collection. If
insufficient ice' is used to ship samples, the laboratory may receive samples with no
ice left in the cooler,. Under these circumstances, the- temperature of the samples
may exceed 4ฐC.
It is further required that volatile compounds in properly preserved non-aqueous samples be
analyzed within 14 days of sample collection for aH volatile compounds.
3.2.2 Review Items
Form I VOA, EPA Sample shipping log and/or chain-of-custody.
-------
noceduze No.: M2-VOA
Revision: 1
Page 11 of 34-
3.1.3
Technical ate. by comparing the on
the BPA Traffic Report'with of ซ,i%fBi"r Y0A
the sample "records t0 if it Is
with the ^-ซ-**ปsaaSK^> -. -
may- an.d Jr
" *
i"'<*;^te^fซ<;^pf'* ,-ปf ^ c '
J,2.ฅ ':' 7
All Aromatics*
None
None
14 Days
All Compounds
AE Compounds
AH Compounds
*Reviewer should use professional judgment to determine if for additional
compounds require qualification.
2. If technical holding times arc grossly (e.g.-, by two the
required time for rolafiles) either on the first analysis or upon re-analysis, the
reviewer must use professional judgment to determine the of the and
the of additional on the results. Should the reviewer
that qualification is compounds
-------
Procedure No,: M2-VOA
. Revision: f
Date:
Page 12 of 34
may be qualified, unusable (R). Positive results are considered bias low and are
with VL". ' ' .
3, ~ When there ate other quality control problems in conjunction with' exceeded holding
; . limes (such as;.suspwted--(M>OEatory contamination), the reviewer should follow the
, _ Werarchy;of^qual|fi^J|^;,particular, If 'for any reas ^TTT- ^ , . . * - . .ป, ซ ซ- ,- . w '- -
degree, sensitivity/ :'Tliese--OTteria"' are not sample specific, Conformance is determined
using standard materials, therefore, these criteria should be. met M' Ml circumstances.
"' '.'. ''';::: ' 'ฃ''?':-..'". ' ' ' \ : ' .'.'''
33.1' Acceptemce "Criteria " -: .- , ."'**:^ . ''
The analysis of the instrument performance check solution most be performed at the
beginning of each 12-hour 'period during which samples or standards as analyzed. The
instrument performance check, bnrniofluorojbenzene' (BPB) for volatile analysis, must meet
the ion abundance criteria given below.
Bromofluorobenzene (BFB)
m/z Ion Abundance Criteria
50 8.0 - 40.0% of m/z 95
75 30.0 - 66.0% of m/z 95
95 Base peak, 100% relative abundance
96 .5.0-.9.0%ofin/z9S
173 Less than 2.0% of m/z 174
174 50.0 -120.0% of m/z 95
175 4.0 - 9,0% of mass 174
176 -93.0 - 101,0% of m/z 174
177 -5.0 -9.0% of m/z 176
-------
Procedure No.: M2-VQA
Revision; 1
' 13 of 34 -
* * , "
NOTE:' All ion abundances must be normalized to m/z 95, the nominal peak,
" even though, the Ion abundance of m/z 174 may be up to 120 percent that of
m/z 95. ' - '--.--
3.3.2 Review^Item
FormVVOAf ,.,-;!:'ซ
'3.3,3 EvalMfamJ'mcii
=.,.' ,j! - , , . v., ,
Compare f^.d^/preKoted' fttt ซch Instrument _' C3iซk
VGA) 'with ซ^^inass?T^g;:iwbinittซI to the, '
- --' - - ป>-'
-Fcปin; Y.r,ฅOA-M:iMPeปnt and completed for eadr 12-notff^teM during
',-^**:;I',W'ซ>-WA , -- * .- . .-.<**ซ.ซซ^^- -
samples .-were-, analyzed.- " - '-
""r "*' :' "'- ' " " "
The appropriate nufliber of significant figures has been rqx>rted (number of
significant figures'given for each ion in the ion abimdanc^ Mteria colymnj
and that .rounding 'is- eoneet (See SOW for requirements)^";?...':',
2. Verify- that Ite'mass-assignment is csoneet and feat the fisting Is'ironiialized to
m/z 95. '.'-''".' - '" -^
3. Verify that the ion abmndanป criteria was met. The criteria far m/z 173, 176, and
177 are calculated by normalMng to the specified m/z.
yOpTEi , AM instalment conditions must be identical to muse used in the sample
analysis.
'3.3.4 Action.
-L If the laboratory has made minor transcription errors which do not significantly
affect the data, 'the date reviewer should make the necessary corrections on a copy
of the form.
2. If the laboratory has failed to provide the correct forms or has made significant
transcription or calcuktion errors, the Region's designated should
contact the laboratory and request corrected data. If the information is not available
then the reviewer must use professional judgment to the data. This should be
noted on the O1DAS form.
-------
Procedure Noซ: M2-VQA
' Revision: 1
" 14 of 34
3. If mass assignment is in error (such as m/z 96 is indicated as the base peak rather
" than m/z 95), classify all associated data as unusable pi). : .
i - **
4. If ion abundance criteria are not met, professional judgment may be to
determine to what extent the data may be utilized. _ Guideiliiies^lo^aid in the
"
. i ...... w~~
The most^important factors to consider _are the et^
* relatively insensi Live -to location on the the type
' of instnimenta.tioa. Therefore, i:he critical Ion for
are ttป ispa/^\-956i;-174/175l 174/176,' -"and "relative
'ate of lower
5. If the ,mden/ajto:bdi^ that iiistmment perfcn^cfieck criteria
were achieved using techniques other than those described im|ffilp|||iw additional
information on the instrument performance checks should be ofetauied. If the
techniques employed are, found to be at variance with the contr^trSjuireriieiits, the
performance and rmx^ures of the laboratory may merit evJl^OB;,^Concerns or
fonnance should be Botco 'luft^TPO "Action in the
ORDAS 'form,' For example, if the reviewer has reason^-to -believe that an
inappropriate- technique was used to obtain background subtraction (such as
background subtracting from the solvent front or from another; region of the
chromatogram rather tea the BFB peak), thai this should be noted for TPO action
in the ORDAS fioinn.
3.4 -Initial CaUbiatton .' :
CtompHance requirements for satisfactory instrument raHbratioi are^atablisliesd to ensure
that the instrument is capable of producing acceptable qualitative and quantitative data for
compounds on the volatile target compound Est (TCL). Initial caMbratioa demonstrates that
the instrument is capable of acceptable performance in the beginning of the analytical ran
and of producmg a linear calibration curve.
3.4.1 Acceptance Criteria .
1. Initial calibration standards containing both volatile target compounds and system
monitoring compounds are analyzed at concentrations of 10, 20, 50, 100, and 200
ug/L at the beginning of each analytical sequence or as necessary if the continuing
calibration acceptance criteria are not met. The initial calibration (and any
samples and blanks) must be analyzed within 12 hours of the
instrument performance check.
-------
Procedure No,: 1M2~VOA
Revision; 1
Page 15 of 3C
2. Separate initial calibrations must be performed for water (or medium level
soil samples) and for low level soil samples. The calibration for water samples and
medium level soil samples is performed with an unheated purge and the calibration
.for lowle^%ซfl^iiiipl^"is performed with a puxgeJ- .; >; V, :':.,, '.
" /vL*"ii'j^i'fo'iป*s'lj^h"v'"ฐ**--1"' - ' ' > '*'**$.
'3. ' Initial caHbratioJjltod^^-KeMve Response Factor (REFs)?for; volatile
'<. .. .
' , ' equatto 6;0^|f^^
' .A; - . --V-,;'.
':-:-:^p^S-, ' ' '..'*'. ,-:f- ;Wr- ' ' ' -.'
4. Hie Percent Relative Standard Deviation (%KSD) from .the irntiai; calibration mist
be less than or eqiMio^p,0% for all cojppounds. (Contractual Calibration %RSD
' '''' : t^^fcl&K-v- '
'
.Form VI VQA^aMW335^^83^1^-
3.4.3' Eto&utfaii _ ^
i. ' Verify that, ifie^'eorieet concentration of -standards were use^-for the initial
. calibratioii (Le., 10,20, SO, 100, and 200 ng/L for water). ^'
2. Verify mat the correct initial calibration was used for water and medium level soil
samples (i.e., unheated purge) and for low level soil samples (i.e., heated purge).
3. If any sample results were calculated using an initial caBbratioii, verify that the
correct standard (i.e., the 50 ug/L standard) was used for calculating sample results
and that the samples were analyzed within 12 hours of the instrument
performance check.
4. Evaluate the initial calibration RRFs and RRFs for all volatile target compounds and
. system monitoring compounds (surrogates):
Verify that for all volatile target compounds and system monitoring
compounds, the initial calibration RRFs are greater than or equal to 0,05,
Because historical, performance data indicate poor response and/or erratic
behavior, the volatile compounds listed below have no conttactual maximum
%RSD criteria. Contractually they must meet a miniinum RKP criterion of
0.01; however, for data review purposes, the "greater than or equal to
0,05** criterion is applied to all volatile compounds.
-------
Procedure No.: M2-VOA
Revision: 1
.
16 of 34
Volatile Target Compounds Exhibiting Poor Response
' *
, * .. . Acetone
- * .-..: 2-Bufiuiooe ' .
tfinilfide . ,
methane , \ -.;.
t^ene (total) ;/. -'.-^^j^f
toorofUBpane,..',,, , , , ,; :.:'-->^l:'?^^
lemonฉ " p " ".'''-!''-'-.!-'
" "e
^ethyl-2-pentanone
' , ,'-.>.|;i.i- .'
NO1B:' eompoiiAds ifi bold ace system monitoring compounds. . .
..>'."..!-'^?Ts1 50%) use
professional judgment for qualifying non-detects as "UJ".
-------
Procedure No.: M2-VGA
Revision: 1
Page 1? of 34-
b. If any initial cattbiation KKP is less thin 0.05, qualify positive results that
have toeeptable spectral identification with._"!ป", and non-detected
aialytesas'oniiable,."R**. * ' 'v ,
' 2, At the reviewer's discretion, a mote in-depth review to minimise the qualification of
data can be icpopptiliM'^:ซon^dciiiig-lhe following:' ": >v--:s'j.ซs^ซซ*?:.. '
- ' /. ' y-f^'i&fcj s.'
l(><"'" ired, volatile compounds have a 9SRSD greater than 30.0%,
the' Mgh .cxrtberlo^-pd^^tterciirve-does not
feltSO* las than or opal to 30,0f&::>:">'I '*;." -:
* i - .... * ** .. * >
forihat
*';' " '".';.'&3%&< ' '
'"~ * ,/ t, .i* 5 >' "j" JI * E "
._. _T__j''anj needed for volatile ^w^p&rfs titat woe- not
:.'jifSi^^^3X Ae is grossly :caccebdedKf.c,ป >50%),
pn3fessional judgment is used to' qualify non-dclects v/itli "UP.
. .!."r^iVi.-lS;.Jii'ฃ..^*X,50%,
professional judgment is to qualify non-defects with **UJ".
c. If the low aid'of the curve is outside of the linearity criteria:
i. No qualifiers are required for positive results in the portion of
the curve,
ii. Qualify low level positive results in the of non-linearity with
(*ฅปป
ซl *
iii. No qualifiers are needed for volatile target compounds that were not
detected'. If the is grossly exceeded (i.e., >50%),
professional judgment is used to qualify non-detests with "UJ".
-------
Procedure No.: M2-VOA
Revision: 1
Date:
Page 18 of 34
NOTE: If a, b, or c options 'are used, a description of the, process most be dearly
. . ' stated in the data review narrative.
3, If the laboratory has failed to provide adequate calibration information, the designated
' representative should contact the laboratory and request the necessary Mormation, If
tie information is not available, the reviewer must use professional judgment to
(he data. ''''''
4. Tle*potmfM-^!ffi^ should be
noted-in fee '
5., If calibration criteria are exceeded, this should be noted on the OKDAS. "
3.5 Costinuiig-C^iiation/' ' * . Y ':'/' -
Compliance reqitiremerits) for satisfactory instrument calibration are establisho! to ensure
that the instrument is capable of producing acceptable qualitative and quantitative data. ,
Continijdng caMbrationi'establishes the 12-hour relative response;. factors on* which the
quantitations are based and checks satisfactory "performance of the instrument on a day-to-
day basis. " - '
'3.5.1 Acceptance CWtertt. ' '>.
.1. Continuing calibration stondards containing both target compounds. and system
monitoring compounds arc analyzed at the beginning of 12-hour' analysis period
following the analysis of the kstrument performance check and prior' to- the analysis of
the method blank and samples. The continuing calibration may either be a part of the
initial calibration or run independently on another 12-hour analysis period. .
2. The continuing calibration RRF for volatile target compounds and system monitoring
compounds, must be greater than or equal to 0.05. . =
3, The percent difference (%D) between the initial calibration BJiF and fee continuing
calibration KRF must be within ฑ 25,0%.
3.5.2 Review Itemฎ
Review Items: Form VE VOA and chromatograms.
3.5.3 Evaluation Pr&cedure
1. Verify that the continuing caHbratioE was run at the required frequency and that the
continuing calibration was compared to the correct initial calibration.
-------
Noป; M2-VOA
Revisioa: i
Date:
Page 19 of 34-
2. Evaluate the continuing calibration RRF for all volatile target compounds and
monitoring compounds: . -
Verify that all volatile compounds and system monitoring compounds meet
:.r-'-3*ป
Becaii^'-'histcra^^peTformance data indicate; podt'msponse.and/or erratic
IL. -.t^1.L1& liss^liffiLSi^S^Kii*."iL*. ***.Jt*m. tSaJLtm.Jk 5^- ittjfcjfciSj^L-*. "i*1 Ji *!it jn.iL'dSi'iSEf'^'ttijI-fl-y, ^1ซ. ^.^il^.,*^^^ ,*!' ซ
equal'
1 - " ." .">?#
3. Bvduatp'flie'%D(
one or
is applied to, all volatile wppwads.
uftf
Verify.
system
above, liave w,contnclnal
* '"
rป fiw ^iaซw"-|ite|ปses'ปiiiej**gfwter or
MF for
%D is witliin ,ฑ 25.0% for all volatile target compounds and
compourfds, ฐ Note Siiose compounds which luve a %D
.edterioo^ - Hie coiitfacttiil^cslripa^teM'aa^yblfc
. contifluing^CaMbration spedfies that up to any 2^
may fail to 'meet minimum RRF or rriawnuim %D as long as feey Iwve
RRFs that are grater ten or equal to 0.010, and %D of less than or equal
. " to 40J%..-For'"daa review purposes, however/ A 'cornqpouods roust be
considered for qualification what the %D exceeds the ฑ, 25^0% criterion.
3ซ5.4 Artion
1. Hie reviewa" should use, professional judgment to determine if it Is necessary to
. qualify the data for aay volatile target compound. If qualification of date is required,
It should be perfomed using the following guidelines:
a. If the %D is outside fee ฑ, 25.0% criterion and the continuing calibration
RRF is greater than'or equal to 0.05, qualify positive results with *T*.
b. If 'the %D is outside the ฑ. 25.0% criterion and the continuing calibration
RRF is greater than or equal" to 0.05, no qualification of non-detected
volatile target compounds is necessary. If the %D is grossly
(>50%), professional judgment may be used to qualify non-detects with
. "UJ".
c. If the continuing calibration RRF is less than 0.05, qualify positive
that have acceptable mass spectral identifications with "L" or use
professional judgment and Include justification for not qualifying the data in
the data review narrative.
-------
Procedure No.; M2-VOA
Revision:' 1
, ' Date;
20 of 34,
d. _ If the oootinuing calibration KRF is less than 0.05, qualify-non-
-------
Procedure No.: M2-VGA
Revision: 1
21 of 34.
3.6.3
1. Review the results of aH asปdated blanks on the forms ?nd cteKnatograms to evaluate
. ~ the presence of target and non-target compounds in the blanks. *
2, * Verify that a meted blank analysis has been reported per matrix, per .concentration
level for each 12-hour time period on each GC/MS system usซi to analyze volatile
sapples* The-iปyiซi&^ VGA) to
identify the san^ples;iซ&yปd MA-each method blank,';, .'"; ?"*'"' ?*!" . ^ .
3. Verify .that the mstrument blank analysis has been perform^ following any sample
_ analysis where a target analyte(s) is reported at high concentration^). :
3.6.4 Action ,."..v,':-"l
' If-the appropriate blanks i&ewfiQii analyzed wifli the frequency described ;in ''Criteria 2, 3,
and 4, then the 'data":?w^iCTw,.should, use professional;jiMgfaeat 'to. determine if the*
.associated sample data' should be' qualified. The reviewer may . need to" obtain additional
Monnation, "from the laboigtQrjr, "-The situation should be noted far IPO'action on the-
OKDASfornv / :. '" %';':": '' ;' . " . "'.',,..'"'..'-
Action regarding unsuitable,blank results depends on the ckcumstances and origin of the
blank. Positive sample results should be reported, and qualified **B", if the concentration
of the compound in 'the sample isiess than or equal to 10 times.(iQx) the amount in any-
blank for the common volatile laboratory contaminants (methylene chloride, acetone, and 2-
butanone), or 5 times (5x) the amount for other volatile-target compounds. In situations
where more than one blank is associated with a given sample, qualification should be based
upon a comparison with the blank having the highest coneentraion of a contaminaat. The
results must not be corrected by subtracting any blank value.
For qualification purposes, consider all blanks in a associated with all samples.
Field blanks measure cปntamination introduced not only in toe -but also from the
laboratory. In general, evaluation of the impact on specific sample results is .handled the
same as with laboratory blanks. The reviewer should use caution in attributing
contamination to .the field as opposed to laboratory sources. However, when field-
introduced contamination is suspected, it is helpful for the reviewer to consult the sampling
group to identify possible sources and prevent future reoccurrences. Verified field sources
of contamination should be noted in the data review narrative. If a field blank has the
highest concentration of a contaminant, then all samples in the associated are qualified
"B", using the 5x and lOx rule. Other field blanks with the are'not
qualified..
-------
Procedure No,: BG-VOA
Revision: 1"
Bige22of34
Specific actions axe as follows:
1. If a volatile compound is found in a blank but npj found in the no action is
taken, If the contaminants found are volatile compounds (or interfering non-
target compounds) at significant concentrations above the CRQL, this should be
noted' '
2. Any volatile compomid{Detected in the-sample (otter than the common volatile
laboratory- contaminarits)^^t was, also detected in any associated blank, is qualified
""B'% when;.'the ample;''eoioratetiQn is less than _fiye times- '(5x) -the blank
concentration. For common volatile laboratory contaminant, the results are qualified
"B", when the j^mple concentration is less- 10 (l{k) the blank
conce&tnttioti.-. ../--.'-.t-/;^"-/'- " _' . - - - .-"'' -
ฐi, fe -* ~ i**** . . _* ~
3, The reviewer should note that blanks may not involve the weights, volumes, or
dilution factors as the, associated samples, These must be taken into
ccmsideiation'.when\apji.^^.ffie **5x*f and **l(bfc" criteria* such tibat^a'.coniparison of
me total amount of contarmriation is actually made. ,.,.-, /" ' / ..
Additionally, may be where little or no contamination was present in
tie blanks,' but qualification of the is deemed necessary. If the
reviewer determines that the contamination is from a source other than the sample,
he/she should qualify the data. Contamination introduced through dilution water'is one
example. Although it is not always possible to determine, instanoes of Ms occurring
can be detected when contaminants are found in the diluted sample result but-are
absent in the undHuted sample result. Since both results are not routinely reported, it
may be impossible to verify this source of contamination,
4. If gross TOntaininatiQn exists (i,e.ป saturated by GC/MS), all compounds
in the associated samples should be qualified as unusable (R) due to interference. This
should be noted for TPO action in the ORDAS if the contamination is suspected of
having an effect on the sample results.
5. 'If inordinate numbers of other target compounds are found at low levels in the
blank(s), it may be indicative of a problem and should be noted for TPO action in the
ORDAS form.
6, The same consideration given to the target compounds should also be given to
Tentatively Identified Compounds .(TICs), which are found m both the sample, and
associated blank(s), (See VGA Section Xffl for "TIC guidance.)
-------
Procedure No.: M2-VQA
Revision: 1
06/30/1995
Page B of 34-
7. If an instrument blank was not analyzed following a analysis which contained
an analyte(s) at high concentrations), sample analysis results after toe high
. concentration sample must be evaluated for carryover. judgment should
be used to determine if instrument cross-contaminatioQ has .affected my positive
compound idenMcatioa(s), If instrument cross-oontaminatioo is suggested, then this
' should be noted for TPO action if the cross
-------
Procedure No,: M2-VOA
Revision: 1
. 24 of 34
Sample result is 'greater than the Contract Required QtiantUation limit
(CRQL), tat is less the 5x or IQx multiple of the blank
6P-.3V7. .30
,- . .30B
' " ", *ฃ' '''' *'*-'^ '*'*'< ,'" " '" ' '-..'...
,1m fc.ewrifte.fiMi-flie "10*** rate, results -leu ton 70, (or 10 x 7)
' 'B**. |i the case/of -tte **5x" nde, less
"'
than aSrpr 7):wiwM be qoaifirf *%**.
Smple"ซtilt isios^'ttan" the CEQL, and is also,leas the 5x orlfa
multiple of the blank result. .;
Blank Result 6 6
CRQL 5 :5
Sample Result . 4J 4J
Final Sample Result 4B 4B
Note tibat data ace reported as 41, that the qualitative
is not confirmed.
Sample result is than the 5x~ or lOx multiple of the blank
Rule
Blank Result 10 10
CRQL . 5 5-
Sample Results 120 60
Final Sample Result '120 60
For both the "10x" and "5x" rules, 'sample results exceeded the
adjusted blank result of 100 (or 10 x 10). and 50 (or 5 x 10)f
respectively.
-------
Procedure No*: M2-VOA
Revision; 1
Page 25 of 34-
3.7 System Monitoring Compounds (Surrogate _
Laboratory performance on individual samples is established by of spiking activities. ,
All samples am spiked with system monitoring compounds (formerly to as
surrogates) prior to pnipfe 'pinging. The 'evaluation of nW'nsdltar-.jaf 'these
monitoring compounds is not necessarily straightforward. The sample, "itself may produce
** * * - r * T-*^ ' , si^ฃ*|> '""^M*"^'** 'S^'^ifflt ' "
." effects due to such fectors as interferences and high Since the
effects of the 'raiBpie'^firil^&aiiiaatty 'outeide-' the* and may
h * *** ,"'--"' ~* "* * , ^"-ifii.^^^OT^^yfe^^^^fejij,- j *"
present relatively unique problems, .the evaluation ana review of dataYbaseW on' specific
sample remits is frequently subjective and demands analytical expn.Sice1'and professional
judgment. Accordingly, this section consists primarily of guidelJB^s," in some with
several ' ' '"
3.7.1 Acceptance 'Criteria*'
1 . Three system inoiiitoting;<ปmpduiids|l >2^cMoiorfhiiie4lJปitlMPofaiieieป and
toluene-dS) are added to all samples and blanks to measure* their recovery in-
environmental samples and blank matrices. .- ",-
*..-,; , , / .-.-' *
2. Recoveries for system monitoring compounds in volatile samples and must be
miMn the litaits in A|^mdซ A and the SOW. _ . " .
3,7.2 Review Items
Form n VOA and chromatograms.
3.7.3 Evaluation Procedures
1 , Check chromatograms to verify the recoveries on the System Momtoring Compound
Recovery Form Form n VOA,
2. The following should be determined from the System Monitoring Compound Recovery
form(s):
a. If any system monitoring compotmd(s) in the volatile fraction . is out of
specification, there should be a xeanalysis. to confirm that the non-
compliance is due to sample matrix effects rather than latoratory
deficiencies.-
NOTE: When there axe unacceptable system monitoring compound recoveries
foEowed by successful analyses, the laboratories are required to report only
the successful ran.
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Procedure No.: M2-VOA
Revision: 1
26 of 34
b. The laboratory foiled to perform acceptably if system .monitoring compounds
are outside criteria with no evidence of re-analysis. . Medium soils must first
be re-extracted prior to re-anaJ,ysis when this occurs.
c, Veriiy that no blanks have system monitoring compounds outside the
3. Any time there :'arao^or^more for a particular sample, the reviewer
'. , . -,ป. ป report Considerations should include but are not
limited -to: , t-^il^ j:i^l ' / ' ..''.-"'*.
-" ">'^fe^Sr;.:v^ . .'.:-.."'.
a. . System monitorirsg compound recovery (marginal versus deviation).
. ' - ~-V.' " ' : ':/'- ', : ,
b.
c. Comparison of the values of (he target compounds reported in each sample
' . , *; ^-t**f:u<**'ttjM<^ w . * . : . -j . f
' : . - V: :.';-- - :
d, Otto QC information, such as performance of internal standards.
Date are quaMfiol baปd on 'system^ monitoring compounds results if the recovery of any
volatile system monitoring compound is out of specification,. For system monitoring
compound reeoYeries out of specification, the following approaches are suggested on
a review of all data from the package, esjjedally considering the", apparent complexity of the
sample matrix. (Also, see Table M2-VQA-6, below),
1 , If a system monitoring compound to the volatile sample has a recovery ftan the
upper acceptance limit:
a. Detected, volatile target compounds are qualified "J" ,
b. Results for non-detected volatile target compounds should be qualified **fjJ"
2. If a system monitoring. compound in the volatile sample has a recovery greater than or
" equal to 10% but less than the lower acceptance limit:
a. Detected volatile target compounds are qualified *T*.
b. For non-detected volatile target compounds, the sample quantitation limit is
qualified as appraidrnated, "TO",
-------
5.
6.
Procedure No.: M2-VGA
Revision: 1
Date: 06/30/1995
Page 27 of 34.
3, If a system monitoring compoorid in a volatile shows less than 10% recovery:
a. Detected volatile compounds are qualified "!/*.' \
b. - Non-detected volatile target compounds are qualified as unusable, "R".
4., If two or three system 'monitoring .compounds in the volatile.-' sample, have recoveries
In 'the special case of a blank analysis with system monitoring -compounds out of
specification, the reviewer must give special consideration to the validity of
sample data.' The basic concern is whether the blank problems^represent an isolated
problem with, the blank alone, or whether ihere is a fundaiserital proWem with the
' analytical process. 'For example, if one or more samples in the batch show acceptable
system monitoring compound recoveries, the reviewer may choose to consider the
blank.pxoblem to 'be an isolated occuneiice. However, wo^if ;tejปdgmmt allows
some use of the-affected date, .analytical problems teซdt^:lbrTK5 action oa
the ORDAS. Also note if are potential contractual problems associated with the
lack of icanalysis of samples that were out of specification,' -"' 'f"i":- ป.' '
'" "" * Ht " * "
Whenever possible, potential effects of the data resulting from, system-monitoring
recoveries not meeting the advisory limits should be noted in the data review narrative.
7. Positive results for compounds already flagged for blank containiiiatioii, "Bf *ป will not
need a separate flag for system monitoring compound recoveries. HoweYcr, these
situations 'should be addressed in the data review narrative and the support
documentation.
Table M2rVOA-
-------
Procedure No,: M2-VQA
Revision: 1
Page 28 of 34
9. When- both the initial analysis "and the reanalysis have system monitoring compound
recoveries - outside of criteria, the date, summary form should -normally -contain the
highest concentration obtained for each, compound detected, provided that system
monitoring compound recoveries in the analysis reported do -not a high
bias., However, if-a laboratory contaminant is in one. analysis
but not- in the other, the negative result may be more to report
. When, the reanalysis of a sample is -within the system monitoring compound recovery
criteria, the Jaberatoiy is required to provide only data fe acceptable analysis. If
both sets of, are provided,' and if a compound was in the initial analysis
> .but not in the reanalysis, then the positive result should be (provided the
' ' compound-is not a demomtrated laboratory contaminant), The reported
be flagged as estimated (J)ป due to possible sample inhomogeneity,
3.8 Matrix Spike/^fatris Spike Dupliciite - -: ,( .- .' :;
Data for matrix spike/matrix spike duplicates (MS/MSD) are generated to determine long-
term precision and accuracy of the analytical method oh various matrices and to'
demonstrate ''compound recovery by the laboratory at-.the,"fee -of
analysis. These data alone cannot "be used to evaluate the precision and accuracy of
individual samples. However, when exercising professional judgment, this date should be
used in conjunction with other available QC information. ~^.
3,8,1 Acceptance' Criteria
1. Matrix spike (MS) and matrix spike duplicate (MSD) samples are analyzed at a
frequency of one MS and MSD per 20 samples of similar' matrix.
2. Spite recoveries should be within the advisory limits provided on Form in VOA-1' and
VOA-2, ' -'
3. Relative percent difference (RPD) between MS and MSD recoveries must be within
the advisory limits provided on Form ffl V'OA-i and VOA-2.
3,5.2 Review Items
Form ID VOA-! and VOA-2, chromatograms.
3.8.3 Evaluation Procedures
1. Verify that MS and MSD samples were analyzed at the required frequency and that
results are provided for each sample matrix.
-------
Procedure No.: M2-VOA
Revision: 1
29 of 34 -
2. Inspect results for the MS/MSD Recovery on Form HI VOA-1 aad ฅOA-2 Mid verify
feat the result for recovery and RPD are within the advisory limits.'
3. Check that the matrix spike recoveries and RPDs were calculated correctly.
4. Compare %RSD results of non-spiked compounds the original result, MS, and
:- MSD,-' .,- ' -;'. -:' _ '". v ".."
3.8.4 ' _ .
1, No action is taken on MS/MSD alone.. However, using informed professional
. judgment, the data reviewer may use the MS*"and MSD results in conjunction with
- other QC criteria to' the for-some qualification of the data.
2. The data reviewer should first try to determine to what extent the results of the
'MS/MSD affect the associated data. This determination should be with to>
the MS/MSD sample itself as well as specific analytes for ill' samples associated with
- ' ' ,' -. , _ __
3. M those insfainces whปe it ran be determined that tte of tfae^ MS/MSD
only the simple spiked, then qualification should be limited .to this sample alone.
However, it may be determined through the MS/MSD results that a laboratory Is
having a systematic problem in the analysis of one or more analytes, which affects all
samples,
4. The reviewer must use professional judgment to determine the need for qualification of
positive results of eon-spiked compounds,
5. When non-spiked compounds are present in either the MS-or MSD results, a table in
the data review narrative is constocted showing original (unspiked) sample results for
non-spiked compounds, non-spiked compounds present in the MS and MSD and the
calculated %RSD,
NOTE: If a field blank was used for the MS/MSD, a statement-to that effect must be
included on the ORDAS and noted for the TPO,
3.9- Internal Standards
Internal Standards (IS) performance criteria ensures that GC/MS sensitivity and response
are stable during each analysis.
-------
Procedure No,: M2-VOA
' Revision: 1
Date: 06/30/1995
Page 30 of 34
3.9.1 Aeceptance Criteria '
. I, Internal standard aim counts must not ฅiary by more than a fector of two (-50% to
+100%) from the associated calibration standard,
2. .The retention time of the internal standard must not way most .than ฑ30 -seconds from
(he retention time of the associated caibiation staodard. '>.--: _,
3.9.2
Form VH VGA and dtomatogiams.
''.*,<
3.9.3
I , . Cheek the internal standard retention times and areas reported on the Internal Standard
Am Summary (ForaiVmyQA). ,
-2. Verify that all retention times and IS areas are within criteria,
3. If there are two analyses lor a particular fraction, the reviewer raist'detonnifie which
' are the best data to report -Consideraifions should, include: l
a. Magnitude and direction of the IS ana shift
b. Magnitude and direction of the IS retention time shift
c. Technical holding times.
d. . Comparison of the values of the target compounds reported in each fraction,
c. Other QC.
3.9.4 Action
L If an IS area count for a ample or blank is outside -50% or +100% of the area for
associated standard, then:
a. Positive results for compounds quantitated using that IS should be qualified
with"!". ,
b. Non-detected compounds quantitated using an IS area count greater than +_
100% should be qualified' "Iff".
-------
Procedure No,: M2-VOA
Revision: 1
Page 31 of 34.
c, ' Non-detected compounds quantitated using an IS area count less than 50%
me reported as. the sample quantitation limit and qualified with
"UJ".' .
d. *. If extremely, low.- counts are feporfed, or if performance a
major abrupt drop-off then a severe of sensitivity is indicated. Non-
detected target compounds should then be qualified as unusable, '"ft".
- ' .' . . '"-" -?,!ป,'* - ' " i _=i ; " ", * *n"
2. If an IS tetrafiGA-l&iKhvuies-b raofe 1nan~3Q-
-------
Roeotare No;; .M2-VOA
Revision: 1
-06/30/1995
Page 32 of 34
discrepancy remains unresolved, the reviewer must use professional judgment to
decide which value is the best value. Under circumstances, the reviewer may
determine qualification of data is warranted. A description of the reasons for data
iqualification and. the qualification that is applied to the data should be documented in
the data review 'narrative and in the document support '.-.,-
2. The reviewer must-'assure that any ..results in etxor'by-*inc^^g^^'percent are
identified ami corrected on the sample data summary. If kborato^ resybmission is
not performed, the reviewer should, document his/her cbangesc|p^hevdata in the
' narrative -and support documentation. Calculation errors should also'be noted on the
- O1DAS. -.' ' " '""""" '"
3, Numerous or significant Mures to properly^eyaluate and adjust^CRQLs should be
noted for TP0 action mtheORDAS. '-' :. .- ..^r*-**^ --*'
3.11 .TentativelyIdentified Compounds'
Chromatographic peaks in volatile fraction analyses Out .are not target analytes, system
rnoaitoring compounds or internal standards are potential tentativdy.identified compounds
3,11.J Acceptance Criteria "--^v
For each' sample, the laboratory must conduct a mass spectral search of the MST library
and report the possible identity for the 10 largest volatile fraction which arc not
system monitoring compounds, internal standards, or target compounds, but which have an
area or height greater than 10 percent of the area or height of the nearest Internal standard.
HC results are reported for each sample on the Organic Analyses Date, Sheet (Form I
VOA-HC). ' . " '' '
JSB2E1: Since the SOW revision of October 1986, fee CUP does not allow the
laboratory to report as tentatively identified compounds any target compound
which is properly reported in another fraction. For example, late elating
volatile target compounds should not be reported as senfivolatile HCs.
3.11,2 Review Hems
Form I VOA-TIC chromatograms,
3.11.3 Evaluation Procedures
1. Blank chromatograms should, be examined to verify that TIC in
are not found in blanks." When a low-level non-target compound that is a common
-------
Procedure No.: &G-VOA
Revision: 1
.Page33of34f
i *
artifact or laboratory contaminant is in a sample, a thorough check of blank
' dromtograois may require looking for which are less than 10 percent of the
internal 'height, 'but present in the blank chxpiratogxam at 'a similar relative
retention time. : .
2. The reviewer should be aware of common laboratory artifacts/contaminants am! their
' ' sources (e.g., aldol _ condensation products, solvent preservatives, and reagent
' contaminants),- ^ซ'ซy be- present in blanks and" not reported 'as sample HCs.
Examples! "'"."' ';'. t , ' : '
a. ' COOMBSฎ: Wxaatary contaiiuiiaflts; 'COj (m/z 44), sSoxaiies; (ra/z 73),
. . ' : " diethyl etf&,.hexane, certak'' terns, (14*2-tricMoro-l,2l24ri:flHCปoc4haiie-or
" . fluoroteditawndfliaiie), and phthalates at levels less than 100 ng/L or 4000
b. .Solvent preservatives such as cydohexene wMch is a., mettyleiie chloride
; presBwative,; Related by-products include cydohesanone, ^clohetenone/
" " cydbheEtnolป;^clohexenolป cMorocycIohexene, and
c. Mdol ;ซซideiiation fwction products of acetone uictade: 4-hydroxy-4-l
methyl-2-pentanoiieป 4-methyl-2-peซten~2-one, and 5f5rdimetfiyi-2(5Ii)-
ftiranone, ' . .-->.
3. Ocoaionally, a target compound may be identified in the proper analytical fraction by
non-target library search procedures, even though, it was not found on the quantitation
list. If the total quaetitation method was used, the reviewer should request that
the laboratory recalculate the resell using the proper quahtit^tion. ion. to addition, the
reviewer should evaluate other sample chramatograms and check library reference
retention times on quantitation. lists to determine whether the fete negative result is an
isolated occurrence or whether additional data may be affected.
4. Target compounds could be identified in more than one fraction., . Verify that
quantitation is made from the proper fraction,
5. TIC concentration should be estimated assuming a REP of 1.0.
3.11.4 Action
1. All TIC results should be qualified "J**, estimated concentration, on the laboratory
Form I-TICs. ;
2, General actions related to -the review of TIC results are as follows:
-------
Proeeduie No.: M2-VOA-
, Revision: 1
"
34 of 34
If all contractually requu^. peaks wwe not library aid quantitated, the
designated representative could request these date from the Wwaratey.'
3, Blank Results . " ....'
Form I-TIC which contains ample results that are questioned by laboratory results,
{ should be .flagged "B' * and a line drawn through these date, for em^liasis (initialed and
dated), cu the Form i-TfClto
\ "'' " " *v"",'1. '""- ^ฃ*. * . ,*. i .
'*"" ' ** * '
', To betxmsldered ftteStionabie, a: sample 'TTC coaceatirfcM-'aiik'wriisitt-iO times
the concentration of one of the -blank results. If different volumes/weights are used,
the total amount of compound in the extract must be compared for sample versus
blank. /For VOA data,; an instrumait Iw^'.aiinprisswviiig.rwed .unless the
'ootttenMnaticซ is. proven '_to originate"*" during . iwp^e^^caage' (before
preparation/analysis). In general, blanks analyzed within the same ease, by the
lab, may be cross-applied to .either sol or water extracted or analyzed on
. other. days. . . = \'..j '.
" ,' t* *,
To question a ample result, only presumptive evidence fir the presence of the
compound in the blank is necessary, 'The presence of the TIC in the blank is
suggested in any of the following situations: ... _','
AE blank results must 'be attached in the support documentation section of the data
review. - ,
4. When a compound is -not found in any blanks, but is a suspected artifact of common
laboratory contaminants the result may be qualified as unusable, **R**, and a line
drawn through the result (initialed and dated) on a copy of the Barm I-T1C that is
included in the validation report.
5. Physical constants, such as boMng point, m'ay be factored kto professional judgment
of TIC results.
6. Failure to properly evaluate and report TICs should be noted for TPO tctlon on the
O1DAS form.
-------
* . _ ' Appendix B - -
Validation
" Ml
A-2 W2
-------
-------
Ml-SVOA
Revision: 1
1 of 19-
Appendix B-l
.'of
' . -' Manual Level if 1 - ,
^
Has to'nraualty-inlldMe, the
uudyte^SV0A)1^^ innovative at Level
mป '**
Ite poซdซซrlf ,^pi^^|^te"*SVOA, the' laboratory
Xtagiam. ; HuriTcogy data to the- QLP SOW
to carry out the procedure,
^^^X^NซS#OTp*JMjSj^.;.. / ' .'.,.._ |
'-Hate lfflld^terf:itfi^*'^^>|i^|3t|ttc am., considered ftr/iflie Wlowkg of-
howe^t;/|^Mป;M$ซ;imist^dcdde on a the
is Hie are:
' .Ofwsl^t'bf activities M%o&er 'parties
Comprison to
*., Initial site investigation
ป Contamiiiation
2. Quality Control Measures Checked
Table Ml-SVOA-1 highlights the quality control (QC) indicators evaluated under this data
validation procedure.
3, Procedure
The following subsections describe for each of the QC indicators the acceptance criteria,
location and retrieval of QC data, evaluation of the QC data, actions taken in the event the
QC acceptance criteria are exceeded, and documentation of the QC violations in a
standardized report form.
-------
Procedure "No.: Ml-SVOA
Revision: 1
2 of 19
; Action Level Notification
Instrument
Jkdtiitf
Contiaxtiiig Galibrstioa (%D)
Raw Data
;;
-------
Procedure No.: MI-SVGA
Revision: 1
06/30/1995
Page 3 of 19
Reporting requirements for Level' Ml are:
* Hand annotate the Form I's, including
Data validation qualifier
Sample ideatffieatiGii number
Sampling location .
A statement that defines Hie level of the data review, i.e. , Ml
Major problems with analysis
ป ,",'' i ' "**
; " ป Include the -foUowinjg atfactaaeiits ' ' "..*';,
- . >IM' of d^-valid^on qualifiers'.' ^ "..'..'>.''
Support documentation including forms that support assigning data
Qualifiers!'; . .-" . , , "
QKon-of-OMtody Jfonn " ; '. ;''.'
3.1 .Action Level NotiflsaHon; '
The purpose behind action lef el" notification is to make the EPA Remedial Project Officer
(RPM) or the Site Project Officer (SPO) aware of the potential human health risk at the
ate. to accordance with the Region ffl Hazardous, waste division policy,, lie EPA KPM or
SPO must be promptly notified of any aantommant exceeding the established* action level or
the 10-day health advisory Emit The data for contaminants exceeding the action levels
must be validated as a top priority and reported to the RPM or SPO. Validation of the rest
of the data may then be completed normally.
J.J.I Acceptance Criteria
EPA's Office of Sold Waste and Emergency Response has established 10-day advisory
limits, or the action levels for several oiganic compounds and elements of special health risk
concerns OR the Safe Drinking Water Act, The semivoktile organic compounds and
their 10-day health advisory limits apply only to aqueous samples and are listed in Table
Ml-SVOA-2. The criteria for action level notification are as follows;
* The contaminant concentration must be equal to or above the established 10-
day health advisory limits.
Data for contaminants exceeding the action levds must be validated as a top
priority.
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Procedure No. }> Ml-SVOA'
Revision: 1
Date: 06/30/1995
Page 4 of 19
The following EPA peraonnd must be notified of ' the action level
occeedtnces: '
- . EPAItPMorSPO . -'/''
'' BPASecticmCMefs:. -,
Site ikves%aiiQn (SJ). . , ;" ". ., .,-,;
- Remedial " . " .. : '"'- '
*w * **#
, , Bnforcement . ... '^~- '
HPA
~. Enforcement ' . ' _ ,.;/ -..
'. ' Superftmd ' . "
. - RCRA , ' :^ ,-
The remaining data validation should be completed per normal procedures.
Any special mstaictfons from the Hazardous Waste Division should be
followed.
Records should be kept of the data review, action level notification and any
follow up instructions and actions.
Table Mt-SVOA-2
SEMOTVOLATELE ORGANIC ANALYTES ANB ACTION
Compound
1 ,3-Dichlorobenzene
PentacHoraphenol
Action
Level*
8,930
300
Compound
1 ,4-DIchlorobaizGEie
Action
Level*
10(700
*AM. units are ug/1.
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Procedure No.: Ml-SVOA
Revision: I
Date: 06/30/1995
5 of 19
3.1.2 Review Kerns
AM date required to perform Lard 'Ml validation, as in tie following are
necessary for iarscymg out action. level notification. '.The location. of the date and their
retrieval procedures axe also discussed below.
3J.3 'Jbmtalfrv ; '. '-. . .,;-;,
' *'"*"> t ., * ป * , *' * , , , *
The evaluation process preceding action level notification will primarily consist of
cwnpaiing .the results om FORD Ps with Ae action levels 'presented k Table Ml-SVOA-2.
Following the identification of the contaminants exceeding the action levels, focused data
validation should be performed using the criteria, and procedures described in the
''
The_ action seauitiiig.' from fbajsad: data 'validation' will be the motifieatioE' of action,
* .
3.1.5 ..!'-' ' '
Copies of Fonn I's can be wed to highlight the wntaminants .above the action levels. The
findings of the focused validation on be summarized k a memorandum, and' the data
qualifiers resulting' from focused validation may be written on the Form Fs. The marked
up forms should be clarified . thai they validation of only the contaminants
exceeding the action levels, and not all data.
3.2 Evaluation of Spectra for the Detected Compounds
The 'primary QC indicator checked in Level Ml is the mass spectra for the detected
compounds. This indicator pertains to evaluating a compound's presence by matching its
mass spectrum with a standard (known) mass spectrum for the compound. No assessment
is made of the reported quantity of the compound or any quantitative quality control
indicators that could lend some uncertainty to the reported value.
3.2.1 Acceptance Criteria
The acceptance criteria for spectral matching are given in the CLP Functional
Guidelines and are as foEows:
All -ions present in the standard (known) spectrum at a relative intensity
greater than 10 percent must be present in the sample spectrum
-------
Procedure No.; Ml-SVOA
BevMon: 1
Date: 06/30/1995
. 6 of 19
The relative intensities of the qualifying ions-(those above 10 percent relative
. intensity) must .be witMn +/-20 percent between the standard and sample
spectra, for example, an ion with a relative abundance of SO percent in the
standard spectrum must be present between a relative abundance of 30 and
,70 percent M the sample spectrum)-. ,/..."... . ..
Ions, present in the sample above 10 percent --felatwe^a^^W'must -be
accounted for. ' ' . . ,. \r-':,f'"'""""'*"
3.&2?Review Items..;; . ' '.''_/
Form Fs for each field sample, field blanks, and laboratory blanks indud^ in a Sample
Delivery Group (SDG) are necessary to compiler list of the.detec^_;compoiinds.. Mass
spectra are then necessary for each of the detected compounds in a'sample.i-The'required
mass spectra include both the sample spectra" as well as the 'standard-
With respect to the blanks, it may be beneficial to evaluate the blanks ;before, the sample
mass spectra are evaluated,' If a compound is found to be a commoa"'cmtaimnant, ie., it'
is present in' any one 'of the blanks and also in tine .sample, the concentratiem iii the ample
should be evaluated with respect to the highest blank contamination using the 5 .(or 10)
times criteria before proceeding with the elaborate mass spectral evaluations. The effort
required for the sample mass spectral evaluation may be sigaificanHy-reduced by
performing the blank evaluation first, . Hie mass spectra for the blanks; however, should be '
evaluated to ensure that the contaminants were identified properly.
.All ample Form Fs are generally located together in front of the data package. Copies of
the Form Fs can also be found in the detailed sample data package oi^amad by sample;
i.e., the Form 1 and its substantiating raw data for a sample are placed together. The raw
date include a quantitation report and mass spectra for each detected compounds in that
sample are, A standard (known) mass spectrum, and two sample mass spectra (one
unaltered and another background-subtected) are generally provided. The presentation of
the mass spectra differs for different instrument manufacturers, but information necessary
for evaluating mass spectra is always provided in some form. Hands-on experience with
different brands of mass spectrometers, although not essential, can be helpful in
. interpreting the information.
Copies should be made of the Form _I's, preferably from the summary data pacloge, if
included. Otherwise, the forms can be pulled out from the raw sample data pactatge. AM
detects should then be highlighted with a marker or other convenient means. The raw data
should then be tagged for every sample for evaluating the mass spectra and the
chromatograms (reconstructed ion current profiles).
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Procedure No.: MI-SVGA
Revision: 1
06/30/1995.
7 of 19
3,2.3 of Mass Spectra
Compare the highlighted Form I*s -with the taw sample data. Verify that raw data
an provided fin* every sample, and a Form I for every sample represented by raw
data. Verify on a sample-by-sample basis that mass spectra are provided for every detected
(highlighted) compound reported on the Form I*s. A cross verification should tea be
performed that all target compounds to which spectra are provia^l are also reported
Mass- spectral comparison routines based on the evaluation criteria earlier _
(presence of major ions and their relative intensities) are built into the instrument software;
therefore, performed automati^lly; A listing of ions' and flieir relative intensities Is not
produced; ' tatter & oo^^ttoi?opAt6e otoat ofrtife' fit-of >in*'<^^^U ?jปotfucedt The-
sooie is fcrt-cA^-SMSf.:l^Mf^lCMIO*'fiM''m perfect Ions
and their relative abundances^^e score is printed on the as a Mq"
value. .. a score- upward ''of 60' percent of -the maximum (imwaril ol.M'Of 600) is 'generally
eonadeiied- toseptaMe foi i^ ''
- '"'", " '. ''" : ;'/' ""* '""'."* 'f -' ". " ,V ' '" '-":?-;'"-'!^;:^,v"-v '-
^ Visual comparison of a mass spectrum involves looking for the base ion (the mass 'fragment
with the highest intensity), the parent Ion (mass fragment equal to the molecular weight of
the oampouttd) and otfior/chaiasrteristtc ions xejiiesentijig' removal' of one or mote functional
groups (such as--CH3ป'-Ci^-ป -Q, -OH, or- a ปmWnaiion th'eveof) 'item tie-parent ion, the
base ion or other ions,' Hie removal of fimctional groujps' is often and produces
a fingerprint pattern for a type of compound; i.e., staaight-dtok hydnocaatons produce a
characteristic envelope of mass, fragments separated by 14 mass units. Similarly, aromatic
compounds produce a peculiar fingerprint. ^ The base ion fepfesents the most stable
fragment; therefore^ it is always present However, a parent ion is unstable and may
not exist at all or may exist at a low abundance or relative intensity.
Compare the standard (known) mass spectrum with the baclpwind-subtracted sample
spectrum for the presence of the base, parent and other characteristic ions. Although
background-subtracted and unaltered mass spectra are generally provided, the former type
of spectra are much cleaner looMng due to the subtraction of. column bleed or other broad-
based interferences; therefore, better suited for comparison. Generally, the presence of
major ions and overall matching of the fingerprint pattern between the standard and the
sample, spectra can be considered satisfactory. Tie comparison is rather subjective, and
requires a trained-eye to deduce the information. .
Interference- still may be present in a background-subtracted -mass spectrum due to coeluting
compounds (as compared to column bleed or broad-based interferences). Unless the
interfering compound is= an isomer or an analog of the target compound in question, the
fingerprints produced by the target compound and the interfering compounds can be quite
-------
Procedure No.: Ml-SVQA
Revision: 1
y Page 8 of 19
different. Inseparable isomers reflect a limitation of the gas chromatography without any
recourse, _ Concentrations for such isomers may be reported as all contribution from
one isomer or the -value may be. divided equally the two ispmers. . For 'example,
difficulties are often 'seen in ben2ป(b)fluoranthene and benzo(k)fluoranthene by
gas chromatography. .These compounds also produce similar spectra; therefore, it is
quite difficult to; Idl^them apart Homologous compounds have different
retention times;^thd^Qre^vinay not be of much concern. Thus, coelutmg ^compounds do
not pose signiflc^t|^^ems when evaluate
- .-_ <- - " '' "
- - - ,
Seldom,does a CLP :W>oratory incorrectly interpret a mass spectrum, but is a
.adjective, deiriait^tal'^s.j-^brtial, Snteipretation. . While working witiun Ac CLP
guddAe3f;vUi^Mป^hi^4i^/liave-&eii' own reportiiig practices at the limit, of the
instrument's -sensity^|^Most^of the identification problems occur die
limit of in the relative are not easily
Special attention should;l>ei^id ia evaluating for compounds detected at low
- f , ,"'.' -l-"liปง^%g4ST~TT'" v :~o . F jr. ....
-?",. -. - ' '-.--.
''
;> . - ...
Rearrangements and other i side-ructions often occur inside a mass' spectrometer. These *
.phenomena pEodu6e.-iiap;-fii^ineiite-tha4 are not easily accountable from the straetee erf
tile parent compoiind. While 'it is desirable that a data validator the .knowledge to
interpret complex mass spectra, for the routine CLP analyses, expertise is
unnecessny. ' r ,' .'/ . ' - ' " ' - -^
3,2,4 Action
In the eฅent tihe mass qiectrum of a detectei compound does not at all resemble the,
standard spectrum or has, extoemely poor matching, the compound should be considered
undetected. In this the "detected value should be changed to the CRDL for feat
and as "U." (MOTE: This action is in to the EPA
Functional Guidelines which recommend rejection of data. It is felt that an outright
rejection of date, is not justified. If the spectrum produced at a compound's
retention time does not match the standard spectrum, a conclusion can be drawn that the
target compound is not present and the spectrum may be due to something else. In
such a the compound should be considered as undetected and should not be
rejected. Make sure that the target compound in question does produce a good
spectrum by inspecting the standard mass spectrum from the calibration and the fit score on
the quantitation report for the daily or continuing calibration. Data for undetected
compounds are usable for many purposes ,such as risk therefore, rejection of
date is not beneficM to a project. The conflict of improper characterization should be
brought up and rectified with the laboratory.)
If there is some evidence of the compound's presence (as determined by visual matching of
the base ion, parent ion and fingerprint pattern despite a poor fit score), the compound
-------
Procedure No,> MI-SVGA
, Revision: 1
06/30/1995
9 of 19 -
should be considered tentatively identified. The reported value should not be in this
case; however, a data qualifier'code, **NISป should be-appended' to ttte date point to denote
tentative identification." .-.*
In both of the above cases, evaluation of additional information such as the retention time
and frequency of detection in other field is warranted. ^ Previous site history is alp
an important er^uation;^ ^ to perform such an evaluation (in
o>nti^t to vaUdation'),iMy;fflot^ it is
incumbent upon a da^TOlidafor;;to make appropriate recommendations to the project
managers ttejeojed^^^
3.2.5'
The inoil:C^vadeit:t^^|f|^i^qtti^g:ttie mass spectral evaluation _is girough a brief
memorandum to appropngte;au^iorities..- The highlighted Forms Is aodjthe 'mass -spectra' in
question should be app^d&to^;:tbje memorandim in support of the conclusions. Also fill
out and attach tlie Mass Specti'sl Evaluation Form, as depicted m Table M1-SVOA.-3, to
the report as a record opwhal;-'was''-done.' Record the date(s) of analyses.; Field Sample
numbers should be teanscnbed from tie chain-of-custody in the Sample Identifier column.
Notations may be placed; under the "MS" column for each sample to .describe the
(spectral evaluation., ;Theltelloiwngiiofatiotis are suggested; :," "
ป * XAcceptable mass sspectram. ' ' -
. ซ NTentative identification. Partial proof of a compound's presence, but all
identification criteria not met.
* U-No mass spectral match. Using professional judgment, the compound is
considered undetected.
RNo mass Spectral match. Using professional judgment, the compound
data are rejected from further use,
3.3 Evaluation of Chromatograms
The purpose behind evaluating the .chromatograms is to get an idea regarding potential false
negatives, and gross analytical errors. Checking for positive data as described under mass
spectral evaluation does not offer any insight into data-that are nof reported (i.e., reported
as nondetects). Laboratory error or gross interference from- other compounds could be-the
reasons for erroneous reporting. The gas chromatograms or the reconstructed ion current
(RIC) profiles are the primary too! used for the false negative evaluation under Level ML
-------
Case No.:,
. SDG No.;,
Data Revlewer:_ _
Site:_
No,: Ml-SVOA
Revision: I
SVOAMass
Data Analysed:
Sample idenlifisr:
1.
4,
3,'"
J,
'.'
9.
1ft'
1,
J
4,
s,
7-
9.
m,
MS
RT
* a-
us
w
"MS
.$ "
MB
RT
MS
nr
MS
MS
it
S
RT
'
(BN!
HUNT
tt!
ffiM
fiWft
fAI
(BN1
4-Chloroaniline
IBM
JBNlffl
_443ito.fo-S-mntahtejปJ_
J1H3
.JjgxaAlptgcyciof CTitedigne _ _ (KfUt
2,4
jsm
fflM
(BN1
CBM
(BN1
-------
Procedure No,: Ml-SVOA
Revision: 1
Compotmd:
srcetDcecf*
Addfc (A)
Bsse/Netrfral (BN'j
MS
ET
MS
ซr
"MS
ET
MS
RT
Sample
MS
RT
MS ftT
MS
MS
RT
MS
RT
10
MR
HT
JUQ
AlB^mBJMjfabBtl^ABC i....ffft
JBHtofflaHka.
JBH
*---*Mt\ ^*
fv. f
_UHj
Aflfe.nsssg^
-iMj
fBN'
IBKM*)
ฐ**^*BBiHliTi
-------
Procedure No.: M1-SV0A
Revision: 1
Date: 06/30/1995
Page 12 of 19
J.J.I Acceptance Criteria.
That axe no EPA-established criteria for evaluating duonutogramji for fete negatives.
The criteria used for evaluating chromatograms are b ased on good laboratory and scientific
practices, and these are flirt hard and fast requirements. '-Hie evaluation criteria
aw: '-"".'.. .-,".'". '.. -, .'i. ' / -sV;': '
.',>':.: '. '"'' ;',;'. . - ." r ' ^f-'
-------
No.: Ml-SVQA
Revision: 1
Page 13 of 19-
Inspect the RIC profile for broad, unresolved envelops, These are generally indicative of
outside interference from a of homologous compounds such as straight-chain
hydrocarbons. Especially, the with the internal and
under the using the counts. The values" that are "far from-
the expected values may be indicative of potential problems with the TCL or
quantification.-'" ; -J ;:.''' ' ' , '-:.-,'".',
' - '
in 'flie'-barfiBj^^SmA-^Mfla oiie- indieatiw 'at-
problems with instrument sensitivity or leakage in the system; : The area counts
from shifted baseline are inaccurate, OF even the detection of a TCL at low concentration
may be missed*" '-'' '-}>" -\':~ ':-_' . , ,"..-;- -..-..
Rapid pe^ rising ror: peak 'taHing indicate problems-'with the gas chromatographic column,
such as depleted stationary phaSe on the column, decomposition of the stationary .-phase or
creation of active sites, . Again, a visual inspection -of the RIC profile will yield information -
' ' '
3.3.4 ._
Professional discretion must, be, when evaluating and qualifying on die
chromatographic evaluations. , An chemist can generally infer the
tod the fiequen&y'of tihe'prolileni ftom the RIC profile. If fee jw^lral; appears to be
systematic, ' then, it should be brought to the laboratories attention, and resolved.
Intermittent problems may or may not require any action. The following guidelines are
suggested when acting on MC profile observations:
* Any unaccounted TCL peak with area equivalent to or greater than the
lowest reportable limit for the sample must be brought to the laboratory's
attention and resolved. Any unaccounted non-TCL (i.e., TIC) peak with an
equai to or than 10 'percent area of the internal
must also be resolved with the laboratory, TICs'with less than '10 percent
are not required to be reported according to the CLP-RAS protocols,
In the event, the discrepancy cannot be resolved with the laboratory, the
problems should be documented and brought to the attention of the CLP-
TPG, the RPM and the SM, The data for unreported TCL or HCs may be
considered unusable until the problems are resolved,
ซ If a peak resolution problem is evident for the samples, and to be
systematic (i.e., present in all calibration samples, QC samples, and field
samples -and increasing as the ran progresses, additional QC such
as tile, continuing calibration percent difference (%D), and ' internal and
surrogate standard recoveries in the vicinity of the affected should be
-------
No.: Mi-SVOA
Revision; 1
Date: '
,' 14 of 19
evaluated to determine if the peak resolution problem could detection
or quantification, If determined so, the positive data may be qualified as
estimated, **J.11 Negative date nay also be ^wUfied as estimated, **tU" if
the ability to detect at low is deemed to -be jeopardized
by pocff ioซiuti^ of 'adjacซt peaks. :. - . ,'.,.' ..-.> .;//--.;,,
, , .. .
,'Broad, .Mv^Qp;vof',:teip^og0iis. .eompoiiids
quantifieatioii.,orieyen,. detection,
envelop, .associated V compounds may also be intafeTed^^yiihV;,, Using
professional discretion, the positive and negative data may beconadeied as
' *
_
met with the^e^timated data^ a^^
s"j^y; peed "tote _- :
' ' '"
,
, in-fhe 'ofcadiป5^"J|idicatiw of
intermittent probleins. If the shift is due to or change in the system
' pressure, the positive , as well as negative data may be considered estimated *
-. f* J"'"-aik "UJ,. .-^pectivdy). . *fte-pซW^a -could beralป*''
-------
Procedure No.r Ml-SVOA
Revision: I
IS of 19
3.4 Evaluation of Retention Times
While not unequivocal in identifying a compound, the retention times are quite helpful in
confirming die presence of a detected compound. Matching of spectrum and
retention time of sample with those of a,standard yields higher credibility and
level to the detection in the sample. ~ On the other hand, not matching file .fetation time
doubt, poor nmtdiiii"M;te.Jrtmtioa'tiJiie may not have on the detection.
If mass matching is unacceptable or only partial, and the retention .times do not
match,' then a strong-doubt 'can beicast on a compound**
3.4,1 Acceptance,fi^r^t\ __ - "*"/'' - ' '''''
The criteria ter"w^tioa:^&''iiB'^iecafied[,m the EPA*s functional 'as follows;
must be within +/-GJQ6. KRT of . . '
.
'3.4,2 Mevlew Items'
Qaantitation i^Jrts for, fee ample and continumg calibration axe tequixed for the
evaluation. These are located in die raw data for and standards. A copy of (he
continuing calibration quantitation reports may be made or the repots pulled out from the
raw data to facilitate a comparison with the sample quantitation reports,
3.4.3 Evaluation -&/ Retention IVmes
For the detected compounds, determine the relative retention time for -the compounds by
dividing their retention times 'with the retention time of their internal in
the samples as well as "in the applicable continuing (or initial) calibrations. The sample
SJRTs must fall in range of standard RRT +/- 0.06 units.
3.4.4 Action
Action for retention time evaluation requires professional, discretion. Action must be
based on other data such as spectra and not on retention times alone. The following
actions are suggested for several potential situations,
* Acceptable matching of the spectra and the RRTs--No action
suggested.
-------
. Procedure No.: Mi-SVGA
Revision: 1
. 06/30/1995
16 of 19,
Acceptable matching of the mass spectra but poor matching of the RRTsNo
action suggested, but the cause of retention time shift may be investigated.
Check to, we if similar discrepancies ant observed -in other'parts of the
chromatogram. .Often high concentration of a compound will cause 'shifts in
the retention times for other compounds in the nearby eluting region, but
shifts in retention times in other areas may, act be observed. Shifts all
' .tiiroigh.ti^.^rofliilcjgiaiii maybe 'indicative of^aii "eiiitic""syjten, such as
flow rate fluctuations, poor temperature regulation, restriction or leakage in
the;,system*. . There are -likely- that- the1' ample m
conditions may be kaccurate.. Positive data may be qualified as estimated,
"*T^ if deemed essential' . - *' :'.,;. '.'V^-'
3.4.5 Reporting,-. '''';.'.'"" ' '' *-";: .''.;'>:'. '.'
" ,'.'.'' ' ' ',"', . ' ' ' 'A'," ' ".'.. ' , '
Ttie form presented, eadtef' in TWbte.Ml-SVOA-3 may be used to.recoid any problems, in
the RRT matching. ' For the detects! compounds in each sample, the calculated RRTs may
be recorded under tijeVRT'* wtenn. A data quaffier code may.be -added to me values,
exceeding 0.06 "RRT and' repairing qudificatton, such as "0.15J1 V 'far a- compound: with' a"
difference of 0.15 RRT units and-where''a professional judgment to estimate the date is
~ exercised. ' '. ' ' '. " . ""''.'''.'
3.5 Evaluation of Blanks - ' '
Laboratory blinks and field blanks "have a profound impact on fete positives reported in
samples; i.e., compounds reported as positive detects but not originating from the samples
themselves. Cross contamination from the sampling equipment, incidental contamination
from the field conditions or (contamination from the laboratory equipment or general
environmental are Mtely sources of false positives in the samples.
3.5.1 Acceptance Criteria
Criteria for blank evaluation are specified in the EPA's Functional Guidelines. In.additions
Region ffl .has some additional requirements modifying the guidance. The .acceptance
criteria for blanks apply equally to any type of blanks associated with either sampling or
analysis, such as trip blanks, rinsate blanks, field or bottle blanks, laboratory method
blanks,. While there ate several criteria for evaluating the blanks, the only criterion
applicable to Level Ml is the comparison of the blank-and sample concentrations. This
criterion is as follows: '
For common contaminants, such as the phthakte esters, the sample
concentration must be minimally 10 times the blank concentration to be
considered a positive detect, Other contaminants must be present in the
-------
Procedure No,: Ml-SVOA
Revision: 1
06/30/1995
17 of 19
sample at or above 5 times the blank concentration before they can be
considered significant detects, The blank with, the highest concentration
must be used (this is, if the laboratory blank has the highest concentration of
naphthalene, and the equipment rinsate blank' has the highest concentration
of 2-mtfoaniIine, both of blanks must be used to qualify the respective
Data requirements and retrieval procedures for 'axe' the as those for the
'field samples because the blanks as well as field samples are validated similarly. . Form Ps,
mass spectra, chromatograms, quantitation reports, etc., are essential for performing a
'validation of the blanks first .- , * - * * . ' /.,""-"' ' -. -,
3.5.3 Jtfenfc Ev^Mpm 'fmceiutt' - -..',';
Validate the blanks same as the field, samples. ' Detailed validation MC described
' above under appropriate sections. Use the validated -blank1 for a comparison with
the sample results. 'Mate certain that the and blanks are evaluated on the- same
of ample weight or volume, dilution moisture, content, etc. Use the 5 (or
10)- times the highest blank concentrations for qualifying the date.
** <,__
3.5.4 ' -
If the sample concentrations do not meet the criteria of 5 (or 10) times me blank,
concentration, the ample results should be considered essentially undetected (or as not
detected substantially above the levels reported in the blanks); therefore, flagged "B" in
accordance with the Region HI data vaEdation- guidelines.
3.5.5 Reporting
Form.Fs may be used to write the "B" data qualifier for the not meeting the blank
criteria,
3.6 Sample Paperwork
The purpose for evaluating the sample paperwork is to determine that the samples being
validated are indeed the ones tafen from the site, and have not been tampered with.
Accurate sample identity is of paramount importance in substantiating the sample data.
Without unequivocal sample identity and chain-of-custody procedures, the sample data may
not be defensible or enforceable.
-------
Procedure No,: Ml-SVOA
Revision: 1
Page 18 of 19
Under the current CLP contracts, -the original paperwork -(i.e., the purge or the
administrative record) is .included in the from me 'laboratory. It is assumed
that the data. is not privy to fee original paperwork; therefore, tite
criteria and procedures described below apply only to the documents that are generally
included in the data validation These documents are the chain-of-custody forms
and Region HI Shipping Record. , -
3.6.1 'Acceptmce, CnierM . . ."..'... . '
* > \ f ,
Catena for acceptability or authenticity of the sampling paperwork, document control 'and
chain-of-custody have established by the National Enforcement Investigations Crater
(NEIC), in support of the CLP. Overall criteria are too numerous and subjective to be
discussed here, but the criteria that apply to data mli'dation are: -
* ' Hie eham-irf-cijstody "form should be property' and' completely filldd out
including the sampler signatures, and time of sampling, sampling
' identification, analyses requested, traffic numbers, tag numbers, etc. These
data ne miiiiinally required to confirm tbe. authenticity of toe.sample and-its '
.data; . ; ' , '
* . Hie chain-of-custody. must be maintained at all times. Hie custody
between, different must be and date!. -. - - .
'3.6.2 Review
A copy of the cham-of-custody form originated! in the field and tot returned from the
laboratory with the data are essential to confirm the identity of the samples. In addition,
the Region HI Shipping Record is essential to identify the field QC samples. The- chain-of-
custody and Shipping Record are generally located in front of the date package.
3.6.3 EvaluaMm 'Procedure
Ensure that the chain-of-custody form was signed and by the samplers, and a time
and date were entered for sample collection. The laboratory copy of the chate-of-custody
must have the signature of the laboratory sample custodian. Any errors on the form should
have been crossed out with a single ine through the entry. Verify that all collected
samples have unique station identification, traffic numbers and sample tag numbers.
Ensure that the Region in Shipping Record correctly reflects the information on the chain-
of-custody,
-------
Procedure No.: Mi-SVQA
Revision: i
19 of 19
3.6.4
The action to be taken in qualifying the data is highly on the nature of the
problem. Some errors in paperwork are practically unavoidable in real situations. An
effort should be made to reconcile the differences by checking the field notebooks
against the sampling paperwork. Occasionally., the may forget to' sign the chain-
of-custody; however, the field notebooks may amply describe the sampling event.
Problems are also7inevitable ftr'itotiiig'"breปte^Eafaiang*Sfflii^e-ta^_nttna^ra*and traffic
- numbers.' Generally, there are several alternate of information to substantiate or
'refute the'problem. .-.'-'',.." ' - .'--'
3.6.5.-Reporting ' '-""" " . . . . .." '-'"" '.-..
'Any discrepancies found in the paperwork must be immediately brought to .the of
the EPA RPM. Clearly define the problems in a memorandum to the responsible parties.
Attach marked copies of the chain-of-custody forms to substantiate the findings.
-------
-------
Procedure No.: M2-SVOA
Revision: 1
06/30/1995,
' Page 1 of 39-
:* Appendix B-2'
Validation, of Semivolatlle Organic Analyte Bata
Manual Level M2
1. Purpose and
This pj^yc^ui&,prQvides^^st^b^s^~im^c&om to msnw&f validate the semivolatile
iHganic aaalyte (S V0A) 'data usiiig 'fbe iniuiiiallniMyviitive data validation sjintoach :'at Levd,
M2. , This approach focuses on the use of information contained on the CLP forms and A
review of chromatograms- as summarized In Table M2-S VGA- 1 , The procedures , are based
on modifications to Regions IH's National Functional Guidelines for Orgam
' , -The- ptooedwe is .^^tisle' -to the SฅOA- data'bbtaitaiBd -the. '.'Contract ILabckatey
'. SGffil); Hetrf ^^ 'date to-tte-lS|96'C!LP
to'cany-oat-tiieproceduxe. . ". ' , -.' '
Data validated using this procedure are considered usable for the following of
' f inposes; . 'howwer^ fce 'data ,useis must-.dedde'on a wfaetter. .the
procedure is suitable -for their intended data uses. The are:
* Oversight of autivMes led by other parties ' . ~^r
* Comparison to action levels
Initial site investigation
* ' Contamination sources .
Nature and extent of contamination
Preliminary risk assessment .
* Risk assessment with known high levels of toxics
- Feasibility study
* Preliminary design
Treatability study
j
ซ Initial cleanup verification
-------
Procedure No,: M2-SVOA
Revision:-; I'
Date: 06/30/1995
. Page 2 of 39
. ' TtttoMl-SVOA-l.
QC FOR M2
GXP
QCMEASIFRES
Action Level Notification
Mia! CaHbration (REP)
Initial Calibration (%RSD)
Condnuing Calibration (RRF)
Laboratory Blank
MSMSD (%Rป 1PD)
InfcmaJ Standard Area
Field Blank
Sample Paperwork
Holding Time
Retention Time
Surrogate Recovery
Dilution Factor
Moisture Content
Mass Spectra
Chromatograms
Raw Data
'Ml
.X-.. ,'
X
X
Manual
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
Procedure No.: M2-SVOA
Revision: 1
-Date: -06/30/1995
,. ' Page 3 of 39-
2. Quality Control Measures Cheeked '..'
Table M2-SVOA-1 highlights the quality control (QC) kdcatora.evaluated under this
validation procedure.. . ' " .
Hie fidlowiag $Bbsecli0fis;tfesQttfe;fซ'weltiO]f the"QC'indiomMS'tfit acceptance prfteria,.
location and retrieval of QC data, evaluation of the QC data, actions taken to the event the'
QC acceptance criteria are exceeded, and documentation of the QC violations in a
staadanfized report form. . .'",..,.
The saraivolatle dak reqwiiaiaats to 'be diecbrf-sie listed Wow:.' . ;. _''
; ^ - ' f
3.1 Action Levjd Notfficttion '. . , ..''.'
3'.2- 'Mu^'BxMty'j^^ ' "';
3.3 pCflyB Instnimeart terfomance Check (CCS) *
3.4 MtM/CMbratiซi (CCS) "
' 3.5 Qmtiniiing Calbration (CCS) ' ""
3.6 ' Blanks (CCS)
'3.7 Surrogate Spikes (CCS)
3.8 Matrix Spikes/Matrix Spite Duplicates
3,9 Internal Standards (CCS)
3.10 Reported Contract Required Quantitadon Limits (CRQLs)
3.11 Tentatively Identified Compounds
Two forms have been developed to in the performance and documentation, of
.implementing Level M2, The first form, M2-SVOA-QUAL, summarizes holding time,
calibrations, blanks, surrogates, and internal standards. The second form, M2-SVOA-SPK,
summarizes surrogate and matrix spike quality control checks. These forms appear on the
following'pages as Table M2-SVOA-2 'and Table M2-SVOA-3.
-------
Procedure No.: M2-SVOA
Revision: 1
Date:
- Page 4 of 39
.Repeating requirements for Levd M2 are as follows:
* Band, annotate the Form Fs, toduding
Data validation qualifiers .
- ; - Sample identification number
Sampling location "..
..
A statement that defines the level of the data review, i.e.. M2
f " ป - "' ' ' ' " '- '<ฃ*"" Ste1*}," ""V **ซ ป ซ*.' B
; Major iitfinfoOT'pfdMฎ1^ ~
HighUght issues that may have affected detection limits .' ;
^ . * t * ป . . ji***"*ฅi " ซ v ^?V^ *
\ f Indude Ae folowiag tttactaettts - -..".
, - . Listof dato valdatioii.qualifipa;-.-.,'.,;, .j:-^'ฃ~:i^-..-''. :
Ssipport documentation including forms that support assigning data
- ' qralfieas \- "* " ' ." -'" "';>,V-;. .,'" /
'* - " f" "-, ซ-ป' 'ป*-: <*^ ,
QBin of custody foam _ ';,-' -";.. "".TV; _ - \ . '
- ^ Samples affect'by calibration should be listed on the appropriate _
,, caliaatioii forms ' "' '"i".'. ''"-V%"."--1 '..."'
"i*"1 - '" , *
'*nป data qualifiers ia.Hus review ate as follows:" ' - ' -:-,' ";; ' .
Codes ' Relating To Mortification " (Confidence ooacenkg presence. ^04 of.
compounds) ."""""
U = Not detected. The assocktel -number Meates approximate ample
concentration necessary to be detected.
(NO CODE) ซ Confirmed identificatioE. ,
B = Not detected substantially above the level reported1 in laboratory or field
blanks.
R = Unreliable result. Analyte may or may not be present in the sample.
Supporting data necessary to confirm result.
N = Tentative identification. Consider present. Special methods may be
needed to confirm its presence or absence in future sampling efforts.
Codes Related To Quafltitation (can be used for both positive results and sample
quantitation.limits):
J = Analyte present. Reported value may not be accurate or precise;
-------
SDG No.
DM* Reviewer;., ._
Site:.
Dtte:
.: M2-SV0A
; I
Table M2-SVGA-2. SVGA QndUw SmHMtty (CaHbratioas, Blank?, Holding Time, Sarrogstss, Ifltcraal
Analysi.
Aoalyxcd Within
12 Hours of
'
IMS. ID:
Ssmnb
Idsntifitr:
1'.
2. v. '
?. " . "
* . . * IV^r _* ฃ ป" ' *-
s. '" " . -'"'Axi ,
ซ,-"*"-, "-" ' ': '
7. '' ' '.
1. - " " -" ." '
9. ''. ' "":''
to,' : : -,
HoU
Time
Qw, dซfi
m
y, ' < ป
/.*;
- "
- , " *"
i\.
, i ,
Am
.V '.
Suadsrfs: (<,>}
Sunrogstc
1
ป
. A7'^*^
, . ...-,
|
* *
V
2
3*
4 -
S
..,ป;-..-,
-r" ,:
6
' t
-
' .
y '
7
/-*,'-ซ
-ป.'.K.
-_-:;
t
--"S >
^ ., ^i
_ -'
* * i
'". '
MV;
i
,-i;-'i.'
?..-
.- -.
&! *
'<,; .
Internal (IS)
2
>
1 ;.
'*ฃ** ',1
''I .'
3
i.-,-, ,
-
4
5
6
Trasa:
'
- -ซc
, AcUte
- ' /
CM.--
*ป>ป'
fUU
4-I-)
..2rO>teMtfttri.,.
JM.
J .4-Dichlorohi
fnmป
2-Mcthvlohf-nnI
f At
IBW
4-Mซhvlohc nol
Ml
ffltfl
fflW
JBN)
, flปp|t|if kffle
2-Chloroninhsktleoe
-------
Instrument ED:
Cซ*e No.:_
No.;
Prti Reviewer*
Site; _.
Procedure-No:: _M2ปSVOA
Revision: 1
- Dite: 06/30/1995
T*bleM2-SVOA-2
(conld.)
Dste:
Tims:
fr' '"-'."
CoarimiagCA
Blaaks
4-M
JBliL
_QufaBA_^
fBM)
RT
"OCs R^wrted to BIซnk(i):
-------
Case No.:_
SPG No.:_
Data Reviewer:____
Site:
Procedure No.: M2-SVOA
Revision: 1
_ Date: 06/30/1995
Table M2-SVGA-3. SVGA Sol Sun-ogate and Matrix Spike Qualiey Control Ssuomary
Surrogate Da to Sum m a ry
Sample Idcnti Sen
f Acceptance Rsngtt %R):
. -
::' ' > - ,- ", ""-
* ซ ซs ) . ' " -
' -a B
Soil Sample Recoveries, %R
SI
23-120
- ". -
.,..
**
... /
\ :'
S3,
30-115-
- ,
': .' '.'
i
' '
S3^
1W37
S4 "
24-113
' S5
25-121
,
i-
j*- r , *
agw ** 1
'
S<5
19-122
,
,
S7
.20-130
-
.
' SS
20-130
..
"
Quaiiew C+/4
)
., .
St
; 52' * 2-auorotiiphonyi, S3 'ซซ lcrphoayl-d!4, S4 <
'
SS ป 2-fiuorophctjoI, S$ > 2,4,6-tribmm0pfeeoo!, S7 = 2-
'
MSfMSH. ttซtn..SiปB jnia
^srccfif)
, CCCOT
Spike Compoaud: Aromatk (Aป)
ปBL SAMPLES
BienAl
2-ChloraphenoI
1 ,4-DieWoซ>bซttBซwe
N-NitaปKHli-n-^nopylซnuHe
1 ,2,4-TrichlorafaDzeiM
4-CWoป-3-me(hylphenoI
Acenซphthซne
4-Nltrophenol
2,4-Dinitrotoluene
Pentichlora^henoi
Pyrtne
Matrix Spake, Recovery,
%R
' Rang*
"26-90
2S-1TO
2S-104
41-126
38-J07
2fi-103
31-131
11-114
28-89
17-109
"35-142
Actual
Matrix Spake DispiJeafe,
Reeo?ซy, %R
Raoge
26-90
25-.102 '
, 28-104
41-126
38-107
26-103
31-137
11-114
21-89
17-109
JS-142
Acted
MS/MSD .
Precision, RPI)
Raiige
35
50
27 .
38
23
33
19
50 ,
47
47
36
Actaal
s
Qualifmrs
C+/4
-------
' Case No.:_
SDG No.:!
. Date Reviewer:,
Site:
Procedure No.: M2-SVGA
Revision: 1
_ Date: 06/30/1995
Tabie M2-SVOA-3. SVGA Aqueous Surrogate sad Matrix Spike Quality Control Summary
'-Surrogate Data Sommary
Sample MeatifieR
(Acceptance Range, %R>:
I. ' . ' ' - '
2, - ' '.''-.
3, .,..''. '
'4. '
S. -
6,
7.. ' ' "
.ซ. .' ' . . .
9. '"
10, * '' "'
Aqueous Sample Recoveries,
SI
35-114
' -
'
:;
m.
43-116'
>'"*
- ' -.-'
S3
'33-141
--
*
- 1 *
'-' -
S4
10-110
,
ss
1MIO
;,. '
* *" \
XR
S6
10-123
-.
- - '
S7
33-1(0
; , ,
I
^
ss
-16-110
"-
-" .
, Qualified {4-}-J
\ *
-
' ,/
.'..'. - - ' "
V ' ' ' *
... --"
51 = NilroitejBป!iฃ-45,S2 = 2-CuorobiplssEyi, S3 = terpfacnyi-di4, S4
lonbซBBeaป44.
, S5 = 2-fluoropbeno!, S6 = 2,4,6-tribi
MS/MSD
in
. ccc c*r
Spike Compound: Aromaifc CAR)
. ' SAMPLES
tteid
2rCU*ปoi>keaol
1 ,4-Dichloปbenzenie
N-Nitroso-di-n-propylmmine
1 ,2,4-TrioMQpebeiKeiie
4-Qilonป-3 -uwlhylplieool
Aeens^hlheui
l-Nilrophencil
2,4-Dinitrotohiene
Pentaehlorophenol
Pyrene
Matrix Sjpske, RetOTerj-,
*m .
Range
12-110
27-123
36-97
41-116
39-9S
23-97
46-118
10-80
24-96
9-103
26-127
Actual
Matris Spike Dt! jfeate,
Rtwvwy; *R '
. Raage
12-110
27-123
41-116
39-9i
23-97
46-118
10-SO
24-96
9-103
26-127
Actual
Precison, RPD
Raage
' 42
40
as
38
IS
42
31 -
SO
38
SO
31
'.Acted
fJ^ttliMSS
(+/4
-------
Procedure No.: M2-SVOA
Revision: 1
,
Page 9 of 39
K = Analyte present.;- Reported value may be biased 'high. Actual value is
expected lower,
L , = Analyte present Reported* value may;be low. Actual value is
/expected to be higher. . ; . "' . .
UJ SB Not delected, quantitation limit may be inaccurate or imprecise. . "
> " ป , ",*"*,"*'**
UL .. ซ. Nc&detectedป/quantiua^ -:' . ' *'
Other Codes . . . . - '-V- : - .;'. ; . -
.Q = No analytical' result .." ''..''"?' ''" ' :
.3.1 Action' Level Nutificatioii' \ ' . /.-' ''"' -1-', "'.'/':
The purpose behind action' level. notification is to' make the EPA Remedial Project Officer
(RPM), or the Site Pcoject Officer .(SPO) awaie of the potential Jumna risk' at fte
site. In accordance with the Region III Hazardous waste division policy, the EPA RPM or
SPO must be promptly notified of any contaminant exceeding the established action level or
the 10-day health advisory Emit The date for, contaminants exceeding/the .action levels,
must be validated as. a top priority and imported to the RPM or SPO. VdMitkMi of Ac rest
of ttie data may then be completed normally. '_ ' ',
3.1.1 Acceptance' Criteria
EPA's Office of Solid Waste and Emei^oicy Response has established 10-day advisory
limits or the action levels for several organic compounds aad dements of special health risk
concerns based 'on the Safe Drinking Water Act. The semivolaffle organic compounds and
their ICMay health advisory Emits apply only to aqueous samples and are in Table
M2-SVOA-4. The criteria for action levd notification are as follows:
- The contaminant concentration must be equal to or above the established 10-
day health advisory limits,
* Data for contaminants exceeding the action levels must be validated as a top
priority,
* - The following EPA personnel must _be notified of the action level
exceedances:
-------
1PM orSPG
EPA
Site (SI)
Procedure No.: M2-SVOA
Revision: i
Date:
10 of 39
RCIA
ซ. . " -
Hie remaining validation should be completed per normal procedures.
Any from the HtzaMous Waste Division should be
followed. ' . . . ' " ~~~
Records should be kept of the data review, action level notification and any
follow up mstajctibns "and actions.
Ikble M2-SVOA-4
SEMWOLAHluE ORGANIC ANALYSES AM) ACTION IJSVELS
Compound
1 ,3-Bichlorobenzene
Pentachlorophenol
Action
Level*
8,930
300
Compound
1 ,4-Dichlorobenzene
Action
Level*
10,700
-
*A11 units are ug/L
-------
Procedure No.:
Revision: 1
Date; 06/30/1995
Page 11 of 39.
3.1.2 Review Items
AH data required to perform Level M2 validation, as detailed in the following sections, are
necessary for carrying out action level notification. The location of the data and their
. retrieval- procedures are also below. ; . " .
13.1.3 'Evaiu^oa Procedure ' ' .
of,
wmpipg the results on PonnTs with the action levds pKseofecl ia;";ittble^M2-SฅdA-4,
Following the identification of the contaminants exceeding the action levels, focused data
validation should be performed using the criteria and procedures described in the
sections bdow. % '''' '' ^ ' '
3.1.4 Action . ' " '-'' " ;, '.-'
, " ' " * -..- *:> -.rป*VS's: ป \ &
The action resulting from focused data validation will be the notification of, action level
exeeedaflee to' the-parsowiel identified above in Section 3. LI.- ' .," /' \ ;: . ,- ' ^ ' ' '
.3.1.5 Reporting ..*'.'. , '*''''.'.
Ctopies of Form Fs can be used to highlight the contemiMiits above the action levels. The
findings of the focused validation am be summarized in a memorandum,, and the data.
qualifiers resulting from focused validation may be written' on the Form Fs. "Hie marked
up forms should be clarified that they represent validation of only the contaminants
exceeding the action levels, and not all date. "
3.2 Technical Holding Times ,
y
The objective is to ascertain the validity of results based on the holding time of the sample
from time of collection to time of sample extraction and analysis.
3.2.1 Acceptance Criteria -
Technical requirements for sample holding times have only been established for water
matrices. The holding times for soils (and other non-aqueous matrices such as sediments,
oily wastes, and sludge) are currently under investigation. When the results are available
they will be incorporated into the data evaluation process. Additionally, results of holding
time studies will be incorporated into the data review criteria as the studies are conducted
and approved.
-------
Procedure No.;, M2-SVOA
Revision: 1
Page 12 of 39
# *
The holding time criteria for water samples, as stated In the current 40 CFR Part 136
(dean Water Act) is as follows:
For semivolatile compounds in cooled- (@ 4ฐC) the maximum
holding time is 7 'days from collection to. extraction and 40 days from,
. sample extractioa to analysis. .
It is further required that semivolatile compounds ia properly preserved non-aqueous '
samples be extracted withiii.J days .from sample collection .and the .extracts analyzed within
4t) days ' '
%.. .
3.2.2' ..'.'-." ' - .- .'-.,-.'
FormlSV^Land'Sy^J&A.Sa^
,- __. ,'- ,. .- , ,,.:-;- .-....:. V _ '
3,2.3
.. . ,..,. . -.. .. .
Technical holding times for sample abaction are established by comparing the sampling
date on the WA_ Sample -Kaffiss Jteport witii *fte .ฉf oo/Foim I Sฅ-l and,'
SV-2. To determine if the samples was analyzed within the holding time after extraction,
compare the of extraction on the sample extraction with the of
on Form I SV-1 and SV-2. ' _ , * . ' ' '
Verify that the C.Q.C. . indicates that fee woป received intact and iced. If the
woe not iced or there were any. problems with the samples upon receipt, then
olscrepancies in the sample cofiffition could the date,
3,2,4 Action
1. If technical holding times are exceeded, flag all positive results as estimated **Jf*
and ample quantitation Emits as estimated-**UJ*f and document that holding times
were exceeded. However, please note that some extractabie compounds aie
extremely persistent in the environmeilt (e.g~., PAHs) in non-aqueous matrices and
would not be expected-..to degrade significantly during sample storage. The
reviewer must use professional judgment in the application of data qualifiers to
those compounds in non-aqueous matrices.
2, If in the professional judgment of the data reviewer a loss of semivoktile
c0mpound(s) is evident due to exceeding Ac holding time criteria, the affected
positive results or the associated quantitation limits may be qualified as low,
**L" or "UL" respectively. The narrative must contain the reviewer's justification
for qualification of the compound results as biased low.
-------
Procedure No,: M2-SVQA
\ ' Revision: 1
, Date:
Page 13 of 39.
3. If technical holding times are grossly (greater than 2 the required
technical holding time), either on the analysis or upon re-analysis,, the'reviewer
must use professional judgment to determine the reliability of the and the
' of'additional on die The reviewer may
; - that positive results or the associated quantitation limits are approximates and should
- .'be qualified with-**!" or. "TO", respectively. The reviewer my-determine, thtt
- . .'non-defect data we (R). , - '' " . -..'.
4. '; Jfceau*ttf limited Jifc
' it is recommended that a comment in- the data review narrative be- to
'- . that aqueous holding times were applied. - \
5;. Whenever possible, the reviewer should comment on the effect of the
holdiiig time on the resiUting data in the d^ta review narrative. '' ,
6. /. When contractual and/or technical holding 'times are exceeded, this should be noted
'.7.., _;', Tte.ieviewer'iibouid'alsb be. aware-of "the "scenario, in whidi the laboratory has
exceeded the technical holding times, but met contractual holding'times. In this
' ' ,, case, the data reviewer should notify the Regional TPO (where were
collected) and/or RSCG that shipment delays' may; have occurred so that the field
. problem -can be corrected. Hie reviewer may this information on* to the
Regional TPO' on the.QRDAs, but should explain that contractually" the laboratory
met the requirements.
8. When there are other quality control problems in conjunction with-exeeeded holding
times (such as suspected laboratory contamination), the reviewer should follow the
hierarchy of qualifiers. In particular, if for any the reviewer doubts' tihe
presence of a compound, the data summary should display only the *'B" or "R"
qualifier, and not the "I/" qualifier. This is because no net direction of bits can be
inferred under these conditions.
3.3 GC/MS Instrument Performance Check
Gas chromatograph/mass spectrometer (GC/MS) instrument performance checks (formerly
referred to as toning) "are performed to ensure mass resolution, identification and, to some
degree,- sensitivity. These criteria are, not sample specific. Conforrnance is determined
using standard materials, therefore, these criteria should be met in ail circumstances.
-------
Procedure No.; M2-SVOA
Revision: 1
'. Date: 06/30/1995
' _ 14 of 39
3.3.1 Acceptance Criteria-
The analysis of the instrument performance cheek solution must be performed at the.
beginning of each, 12-hour period during whieh samples or standards see analyzed. The
instrument performance check, decafluorotriphenylphosphiiie (DFTPP) .for semlvolatile
analysis, must meet the ion abundance criteria given below. - ,
9 > *
_ Decafluoroti%>haiylphospMae (pFTPfj) * '"'.;'
IB/JE '.". :- ' ''
- 51 30,0 -80,0%"
68 .- ; Less than" 2.0* "of m/zฎ . . ". ' '">
' .69 -.- "Resort ; ,' .- *-/;* .":.,")'. . ''..
'70 ' ' /Lessthm2."o%':ฉfin/zฎ' '.'" . ; ' .-'
... 127 ' 25.Q-75J%--ofm/2l98- " ' - ''- - ' /
197 ' _ ,Lesstliaiii;o%ofia/zl98_x ; ...
. 198 ' ^ Base-peak, 100% relative abxmdafice
'- 199" '. '5.0-9.0%ฉfp/z-19g/ .- -.. *
275 . 10.p- 30.0% 6fm/z 198 ..- ' - -
'365-, . Orator than 0;75% of ffl/k- 198 \. ''-
441 ' ' Prestot, but less than m/z 443' - :.
442 - 40.'0 --110.0% of m/z 198 ' ' '--,
443 15.6- 24.0% :of m/z 442
All ion abundances must be nonnalizecl to m/z 198, the nominal base peak,
even though the ion abundances of m/z 442 may be up to 1 10 percent that of
m/z 198.
3. J.2 Renew Items
Form V SV.
3.3.3 Evaluation Procedures
1. Compare the data presented on each GC/MS Instrument Performance Check (Form
V SV) with each mass listing submitted and ensure the following:
a. Form V SV is present and completed for each. 12-hour period during which
samples were analyzed, ,
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Procedure No,: M2-SV0A
Revision: 1
Date:
Page 15 of 39-
b. Hie appropriate number of significant figures has been reported (number of
significant figures given for each ion in the ion abundance criteria column)
' and that founding is correct. , ,
,c. '*' 'The laboratory has not made any calcpMtion -- .- ' .
2. -.. . Verify that the ion abundance criteria were. met. ~ The criteria for- m/z 68, 70, 441,
and 443' BIB- calculated byvnonE^Mng to the'-speofied-in/z.' -.."" - " '"
, - .-'> f
3. ' If" "possible, 'verity? Jl^*8peete"*weisr generated ; using'- appropriate - background'
- - ' . OTbtraetiott '- Since - the ' DFTPP is _ .obtained from.
chromatographie peaks that should be fmm coelution problems, background
- subtraction should be done in accordance with the following procedure. Three
' - (the apex scan and the scans^mmediately preceding and following the .
" apex) are acquired and averaged and background subtraction must be accomplished .
using' a'nngle -scan'ftipr^-to" flw dution of DFTPP. : ' :-'~:- -:-:'':" '': " "'
'Alln'iiistruiiBent ajntoons must 'be 'identical' to 'ttose used in the
sample analysis. Background subtractior! actions resulting in spectral
distortions for the sole purpose of the contract specifi.cations
are contrary to the quality assurance objectives and are
3.3.4 Action , > '
1. If the laboratory has made minor transcription errors which do not significantly
affect the data, the data reviewer should make the necessary corrections 'on a copy
of the form. -
2. If the laboratory has foiled to provide the correct forms or has .made significant
transcription" or calculation .errors, the Region's should
contact fee laboratory and request corrected date. If the information is not
available, then the reviewer must use professional judgment to the data. The
Regional TPO should be -notified by noting the problem(s) on the ORDAS.
3. If mass assignment is in error (such as m/z 199 is indicated as the base peak rather
than m/z 198), classify all associated data as unusable, (R).
4, If ion. abundance criteria are not met, professional judgment may be to
determine to what extent the data' may be utilized. Guidelines to aid in. the
application of professional judgment in evaluating ion abundance are
discussed as foEows:
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_ < Procedure No.: M2-SVOA
' Revision: I
Date;
16 of 39 ,
a..- 'Some of -the most critical factors1 in the DFTPP criteria , are the
.' mm-instrument specific requirements that are also not unduly affected by the
location of fc spectrum on the chromato|faphic profile, lie m/z for
198/199 and 442/443, are critical. These are -based on the natural
abundances of carbon 12. and carbon 13 .and, should always be met,
. _. Similarly, the relative abundances for 'm/z 68, 70, 197, and 441. indicate the "
coadition of the instrument and the suitabiMty of the resolution adjustment
: arid are vety important Note that all of the foregoing abundances .relate to
'' ' adjacent ions; they are relatively insensitive ; to differences in instrument
- ; design^ and position of the specmjm. on the chromatograpMcp^
b. - '" For the ions at m/z(51ป 127, and 275, the actual-idatiye abundance is not as
critical...-. For 'Instance, if m/z 275 has 40% jeMw" abundance -(criteria:
_ . ' 10,0-30.0%) and other criteria arejnet*. then,- te.defttieney is mioor. .
c. The relative abundance of m/z 365 is an indicator of suitable instrument zero
-. adjustment ; If -relative -abundance for m/z 365 >is zero, ininimiim
limits may be affected. On the other hand, if m/z 365 is present, but less
the 0/75% minimum abundance criteria, the deficiency Is not as:
5. Decisions to use analytical dab associated with DFTPP instrument performance
' checks not meeting contract requirements should be clearly noted in the data review
narrative. ""-,
6. If the reviewer has reason to beieve that instramettt perfbraianoe check criteria
'were achieved using techmques other than those specified' in the SOW and in
subparagraph a. above, additional information on the DFTPP Instrument
performance checks should be obtained. If the techniques employed are found to be
at variance with contract requirements, the procedures of the laboratory may merit
evaluation. Concerns or questions regarding laboratory performance should be
noted for TPO action on the GKDAS. For example, if the reviewer has reason to
believe that an inappropriate technique was used to obtain tedqjround subtraction
(such as background subtracting from the solvent front or from' another region of
the chromatogram rather than the DFTPP peak), then this should be note! for TPO
action on the ORDAS.
3,4 Initial Calibration
Compliance requirements for satisfactory instrument calibration are established to ensure
that the Instrument is capable of producing acceptable qualitative and quantitative data for
compounds on the * semivoktile Target Compound List (TCL). Initial caHbration
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Procedure No,* JM2-SVGA
Revision; 1
, - . -
' Page 17 of 39-
demonstrates that the instrument is- capable of acceptable performance in- the beginning of
the analytical run and of producing a linear calibration curve. .
3.4.1 Acceptance Criteria *
1, MUM calibration containing both semivolatile compounds and*
are analyzed at of 20, 50, 80, ^ 120, and . 160 ug/L at the
beginning of each analytical sequence or as necessary if the continuing calibration
acceptance criteria are- not- met. The iaitiai calibration (and any associated
and blanks) must be analyzed within 12 hours of the associated instrument
performance cheek. _
2, Minimum Relative Response Factor (RRF) criteria must be than or equal to
O.QS. Ccmtnttnal'KRP criteria are listed^* Appendix A.
3. He Peweot-RdaHve.Standani Deviations "(%RSD) &r the KRFs^ia* the initial'
"
3.4.2 Rev tew' 'items _;"'.'-.
Form VI SV-1 and SV-2 and'clm)inatcigraifi&,
3.4.3 EvolttoOom
1. Verify ttiat the wirost concenteafion of standards used for the initial
calibration (i.e., 20, 50, 80, 120, and 160 ug/L). For the eight compounds with
higher" CRQLs, only a four-point initial caHbiation Is required (i.e., 50, 80, 120,
and 160 ug/L).
2. If any sample resulte were calculated using an initial calibration, veriiy that the
correct standard (i.e,ป the 50 ppb standard) was used for calculating sample results
and that the samples 'were analyzed within 12 hours of the instalment
performance check.
3. Evaluate the KRFs for all semivolatile target compounds and surrogates:
Verify that aH semivoiatile target compounds and surrogates have RKFs that
are greater than or equal to 0.05. If problems are with low
response factor or compound identification, also check elution order.
historical performance indicate poor and/or
erratic behavior, the semivolatile compounds listed above have no
-------
Procedure Ho.: M2-SVOA
RevMon: 1
Bate;
18 of 39
contractual maximum %KSD criteria.- Contractually they must
a miniinum RRF-criteria of 0.01; however, foe' date 'review
purposes, tile "greater than or equal to 0.05" criterion.Is applied
, to all semlvolatile compounds.
Semivolaiile Target Compounds Exhibiting Poor Response . ,_
.4-CMofwniMiie' ;' -
HeKachfonbtttadiene-' .. .
Hexachlorocyclopentadiene
' 24Qtraaoifiiie .
, >.' ___, Ju ,{;Jป-iy j );{' "'*
3-MtrQanffitte'
.'' ซ..-"'< .> "ป:r ,-
i*.;:'^f-J', r" f
',' '.'-"?-^> '. &'? ' "''5', '^
ฎ
@
ฎ
4-NitaMfflpiue
4ป6-DMtro-2-mdhylplimol
Di-n-biiQrlphthalate . '
Butylbenzylphthalate '
3-3 '-BicMorobซziciiie
4, Evaluate the %RSB for all ซmivolatile terget compounds and surrogates.
a. . Verify that all senuvolatile target compounds have a %RSD of less than or
equal to 30%. The contrachialtcriteria for an acceptable initial caMbratioii
specifies that up to any 4 ซmivolatile target compounds, may fail to
mkuiMim RRF or maximum- %RSD as long as they "'have KRFs that .are
greater than or equal to 0.010, and %RSD of less than or equal to 40.0%.
For data review purposes, however, an compounds must be considered for
qualification when the %RSD exceeds the +. 30.0% criterion.
b. If the %RSD is greater than 30.0%, then the reviewer should use
" professional judgment to determine the need to check the points on the curve
for the cause of the non-linearity. This is cheeked by eliminating either the
high point or the low point and recalculating 'the %RSD.
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Procedure No.: M2-SVQA
Revision: I"
06/30/1995
19 of 39
3.4.4 Action'
I. AM semivolaffle compounds, Mdudkg the 19 "poor performers,*1 listed
above, Witt be qualified using the following criteria:
a.'' If the %RSB is gfeater than 30.0*' and the RRF is greater than or equal to
. 0.05, qualify positive results with "J**ป and $eaiivolatie
b, If ft^MP'S less ffian (MET, 'qualify positive1 "tesoltf thaf'-have acceptable
' mass spectral identification with "I" using professional judgment, and non-
detecft it iiniisable.CR).-' . ' . ' ,
At the reviewer's 'discretion, a more in-dapth. review to mMinize .the qualification
' ' -. '
a. , .If any of .the required semivoiatile compounds' have a %RSD greater than
. 30,0%i'and if-diniinating cUber toe Mjgh or Ae.tow'pokt of the curve does,
.' not icstote the XRSD toless than dr equal to 30.0%: 'v
, ซ # u * *
: ' L < Qualify- jtositive'xesults fiar-thal ซompoimd(s) wifli "J".
ii. Qualify non-detected semivoiatile target compounds based on
" . professional judgment. ' . " -- '
b. If the high- point of the curve is outside of the linearity criteria (e.g. due to
saturation):
i, No qualifiers are required for positive results in the linear portion of
the curve.
ii. - Qualify positive results outside of the linear portion of the curve with
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Procedure No.: M2-SYOA
Revision: 1
Date:
Page 20 of 39
Mi. Qualify noiwieiected sendvolatile target compounds using
professional judgment '
3, . If the laboratory- has .'failed to provide the"
designated representative should contact the laboratory and request the
- 'information.' ff-theirformationis'ndt available, the reviewer must use professional
. judgment to.assess the data, -. " "
, .. ''.- \ ,',- " ' ' . . ; - . " '
4. -Whenever possible, the potential effects oa the data resulting from a failure to ~
, . calibration crateffc&ould-be noted-in the date review.namtiye.. \ -
5. > If raUbration criteria are;grdssly exceeded, this should be noted for IPO action on
' .., '' the OMDAS. - . . \
i,' .' j -''/ ' * ** "
6. ' When it is suspected thai relative response factors were incorrectly from
" or -incorrect .aim the laboratory should be
; ' contacted 'to xequantiiate RKFs and associated sample results, The ORB AS
should identify affected results and document the cause of the reviewer's suspicions.
In addition, a CO" telephone log must be completed. ._-.'''
," "" *!
7. ' Positive results for compounds flagged for blank contamination (B) will not need a
flag (I) in ttie summary jGonn for.miiiimimi IMP, %lSDt or %D
outside criteria. However, situations should .be in the review
nanative and1 issues, pertaining to Eonconaplianee should be on the
OSDAS,
3.5 Continuing Calibration
CotMpManee requirements for satisfactory instrument calibration are estebished to ensure
that the instrument is capable of producing acceptable qualitative and quantitative for
semivolatile target compounds. Continuing .calibration establishes the 12-hour relative
response factors on wMeh the quantitations are and checks satisfactory performance
of the instrument on a day-to-day basis.
3,5.1 Acceptance Criteria,
1, Continuing calibration standards containing both target compounds and surrogates
are analyzed at the beginning of each 12-hour analysis period following the analysis
of the instrument performance check and prior to the analysis of blanks and
samples,
2. The minimum Relative Response Factors (RRF) for semivolatile target compounds
and surrogates must be greater than or equal to 0.05.
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Procedure No.: M2-SVGA
Revision:' 1
Date: ' 06/30/1995
Page 21 of 39-
*
3. The percent difference (%D) 'between the initial calibration ERF and the continuing
calibration KEF must fee within ฑ. 25.0% for all compounds.
3.5.2
Form VH SV-1 and SY-2 and
. 3.5.3
1 , Verify that the continuing calibration wr run at the required frequency and' that the
continuing calibration was compared to the correct initial calibration.
2. Evaluate the continuing calibration RRF for all semivolatile target compounds and
. suirogates. ; > ,:,. .;\ ' " , . . '/ ***" . . ,
Verify that all, semivolatile target compounds and surrogates have RRFs
within
MQTE: Because historical performance dab indicate poor response and/or erratic
behavior, the compounds listed in Section 3.4,3 have no contractual
maปtaซffl-%Di: criteria.' Contractually' .Ihejpmust inert a"minimuii RKF
criterion of 0.01; however, for data review purposes, .the "greater than
or equal to 0.05" criterion is applied to all semiyo!fltile;compoimds.
3, Evaluate the %D tetweea MiM caEbration RJRF and continuing calibration ERF"
for one or more semivolatile compounds.
Verify that the %D is within the ฑ. 25,0% criterion, for all semivolatile
target compounds and surrogates. Note those compounds which have a %D
outside the ฑ 25.0% criterion. The contractual criteria for an acceptable
continuing calibration specifies that up to any 4 ซซMvolatUe target
compounds may Ml to meet minimum RRF or, maximum %D as long as
they have RRFs that are greater than or equal to 0.010, and %D .of less than
or equal to 40.0% . .For review puiposes, however, all compounds must
be considered for qualification when the %D the ฑ 25,0%
criterion.
3.5.4 Action
1. The reviewer should use professional judgment to determine if it is to
qualify the data for any semivolatile target compound. If qualification of data is
required, it should be performed using the following guidelines:
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Procedure No.: AC-SVOA
Revision: 1
Date:
Page 22 of 39
If the %D is outside the ฑ, 25.0% criterion and the continuing calibration
KEF is than or equal to 0.05, qualify positive *T*.
b. , If the %D is outside the +. 25,0% odterion and the continuing calibration
KRF is greater than or equal to 0.05, qualify non-detected semivolatile target
compounds based, on pMesstoflal judgment, . " -
c. If 'the continuing calibiation RRF is less than 0.05, qualify'posMve results
' . that have acceptable mass spectral Identification with "I** of use
-'" '. fwoffesmwA.judgment, -
"' - d," If the .continuing calibration RRF Is less than 0.05, qualify." notHlefeeted
semivolatile target compounds as unusable (R).
*',.*" \ X '
2. If the laboratory ' has failed ' to provide adequate calibration Information, the
. designated rqjresentative should, contact the laboratory and request 'the necessary
' information.- If'the1 information is not amiable, the reviewer -must use professional
: judgment to assess the data.
ซ. " t " " P ' "*
3. Wheoeva-'posAtei the potential effects on the data rwulfing' from a Mlure'to meet
calibration criteria should be noted in the data review narrative. '; *
4. If calibration criteria axe grossly exceeded, this should be noted for. TPO action oa
' ' IheOlDAS. '.'"' " 'C:'
5. When It is suspected that relative response factors were incorrectly generated from
misidentified peaks or incorrect area measurements, the laboratory should be
contacted to requantitate these RRFs and associated sample results, The ORDAS
should identify affected results and document the cause of fee reviewer's suspicions.
In addition, a CUP telephone log must be completed,
6. Positive results for compounds flagged "for blank contamination (B) will not need a
separate flag (J) in the data summary form for nummum RRF, %RSD, or %D
outside criteria. However, these situations should be addressed in the data review
narrative and issues pertaining to noncompliance should be documental on the
ORDAS.
3.6 Blanks
The purpose of laboratory (or field) blank analyses is to determine the existence and
magnitude of contamination problems resulting from laboratory (or field) activities. The
criteria for evaluation of blanks apply to any blank with the samples (e.g.,
-------
. Procedure No.:- M2-SVOA
Revision: 1
Date: 06/30/1995
Page 23 of 39
method blanks, instrument blanks, trip blanks, and equipment blanks). If problems with
my blank oust, all associated date 'must be carefully evaluated to determine whether or not
there is an inherent variability in the data, or' if the problem is 'an isolated occurrence not
affecting other data. , ' ' '
3.6.1 Acceptance 'Criterta ' . '
1. - No contaminants should "be found in the blanks, '
2. The method blank must be analyzed on each GC/MS system used to analyze that
specific group or set of samples,
3.6.2 Review Items .','..-
' . , .* ** . ' .
Form I SV-1 and ,SV~2ป Form IV- SVand^hromatograms. -V. , ; '.
3.6.3. Evaluation
.ซ,,,
1. Review the- results of -all 'associated blanks,"- Form I' SV-1 . and "SV-2,- and
chromatograms to evaluate the pfesenee of target and non-target compounds in the
. blanks.. ;"'" . .
2. Verify that.a method blank analysis has been reported per matrix, f^- concentration
level, for each extraction batch and for each GC/MS system used to analyze
semivolatfle samples. The reviewer can use the Method Blank Summary (Pom W
. SV) to assist in identifying samples associated with each method blank.
3,6.4 Action
If the appropriate blanks were not analyzed with the frequency described above, then the
data reviewer should use professional judgment to determine if the sample
should be 'qualified. The reviewer may need to obtain additional information from the
laboratory. The situation should be noted for TPO action on the OKDAS.
Action in the of unsuitable blank results depends on the circumstances and origin of
the blank. Positive sample results should be reported unless the concentration . of the
compound In the sample is less than or equal to 10 times (lOx) the amount in any blank for
the common phthalate contaminants, or 5 times the amount for other compounds. In
"instances where more than one blank is associated with a given sample, qualification should
be upon a comparison with the associated blank* having the highest concentration of
a contaminant. The results must noj be corrected by subtracting any blank value. ' '
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Procedure No,: M2-SVOA
Revision; 1
Date; 06/30/1995
Page 24 of-39
* For qualification purposes, to determine .the highest concentfatioii of a
'contaminant, consider all blanks in a case associated with all samples.
Field blanks measure contamination 'introduced- not only in the field but also from the
laboratory. In general, evaluation of the impact on specific ample results is handled as
with laboratory blanks. The reviewer should .use caution in attributing contamination to the
field as opposed to laboratory sauces. However, when fieM-introduced contamination is.
suspected, it is helpful for the reviewer to consult the sampling group to identify possible
sources 'and prevent future reoccurrences. Verified fidd sources of contamination should
be noted in the data reฅiew. narrative. If a field blank has a highest concentration of a
contaminant, then all samples-in the associated arte qualified **B'% using the 5x and,
lOx rule. . Other fidd bknto associated with the case are not qualified. , . "
' * ' " ,
Specific actions areas follows:, " ' . ' ^ .
1. ' If a semivolatile compound is found in a'blank but not found in the sample, no
action,is taken. If the contaminants found are. volatile target compounds (or'
.. " interferifig' nom-taigfit-ซiiipoซads) at significant concentrations above ttie CRQL,
then this should be noted for TPO action on the OR.DAS.
2. Any' semivolatile. compound detected in the sample (other than the common
phthalate contaminants), that was also detected in any associated blank, is qualified
"B" if the sample concentration is lea than five tunes (5x) the blank.concentratiQn.
For phthakte contaminants, the results are qualified **Bf * wtei the ample is
less than l(k the blank concentration.
In using the 5x/10x rule to compare blank results to sample results which were
calculated using different weights, volumes, or dilution factors, the reviewer must
choose between comparing the levels delated with the instrument, the total amount
of compound (ug of contamination) present in the extracts, or the final concentration
of the contaminant in the sample alquots. Often, more than one approach will be
acceptable and wffl yield the equivalent flagging of sample results.
a, Comparisons involving sample dry weight correction factors, but with all
other calculation fetors the same for sample versus blank:
In this case, the reviewer can compare the wet ...weight
concentrations, instrument levels, or the toted amount
of compound (ug of contaminant) in the extracts. All
of these approaches wiH be acceptable and will yield
equivalent flagging of sample results.
b. When the ample has a smaller initial aliquot size than the blank (purge or
extraction weight/volume), but all other calculation factors beyond this
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Procedure No.: M2-SVOA
IcvMon: 1
-. ' . .Date
' 25 of 39 -
analytical step are .identical (Le,ป same final extract volumes, injection
volumes, and extract dilution factors for sample versus blank):
* In this case, It is acceptable and equivalent to compare either
' ' instrument levels, the total, amount of compound (ug of contaminant)
in the extracts, 'or the concentration .of eonteuninant in the extracts,
*'- :,: * ". ' 'Filial conc^tniions of sample varan 'tปlaft%'sfปiM not tre-compared..
c. * When the sample has a larger final extract volume or a greater dilution
. than the" .blank . ป ; i '.-"'''' . ,- -"-''.
' '; ':" >:-*' -\ "' if Ae laboatary contaminant;, may tove-'b^:'-fatiiiccd,.aftM' or
"''. ' .'during' the.- sample - dftutian*' Step, tfam.,";a*;;dlie^":-ocปiiifซiiซป .of
" ;"" ซ ''" instrumait " levds is aj^roprlate. ' 'For v.wmpamig the
- :; ': fastniment level. result fir, a' water satoj^6^tfil''vas-"'ซ!ilited 1:.100
prior to injection would take into aoปunt possible laboratory
\ contamination of the syringe, instrument or dilution solvent.
' *. On the other' band, if it is highly probable that the contamination
originated before the dilution step, then it is more appropriate to
' calculate and- compare the total amount of compound (ug of
' ' con taiTiinant) present in the undiluted extracl of the sample versus the
.'blank. For example, a B'NA" attract diluted MOQ'pior to injection
may only be subject to phthalate conteroiiation prior to the dilution
step (i.e., during extection/concentiaiion),
* . If the results of a dilution run are to be flagged (B) because of blank
contamination, -the reviewer should attempt to determine' whether an
undiluted run was also performed. If so, the undiluted run may be
used to verify the presence of a compound detected at levels too high
to be questioned or, conversely, to prove that a compound was
actually not present at levels multiplied by a dilution factor.
"The reviewer should note that blanks may not involve the weights, volumes,
or dilution factors as the associated samples. These factors must be taken into
consideration when applying the "5x" and "lOx" criteria, such that a comparison
of the total amount of contamination is actually made.
Additionally, there may be instances where little or no contamination was present in
the associated blanks, but qualification of the sample was deemed necessary.
Contamination introduced through dilution is one example. Although it is not
always possible to determine, of this cKcurring can be when
contaminants are found in the diluted sample result, but are absent in the undiluted
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. ._ No,:
' ' Revision: 1
26 of 39
sample result. Since both results are not routinely reported, it may be impossible to
verify this source of contamination. However, if the reviewer determines that the
contamination is from a source other than the sample, -should qualify the
data. An explanation of tiie rationale used for this determination should be provided
in the narrative accompanying the Regional Data Assessment Summary. - _ -
3. If gross contamination exists (i.e., : by GC/MS), all
- . . compounds in the associated samples should be quaMfied as unusable (R), due to
. iaterfereace. This should be noted for TPO if the contamination is suspected
of having -an* effeettปthง,-Kmp I&2BSUI& - -:-..--. ".- '.-' >.::.-/.' -v": ';;,. :.-; ' -,
4. - If inordinate amounts of other target compounds are found at low levels in die
blank(s), it may be indicatiye of a problem and should be noted for TPO action.
" . ;:-x^y^?r-$|!^^ '"' . " . -
5.. _ The consideration given to^^^^^fe should also be given to
.TenMvdy/^ottifii^iCm^im&^^Cs) which are found in both the .and
ti ' '' '
_. . .. . ,
6. If an .instnimcatlbla&;V'Wia>iiM ' analyzed -.ibllowing .a sample analysis which-
' contained an analyte(s) at higii concentration(s), , sample analysis results after the
. " high concentration sample must be evaluated for carryover. Professional
' judgment should be used to determine if mstrument cross-contamination has
affecsled my poative'OTi^otod ideatificatkaiCs), ...ff instaiinent^cross-
contontoation is suggested, _then this should- be for TPO if the
cross-contamination is suspected of -having an on the sample results,
7. Blanks or run after a matrix or standard should be carefuly examined
to determiiie the occurrence of instrument or syringe carry-over. Since the
efficiency of sample transfer can vary dramatically according to and
operator techniques, professional judgment should be in each to determine
whether or blank results are ^attributable to carry-over. Some common
examples are as follows:
ซ Zero to one percent syringe cany-over occasionally in SNA runs,
Higher percentages of carry-over following BNA runs that are saturated.
Sample results which are possible artifacts of carry-over should be as
unreliable (R).'
8. When there is convincing evidence that contamination is restricted to a particular
instrument, matrix, or concentration level, the 5X/10X rule will only be applied to
compare contaminatel blanfat to certain associated samples (as opposed to all
samples in the case). Some examples are as follows:
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Procedure No.: M2-SVQA
Revision: 1
Bate; 06/30/1995
Page 27'of 39-
* Column bleed (siloxanes) may be localized to a particular Instrument.
* Common laboratory contaminants, such as methylene chloride and
phthalates, ate generally too unpredictable to safely assume contamination m
restricted,to a pailicular'iostiiiment, matrix, or concentnudon level. . ,
'The following are examples of applying the blank qualification guidelines. Certain
drarastanees iaay wairant donations fiom these'gmddines, * .'....- \ .v ; ,
Eiampte 1: Sample result is than the Contract Required Quantitation
. Limit (CRQL)j but- 'k less' ton the Sx or, IQx multiple .of 'the blank
. . ." . result "':' . ; .',-' , ''.. -;.-, ;-. - *
- -Hank Result ' ;' ,--7. -:' .7- '?-. < -. ' "
'. ''.-.qUJL '-...- , ' ' 5 ; -S."..;'" . ,,'-.
;- Sample lesult ' . 60 , '.30 . ' ' .
' ''Quafified Sample ;60B 301 ' .
' In'Oe example for the **i(k'* rate, less than 70 (or 10-
x 7) would be qualfied "B". In the case of the **5x" rule,
results less than 35 (or 5 x 7) would be quailed **B".
gxample.2: Sample result is less than CRQL, and is also less ton the 5x or lOx
multiple of the blank result.
Rule
A
Ife Ss
Result 6 6
CRQL 5 5
Sample Result 4J, 4J
Qualified Sample Result , 4B 4B
Note data are reported as 4B, indicating that the qualitative
presence is not confirmed.
-------
Procedure No.: M2-SVOA
Revision: 1
Date; 06/30/1995
, Page 28 of 39-
Ikanijpte:n3: Sample result is than the Sx or 10* multiple of the blank
result, i ' "
, ' ' "
= , ' "
'.-.'.- ' : ,,''./ 'ISM Si .'", ^
' Result ' .-. . -10 ' ' 10- / './'.^ -,',V . ./
. s ". 5, ' '5*v ' ,
"Sample. Jtetit , '' ;"' -12ft, 'CO.-'
" . 120*;: :6Q.
. , For '.both ite/'ife'' -and "Sx**1 rules, results .eacbeeded the
^ :adjii^^b|arik\iซults>'of*i00v,(ar -IQklQ) aad.SO.iw- 5x1%
' , respectively.-.^ '''/*', : ' ' , - '- ' : ' - ' '" """ "
3.7: Surwigate Spites ,'. . ';;v:;.' " ' ' . ,. _': :. '
. Laboratory performance on individual samples is* established by means of spiking activities. '
All, 'samples are spiked with1 surrogate compounds prior to sample preparation. The
evaluation of the results of these surrogate spites is not necessarily stiaightforward. Hie
sample itself may produce effects because of such factors as mterferences and high
concentrations of analytes . Since the effects of the sample matrix are frequently outside the
control of the laboratory and 'may present relatively unique problems, the evaluation and
review of data bawd on specific sample results is frequently subjective and demands
analytical experience and professional judgment. Accordingly, this section consists
primarily of guidelines, in some with several optional approaches suggested.
3.7.1 Acceptance Criteria.
I, Surrogate spites, 4 acid compounds (3 required and 1 advisory) and 4 base/neutral
compounds (3 required and 1 advisory) are added to all samples and blanks to
measure tfiek recovery in sample and blank matrices.
' 2. Surrogate recoveries for semivoMle samples and blanks must be within the
limits specified on Form n SV-1 and SV-2.
3.7.2 Review Items
Form II SV-1 and SV-2 and chromatograms.
-------
Procedure No,: M2-SVQA
. Revision; 1
29 of 39.
3.7.3 Evaluation Procedures
1. ' Review chromatograms to check the surrogate spike recoveries on the
Recovery Form n SV-1 and SV-2.
2, . The following should be determined from the Surrogate Recovery forra(s):
'-'-a. If any two base/neutral 01 add surrogates are out of speciScatioii, or if any
.?>' , ฐ '"one taae^eutat'oc arfd;oซl90t^^suiiOfgiite-tes'fi-i3Mป^.;of 1^ ftan
, . ' ; * -t 10%, then there should be a reanalysis to confirm that the non-compliance is
. - because of sample matrix rather than laboratory
followed, by
run:/
The WwrMory ftas- fidied to perform satisfactorily .if recoveries are
'btt'bf' jqjpdficatiott'-and is no evidence of ranjedioa-of fte extracty or
_
" ''- , v ' 'ซ.'' Verily 'that no blanks fiave surrogates recoveries outside the "criteria. .
3. Any are two or more for a particular fraction the reviewer most
- determine which are the best data to report. Considerations should include but are
not Bruited to:. ''.--.
a. ^ Surrogate recovery (marginal versus gross deviation),
b. Technical holding times.
c. Comparison of the values of the target compounds reported -in each fraction.
d. Other QC information, such as performance of internal standards,
4. When both the initial analysis and the reanalysis have surrogate recoveries outside
of criteria, the data summary should -normally contain the highest concentration
obtained for each compound detected, provided flat in the
analysis being reported do not suggest a high bias. However, if a demonstrated
laboratory contaminant is in one analysis but not the other, the negative
result rnay be more appropriate to report.
When the .reanalysis of a fraction is within surrogate recovery criteria, the
laboratory is required to provide only data for the acceptable analysis. If both
of date are provided, and if a compound was detected in the initial analysis but not
-------
. , Procedure No,: 1*Q-SVGA
Revision: I
Page30'of39
the reanalyas, then the positive result should be reported (provided the compound is
not a demonstrated laboratory contaminant). The reported result should be flagged
as estimated (J),-due to possible ample infaGmogeaeity.
5. If advisory surrogates are outside established criteria, professional judgment will be
used in qualifying the sample results. If the results me outside the criteria, then
qualification would only affect similar target compounds..
3.7.4 Actim ' . . ..".' <\.~:>~^'{ ./. ' ' ''"'".'''.
Data am not qualified with respect to surrogate recovery unless two or moce semivolatile
surrogates, within the same fraction (base/neutxa! or acid fraction), are outof specification.
For surrogate spike recoveries ' out of specification, the following approaches are
based en a review- of all data from the case, especially considering the apparent complexity
'
Jfflffi: . These atttk^agpiy- to ill sunraffites,; for **advi80fy" sarogites,
Professional judgment should be used in quaEfying sarnple results based oa
. . advisory surrogate recoveries. Qualification based on advisory surrogate
" . recoveries should be applied to similar compounds in the sample only.
Specify in the narrative any actions taken based on advisory surrogate
recovery. ._.-'. '
1. If' two or more surrogates in either semivolatile fraction (base/neutral 01 acid
fraction) hive a iccowory than the tipper acceptance limit (OL):
a. Specify the fraction that is being qualified, i.e. acid, tee/neutral, or both,
b. , Detected semivoktile target compounds are qualified Mgh, "K**.
c. Results , for non-detected semivolatile target compounds should not be
qualified,
2, If two or more surrogates in either semivolatile fraction have a recovery greater
than or equal to 10% but less than the lower acceptance limit (LL):
a. Specify the faction that is being qualified, i.e. add, base/neutel, or both,
b. Detected semivolatile compounds are qualified biased low,. *'t".
c. For non-detected semivolatile .target compounds, the sample quantitation
limit is qualified as biased low, "UL".
-------
Procedure No.: M2-SVOA
Revision: 1
Page 31 of 39-
3. If any surrogate in either sefnivolatile fraction show less than 10% recovery:
a. Specify the fraction that is being qualified, i.e. acid, base/neutral, or both.
b. Detected semi volatile target compounds ate qualified biased low, "L". ' '
f **
c. _ Non-detected semivolatile compounds -may be qualified "as unusable
(R), (If advisory are' not met, use professioaal judgment to
' '
. .. -.:: -\. <-vS>--frbfeM2ฃVQA*5 ' ^ ' ' : ' V .--. >t ,
. -
.. '.'\ "--';.; V' "SORlftpGAra.KECOTEII^ '
' - ' ...-.'.'', "' "
'Directed analytes- ' ... '.--
Non-detected '
2 or 3 .
AHIBgli
;;'^'" '"
/None '
,2 or 3^'
An LOW"
:.;;L"
-. UL-
/: 2Lcr 3 --..
M ked High/I^)w
:.J'x- :.--:.'
W "-; _,
' '-1 ay. More
< ilKKRee.-*
' '' ' L'
- 'R"
4. If two or more surrogate recoveries in semivolatile fraction (base/neutral or
. acid fraction) are outside recovery limits, 'and one of the is
below the lower limit (but > 10%) and the otfaer'secoviefy is above the upper Emit:
a. Specify the fraction that is being qualified, i.e.j acid, base/neutral, or both,
b. Detected semivolitile compounds are qualified as estimated, *T*.
c. Non-detected semivolatile target compounds are quaEfied as estimated,
"TO".
5. In the special case of a blanlc analysis with surrogates out of specification, the
reviewer must give special consideration to the validity of associated -sample data.-
The basic concern is whether- the blank problems represent an isolated problem with
the blank alone, .or whether there is a fundamental problem with the analytical
process. For example, If one or more samples in the batch show acceptable
'Surrogate recoveries, the reviewer may choose to consider the blank problem to be
ah- isolated occurrence. However, even if this judgment allows some use of the
affected data, analytical problems should be noted, for TPO action. Also note if
there are potential contractual problems with the lack of re-analysis of
samples that were out of specification.
-------
Procedure No.: M2-SVGA
. '. - Revision: 1
32 of 39
6. Whenever possible, the potential effects of the data resulting from surrogate
recoveries not meeting the advisory limits should be noted in the data review
narrative.
7. Positive results for compounds already flagged for blank contamination will not
need a- flag for surrogate recoveries. However, these situations be
addressol in the narrative or the support documentation. .
:*'/' "i .'" ..! -">."-' " " >';",' . ', ," '"-'".,
:"*^*" ~. "'.""'' " .'-.!. "" .- '., -; " ' r -j." -. ", '' . >' ' . "
8. When :
-------
No,: M2-SVOA
Revision: 1
Date: 06/30/1995
Page 33 of 39
3.8.2 Acceptance
I, Matrix splice and matrix spite duplicate samples are analyzed at frequency of one
. MS and MSB. per 20 samples of similar matrix. .
* ' ". ' ,'
2. ' Matrix spike and matrix spike duplicate recoveries should be within the advisory
',' " , limits on Form HI SV-I and SV-2. .:' ' ;.
;3^ ; Tte- IWlaiiTO'PeK^ and matrix spite
.dปpioite"iittปvafflKi should 'tie Mihin'the'adwsoiy limits listed cm: Form fit SV-1'
and SV-2. ' /' ';...- ' ' ''--.
^ 3.8,2 Daiu Requirements and Data Retrieval ' " .
'* ,, "n f** " ,ป?*: S " * * * , ป, ซ
*'".""""'"'" ' jit* *" " "
Form ni'SV-i'and 'SV-2 -and clyooraatogianis. _-- '..'' , . .
' Pmce Aires . ~ ''-ป'' - '''
1. ' ' Voify that MS -anil MSP 'samples weป aMyased at tte'iieptorf fiteqoซ<^ Md that '
results are provided lor cadi sample' matrix. '. .
2. Inspect' results far the MS/MSD Recovery on. Form ffl SV-1 and. SV-2 md verify
that the for-iwปฅery and RPD aye within the adviปfy limitsir
t
3, Compare results (%RSD) of non-jjMfced compounds "between the original result,
MS, and MSB.
3.8.4 Action ' . ,
1. No action is taken on MS/MSD data alppg. However, using informed professional
judgment the data reviewer may use the matrix spike and matrix spike duplicate
results in conjunction with other QC criteria -and determine the need for some
qualification of the date.
2. The data reviewer should first try to determine to what extent the results of the
MS/MSD affect the associated data. This determination should be with
regard to the MS/MSD sample itself as well as specific analytes for all samples
associated with the MS/MSD. , ' '
3, In those where it can be determined that the results of the MS/MSD affect
only the sample spiked, then qualification should be limited to this sample alone,
However, it may be determined through the MS/MSD results that a laboratory is _
-------
Procedure No.; M2-SVGA
Revision; '1
Date: 06/30/1995
Page 34 ฉฃ39
having a systematic' problem in the analysis of one or more trialytes, which
ail associated samples. ,' . '
4 . Hie reviewer must use professional judgment to determine tie need for qualification
' of positive results of non-spiked compounds. ~ * -, - ,
: , ,.,(. ., " ' ' * - . ' , .".". '
If a field blank was used for the M.S/MSD, a statement to that effect must be
"
. .. . ....,, .... . ,
5. When- exteemdyi' tew-f,S." w&avmm am notedr -qualify f jdataofbir all affected
compounds using professional judgment "' ., ' ' /"'; i .
6. When non-spiked compounds are present in either the MS or MSB resultss a table
in the data, review narrative is construct^L- showing original (imspifced) sample
results for non-spiked compounds, non-spiked compounds present in the MS and
MSD ' '' ''' ' "'
3.9 Internal
Internal Sfcmdard.s (IS) performance, criteria ensure that GC/MS &aisitivity and 'i^ponse are.
stable during every analytical tun. '""'."- ' ' ., -
3.PJ Acceptance -'Ctitk A- f.^ ' '^.
L Internal standard area counts for simples and blinks must not vary by more than a
factor of two'(- 50'%' to + 100%) from the associated calibration standard.
2. The retention time of fee internal standards in samples and blanks must not vaiy by
more than ฑ*30 seconds from the retention time of the associated calibration
standard,
3.9.2 Renew Hems
Form Vin SV-1 and SV-2 and chromatograms.
3.9.3 Evaluation Procedures
1. Check raw data (e.g., chromatograms and quantitation lists) for samples and blanks
to verify the Internal standard retention times and reported on the Internal
Standard Area Summary (Forms VHI SV-1, VHI SV-2).
2. Verify that aU retention times and IS areas are witMn the required criteria,
-------
Procedure No.: M2-SVOA
Revision: 1
" Date: 06/30/1995
35 of 39-
3, If there .are two analyses for a particular 'fraction, .the reviews must determine
which' are the best data to report. ' Considerations should include:
a, Magnitude and direction of the- IS area shift
';b. 'Magnitude and' direction of .the IS retention time shaft. -' -..,...
"" v , ;..c, ' TaAMofl loldiig ttoira. ' .;: -. - ;-,_ ;^V,Y '-,: ' "--"'',-
; ' d. . Comparison of the values of the target compounds reported in fraction.
3.9.4- 'AeHtom '*-'-' ' . - ' . '..-'. .-. .
' * - ...'-- - v , *
- - . , ' < , ',.*ป'. 5
-1. If an IS. area : count for' a or btenfeiroutside - 50%. ฉr + 100% of the ana'
" ' '
. ".,
a, '- .'/Podlive.residts: fpc compounds quantitaJted using that. IS shQuM be
~ ' ' ' ' ''
b. . ' Non-detected compounds quantitated using ' an IS area count greater -ten
-. ' .+100% 'should be, wifh"UTf.. ' .'..''";
c. Non-detected compounds quantitated using an IS count less than 5Q%
are reported as the sample quantitation limit and qualified with
"UJ". ' , . . ,
d. If extremely low area counts are reported, or if performance exhibits .a
mstjor abrupt drop-off, ftten a severe loss of sensitivity is indicated. Non-
delected compounds should then be qualified as unusable (R).
2. If an IS retention time varies by more than 30 seconds:
The chromatographic profile for that sample must be examined to "determine if any
false positives or negatives exist. For shifts of a large magnitude, the .reviewer may
consider partial or total rejection (R) of the data for that sample fraction. Positive
results should not need to be qualified with "R" if the mass spectral criteria are
met,
3. If the internal standards performance criteria are grossly .exceeded, then this should
be noted for TPO action. Potential effects on the data resulting from unacceptable
internal standard performance should be noted in the data review narrative.
-------
Procedure No.: M2-SVGA
Revision:- 1
Date: 06/30/1995
Page 36 reseatative to obtain additional information thai cowld resolve any
differences. If a discrepancy remains unresolved, the reviewer must use
professional judgnient to decide which value is the best value. Under
circumstances, the reviewer may detonnine qualification of data is warranted.
Decisions made on date quality should be included k the date review narrative. A
description of the for. date qualffieatMMi and the qualification that is appEed
to the data should be documented to the review narrative.
2, , Numerous or significant failures to properly evaluate and 'adjust CRQLs should be
. noted for IPO action.
3, Hie reviewer must assure that any results in error by more than 10 percent are
identified and corrected on the sample data summary. If laboratory resubmission is
not performed, the reviewer should document his/her changes to the in the
narrative or support documentation. Calculation errors should also be noted on the
ORDA,
-------
Procedure No,: M2-SVOA
Revision: 1
Date:. 06/30/1995
37 of 39-
3.11 Tentatively Identified .Compounds
Chromatographic peaks in semivolatile fraction analyses that are not analytes,
surrogates, or internal standards are potential- tentatively identified compounds (TICs).
TICs must be qualitatively identified by a National Institute of Standards and Technology
(NISI) mass spectral library Midi' and the identifications by the data reviewer,
' '
wMchs
volatile
"-.'..f.vt .:. - .
For each sample,' tlie laboratory must conduct' a mass spectral search of the NIST library
and report die possible id^itity for the 20 largest semivolatile faction peaks which ire not
surrogate, internal standard, or,target compounds, but which have area or height greater
than 10 percent of;therar^Sr|pight of'the nearest internal' standard. TIC results are
oported for fe& Analyses'Data (Form 1 'SV-TIQ.
r_ , _j ..,..._.i^i^^a-j^fflrSSIKSft,^ J ...*f.. *
ป ' " ' ^ S **ป ** J?
UfiZffl;.. -, _ of Ctetolw 19E6, Ae CTP idoiM. not'allow the
j^fa&tiivdy identified "coaajwandi, any torgtt, oonixmitd
'in;another fiacdonu-' For ocample, Jate elating'
inds should not be reported as sernivolatile TICs.
:. .)/.-/.:J":^.-^.; " '
J.11.2
Form ISV-TIC, ctanointtogianis.'' ' . .' --T."'
3.12.3 Evaluation 'Procedures
1. for tentative identification are as follows:
Ensure that.TIC results are reported on Form I's.
2. Blank chromatogiinis" should be examined to verify that HC peaks present in
samples are not -found in blanks, _ When a low-level non-target compound tot is a
common artifact or laboratory contaminant is detected in a sample,. a thorough
check of blank chromatograms may require looking for peaks which are less than 10
percent of the internal standard height, but present in the blank chroniatogiani at a
similar relative retention time.
3. The reviewer should be aware of common laboratory arttfacts/contamirtants and
their sources (e,g.ป aldol condensation products, solvent preservatives, and reagent
contaminants). These may be present in blanks and 'not reported as sample TICs.
Examples:
-------
Procedure No.:^ M2-SVOA
Revision: I
Page 38 of 39
a. Common laboratory contaminants; CCfe (m/z 44), aloxanes (m/z 73),
diethyl ether, faexane, certain freons (lfl,2-McMoco-lป2,2-tifflioroel!ianeOT
fluoro-trichlororaethane), and phthalates at levels less ten 100 tig/L or 4000
ug/Kg. .-- ' ' . i '
b. Solvent preservatives,, such as cyclohexene which is a methylene chloride
. preservative. ' Related by-products include cyclohexanone, cyclohexenone,
AMol -teactioflK products of acetone, include:
pentanone, "4-mAyl-2"paiten-2-onct and
4. ' Occasionally,' a target compound may be Idaatifirf
' fraction by non-target library search procedures, even though' it was ant found on
the quantitation 1st If the total area quantitation method was used, tile reviewer
, should request tJiat the laboratory recalculate the result using the proper quandtation
. ion. In addition, the reviewer should evaluate other sample chromatograms -and
check library reference retention times on quantitation lists to determine whether the
false negative result is an isolated occurrence or whether additional date' may be ;
: affected. /' " - " , ' ,\ '
5. . Target compounds may be identified in more than one fraction. Verify that
quantitation is made from the proper fraction, ^
3.11,4 Actum . '
1. AH TIC results should be qualified *'J", estimated concentration on the Laboratory
Forml-TICs,
2, Bbmk Results
Form I-HC wMch contain sample results that are questioned by blank results,
should be flagged "B" and a line drawn through data for emphasis (initialed
and
To be considered questionable, a sample TIC concentration must be witMn 10 times
the concentration of one of the blank results. If different volumes/weights are used,
the total amount of compound in the extract must be compared for sample versus
blank. In general, blanks analyzed within the same case, by the same lab, may be
cross-applied' to either' sou* or water samples extracted or analyzed on other days.
AH blank results must be attached in the support documentation section of the data
review,
-------
Procedure No.: M2-SVGA
Revision: 1
39' of 39-
. 3. When a compound is not found in any blanks, but Is a artifact 'of common
laboratory contamination, the reviewer should cross off the reported TIC result on
the copy of the Form I-TIC and-note the nason(s) in fee narrative.
4. Physical constants, such as boiling point, may be factored into
judgment of *HC results. '
5r' Palme to properly evaluate and report HCs should' be noted for TPO action.' -."
-------
-------
Procedure No.: Hl-PteST
-Revision: 1
Date: 06/30/1995
Page I of. 20:
Appendix C-l
Validation of Pesticides and PCB Analyte Data
" Manual Level Ml
1ป . Purpose; anfl Applicability-
, " TMs ptwedrae^rowdw'-s^by-s^'inSWflctions to. manually validate pesticide and poly-'
. ( . .cMorin^d biphenyl (pest/PCBs) data, rang the manual Innovative
', 'at Level ML . " ". " ' .''. -' ;
. "_ " '. The" procedure is' applicable to*- the PestiddefPC|B" data obtained -using" the Cow mot
" - ; . -LMioiatory Program Statement of Work tCLP SOW). , Hard copy data confonmng'to' the
C3JP' SOW spedfieatioffii are in ORler'to cany, out .the procedaie,
validated using iffis.'procedure are considered .usable for -the" following types of
proposes; however, the. .data must .decide'on a. case-by-case, biuos - whether'nSe
'procedure is suitable for their intended uses. The suggested are: .:
. Oversight of activities led by other parties
* Action level comparison "" ' "-,
* Initial site investigation
Contamination sources
2. Quality Control Measures Checked
Table Ml-PEST-1 highlights the quality control (QC) indicators evaluated under this data
validation procedure,
3. Procedure
The following subsections describe for each of the QC indicators the acceptance criteria,
location and retrieval of QC data, evaluation of the QC data; actions taken in the event the
QC acceptance criteria are exceeded, and documentation of the QC violations in a
standardized report form.
-------
Procedure No.: Ml-PpST
Revisioq: 1
Date:
2 o'f 20
Table Ml-PEST-1 -
QC CHECKLIST POM LEVEJL Ml .
'QCMMSOKES-
Action Lewd Notification
GClBCD
ป?
Manual ;
wa
MtudCซlibntioa'(CF)
'MtulOdibfBtum(%RSD)
Conliuukig Calibration (KPD)
MS/MSp'(ffR.APD)
Field Quality Control (dup., blak., PB'auap.)
Sample Paperwork
Holding Time
'Retention Time -
Surrogate Recovery
X'
X
x
X :'
X
X
Dilution Factor
X
X
Moisture Content
X
Pesticide Cleanup Checks
Ctiromatograms
Raw Data
X
X
-------
Procedure No.; MI-PEST
Revision: 1
Date: 06/30/1995
Page 3 of 20
Reporting requirements for Level Ml are:
ป Hand annotate the Form Fs, including
Data validation qualifiers ' -
Sample MoTitificalion- number
Sampling ' location
* '"Piwide a narrative that includes
" - Ai frtatMM^^that< defines the level' of the data review, i.e.; Ml
s associated with .analysis . '
. * . 'Include fee- following attachments
. . - ' , list of datjBt validation qualifiers
.' ''-" Support documentation indudlng forms that support assigning data
qualifiers' " ' . - '
..-'. Cham of custody form
" : *
3.1 Action- Level Notification - -.- ."';
The purpose behind "action level notification is to make the EPA Remedial Project Officer
or:,the Site Project Officer (SPG) aware of the, potential human health -risk at the
ate. In accordance with 'the Region HI Hazardous Waste "Division policy, the EPA 3p*M
. or SPO must be promptly notified of any contaminant exceeding the established action level
or the 10-day health advisory 'limit. The data for contaminants exceeding .the action levels
must be validated as a top priority and reported to the RPM or SPO. Validation of merest
of the data may then be completed normally,
3.1.1 Acceptance Criteria
Region in Hazardous Waste Division has established 10-day advisory limits or the action
levels, for several organic compounds and elements of special health risk concern. The
pesticide organic compounds and their 10-day health advisory limits apply only to aqueous
samples and are listed in Table Ml-PEST-2. The criteria for action level notification are
as follows:
* The contaminant concentration must be equal to or above the established 10-
day health advisory limits,
* Data for contaminants exceeding the action levels must be validated as a top
priority.
" The following EPA personnel must be notified of the action level
exceedances;
-------
Procedure No,: MI-PEST
Revision: - 1 '
Date: 06/30/1995
Page 4 of 20 ..
EPARFMorSPO
EPA Chiefs: -
- Site Investigation (SI) .
Remedial ,. ., - _ '
-; Enforcement - '"'-.- '
'- RCRA . . ' *,' ' ' ,
'.>"'
- _ ''EPA'Section Toxicologists:^. .;_, ''
Enforcement , , t ' ,
Superfinid ,, ' - . ' . " ,^
* -< , \ ฐ > ,
'RCRA' _ . ' '
The'raaauimg data valdaiion should be completed pear ncmiMl piocaiiires.
Any special instructions from the Hazardous Waste DivMon should be
followed.
Records' should be kept of the data review, action level notification and any
follow-up instructions and actions.
Table Ml-PEST-2
PESTICIDES AND POLYCHLORWATBD AND ACTION
LEYELS
Compound
Chlordane
Heptachlor
Methoxychlor
Action
Le?el*
63
10
2,000
Compound
Endrin
Lindane
Toxaphene
Action
Level*
5
1,200
80
*AI1 units are ug/L ,
-------
Procedure No.: MI-PEST
Revision: 1
Date; 06/30/1995
5 df-20
3.1.2 Review Items
All data required to perform the complete Level Ml validation, as detailed in the following
sections are necessary for carrying out action level notification. Hie location of the data
.and their tetrieval pnx^ure arc a^ -
' ' J'v' ' . /
311,3' 'Evaluation
Hie evaluation process preceding action level notification will primarily consist of
comparing the results .on Fork fs with file action levels presented in "Mile- Ml-PEST-2.
Following the.identification of fee contaminants exceeding the action levels, focused jdata
validation should: be performed -pang the criteria, and procedures , described < in j the
'-section's '
3.1.4 "Action \ - '''. " '
The action resulting from focused., data validation will be the notification of action
exceedance to the personnel identified above in Section 3.1.1. : - ;
v
3.J.5 Reporting .:''''" ' '
Copies of Form Fs can be used to highlight the contaminants above the section levels. The
findings of the focused validation can be summarized in a memorandum, and the data
qualifiers resulting from, focused "validation may be written on the Form Fs, The marked
up forms should be clarified that they represent validation of only the contaminants
exceeding the action levels, and" not all data.
3.2 Evaluation of Retention Times
Retention times are the only tool (in the event that a mass spectral analysis was not
required) that allow for the identification of the pesticides and PCBs. While a retention
time from a single column is not an unequivocal proof of a compound's presence, if the
retention time of the suspected compound on a second column also matches that of a
standard, then the compound's presence is deemed confirmed. There is reasonable
probability that a non-target compound may have the same retention time as a target
compound on one gas chromatographic column, but the probability of the two compounds
having same retention times also on a secopd column is indeed very remote. For this
reason^ the methods utilizing non-specific detectors require, that the'analyses be performed
under two separate sets of chromatographic conditions
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Procedure No.; MI-PEST
" Revision; 1
Date: 06/30/1995
Page 6 of 20
3.2.1 Acceptance Criteria'
mention 'time acceptance criteria have been established by the EPA and Region m as
jJlpws; , ,
The retention times of both of the surrogates, matrix spites, and reported ', -
compounds in each sample must be within the calculated retention time ;
. " windows ;oa'both! columns., ^The acaptable^windows are ฑ"0.05 ~ minutes for' .
'xttm^itidte^du^^ ฑ0.07 'minutes far , '
compounds eluting after and including heptachior epoxide. The retention ;_ .
"time for the surrogate 'tenachloro-m-xylene CTCX) must be within ifO.05 .
minutes of the mean retention time determined from the initial calibration
'and that' for decacMorobrpnenyl (DCB) must Be wfthfa'ฑ0.10 mantites of the
, mean retention time determined from the initial calibration.
3.2,2 ' Review Items . ;, . . _ "
The instrument teVeL printouts-, or "."the quantitation reports are required to, obtain, the"
intention times for the detected compounds. These are included in the raw data sections of
the data package for "the calibrations as well as the samples. 'Additionally, Forms VIII 'and
x would be helpful in substantiating, and documenting any discrepancies. It also may be
helpful to use a copy of the necessary 'calibration quantitation reports for a jbompaiison with
the sample 'retention times.
3f,2.3 'Evaluation Procedures
*ป*<*"
Note: It is important to emphasize that the evaluation of the retention times goes hand-in-
hand with the chramatographic evaluations. During the evaluation of any one of these QC
measures, a substantial use, of the other QC measure is involved. Therefore, it may be
beneficial to carry out these two evaluations together,
Review the quantitation reports and chromatograms for retention times in the
standards and samples. Use Forms I, VIII and X as additional tools for
documenting and confirming the accuracy of the reported date. Confirm
reported detected analytes by comparing the sample chromatograms to the
tabulated results and verifying peak measurements and retention times.
Acceptable ranges for the pesticides and PCBs 'are presented m Table Ml-
' PEST-3. Ensure that the sample retention times are witMn these ranges for
the compounds reported as detected and confirmed by tiie second column
analysis. Perform a similar evaluation of the associated blank data for a
confirmation of the reported laboratory contaminants, if any,
-------
i s '" " Procedure NQ.: MI-PEST
' . 'Revision; 1
;. ' Date: 06/30/1995
I . Page7of20::
r
| ' ซ For multi-component target compounds (Toxaphene and Aroclors), the
retention times and relative peak height ratios of major component
[ . should be .compared against the appropriate standard "chromatograms,
.. - 3.2.4"-Action'' ' . . * ''-'.- : -..-;.'
. * '" " .-""-, i "
;ff the qualitative criteria for both"wiu|HM weซ not -met* all: target compounds thai are
- - icgittltotf 3ftUtt^ "". !thft' leriewer. may need-to UM- the
;"' -qualifiers that are specific to pesticides. The feviewor should use professional judgment' to
1 . ' an appropriatequantitatiG.n:limit using the fbUowing guidance.,.'.. ' - \
" ' . ' - . - .''' '.'.-" '''. . ' 'i
''.. If -the misideniified peak vitas. sufficiently outside ^the :target pesticide-
: , _ retention time window, then the R^ttrf.values may^he a,fete poative;and-
-, ' ' should te'replaoed. with the ample CRQLvalue, v ' ._ .-. i:,.! -" .-' -' /
ป ' If $he" mMdentified'pedc poses an intwferatta with' potential 'detection :of a'j
- _ target peak-,-"the report^- value should-be; considlered and .qualified as
. , -unusable (R). . ' . '/'"., ,- ..--.'''."'.
ซ If the date reviewer, idซtifies a peak to both. GC column -analyses that falls
within the' appropriate retention time window, but- was." reported ;as a
.nondeteet, then the compound may be a negative.^- Professibnal
judgment should-be used to decide If the compound should tie included.
All conclusions made regardkg target compound identification should be
Included In the data review, narrative,
3.2.5 Reporting
Include one or more-Forms*Ml-PEST-WNDW (example provided by Table Ml-PEST-4)
to represent the acceptance windows for the retention times based on the calibrations.
Record any deviation^ of the retention times on the Form Ml-PEST-RT for the detected
compounds In each sample. Include these documents in the report for Level Ml data
validation results. If the data need qualification, enter appropriate qualifier code on the
sample Form Fs, and attach these to the report,
3.3 Evaluation of Chromatograms For Detected Compounds
The purpose behind evaluating the chromatograms is to get an idea regarding potential false.
negatives, and gross analytical errors. Some idea as to the false positives may also be
derived by checking the chromatograms. Evaluation of the positive data as described under
-------
Case No.:_
SDGNo.:.
Data Reviewer:
Site:
Procedure No.; MI-PEST
- Revision: i
., . _ Date: 06/30/1995
8 of 20
Daies Analyzed;
Instrument !D:
"MMฎ Mi-FESM
, ' Pestkidis/PolycUoriiialed Biptesyk Retention tiaie Windows
Cosnpoaad '
lifehfrtiltC. , . . ; " ' ..' ,
bcta-BHC . ,
fetoriRRCf \ . ' . '" ;
ganBBS-BHC (Uodajoo)
HiptieUtaf ' * . , % .
HcptacUor epoxMo * ' ',-:..'..'
Budbisilfiiii' ' * :; ~ " ' " ฐ
. ..^.. .. . ^.
BWBita . . '-.'-' .
M'^Bpfe' ' ' '.'"''(.
ftป*fai . .. ":/ '.'
Rrffflfflil^it. d
_ป. " r.
4ป4*4>Iป . '-. .'
SBsdofgdfilA sulfate
4,4**DT
MeskojcyttWor
Endrb ketoas , .
Endtut aidciiydc
alpha-CHofdanc
ganima-ChlordaDe,
Taxaphcne
Aroe!ซ 10W
Aioclor 1221
Aiwlor 1232
Arocter 1241
Areeter 1248
Aroelor 1254
Arocior 1260
Tetปchlom-ni-KyleiK (Surr.)
Decaehlorobiphenyl (Surr.)
Reteoiion Tmse
WlaJowta
; Mtaites
ฑ0^tf-.'
ฑ0'
-------
Case No.:_
SDG No,:.
Data Revlewer;_
Site:
Procedure No.; MI-PEST
Revision: 1
_____ Date: 06/30/1995
9 of 20
Table Ml-PEST-4
PEST/FCB Retention Time Evaluation Summary
Dates Anaiyzcd:
/'
' Instcusnsot ID: . .
: , * CJatann (1): ' - -
, . Column (2):
Oftffl^Nwml* ฐ s *
^i-iiie ^
lnftSiC . " . ' ' -
tufnic
gaiamป-BHC (Undtus) . . ~
HejJtscMw
Heptachlor epoxido
EodcBwlfiinl , .
Drfsr"
4,4"MBD| '
Eadrin
Bndosulfen 0
M'-DDD
Eodosulffin aailfate
4,4"-lDOT
Methexychlor ,
Endrin ketoue
Endrin aldehyde
alpha^hJordsnc
gamstia-chiordane
tejMpiiene Peik I
Peซk2
Psak3
Aroclor 1016 Peซk 1
Peซk2
Pteซk3
Aiwter 1221 Fwk 1
Pttak'2
Pซak3
AMcIot 1232 . Peak I
Pซk2
PeikS
'Aroclor 1242 Peak 1
Pซซfc2
Peak 3
Aroclor 1248 Peซfc 1
Peak 2
Pซk3
Aiwstor 1254 Peak 1
Pwk2
Peak 3
Aroctor 1260 Pซk J
Peak 2
Pซk3
SarapSe Idcnufier:
1..
2.
3.
4, . " " ;
5.' /
*. ' - - , , : '
7. ; ;. >
i. ' .''"",
9. =
ilฐ" ' ',' ,,,r
Comroenls ,
L -
2, ' - -
I.
4. .'..
5. , " . . . ' .
ซ... . . - .- . r
?;, .^ - , .
'i. . . ......
'9. , . t .-....-
10. '
Sample IdmtiRer & R^eaiion HUMS for MiBซry CoJtusm (|)" aad Secoadaiy Cotesau ft)
1 .
w
.
a>
} ;'
CO
.
.
ซ'
* ฐ
,'J-
a?
>
m
i -
01
ป
*'j
(U,-
.
'ซ'
. 6
Hi
0)
,
T .
(i)
,-,
m
" f .
m
,
'01
."
^^
t-
<0-
w
ป,.
0)
0}
in
-------
Procedure No.; MI-PEST
Revision: I
. Page 10 of 20 -
mass spectral evaluation does 'not 'offer any insight into data that are aot reported (i,e,,
reported as nondeteets). Laboratory . error or from other compounds
ebulcf be the for Tie gas profiles' are fee
primary tool used. for the evaluation under Level Ml. ,'
4.3. 1 Acceptance Criteria '-",....:'. - ' - :'.'.
. are no EPArซtabflshed;>'fnnrtitelive for diroiriatograms fas Mm-
negatives. The criteria used for evaluating are on good laboratory
and scientific ^practices, \aiwl are -not hard and fast, requirements. 'The suggested.
.evaluation, criteria -ajB as "fottows; _'.- - ,, ' ; "..
* * ",'-"'" I ฐ * , " - *
:-.' * Ctoinatoirains-; nnist display, .singl** component pesticides-- detected in the
I *'.'" jsample and jhe of any nmM-ปmponeitt analyte'detected in the
'. i .' ' sample, at- less tiianfii&'scale. ' . -. _ .'"-' ,-: - '- -. "
,ff an e^Krt"mttat'be.iiliitedf'ctooniatopams must'di^pky angle coxriponeaC *
between- 10 and 100 of full scale, -and- multicomponent
- analytes between 25_aBd 1W of full scale.' . '
For any sample, -the of the chromatogram returjt to bdow 50
percent of Ml the elation time of alpha-BHC, aiSd;alK> return to
below 25 percent of fall after the elution time of alpha-BHC and
before the elufion time of decacWorobiphenyl,
If a chromatograin is replotted electronically to rfieet these requirements, the'
scaling factor used be displayed on the chromatogram,and both the
initial chromatogram and the chromatogram must be submitted in
the
There' should not be any significant in the chromatograms that ' are
accounted for as TCLs. Significant are those with a minimum peak
height of 10 percent of the Ml deflection,
The ehromatograms should ideally have base-line .resolution between
adjacent peaks. Also, there should not be broad (unresolved) envelops in the
chromatograms.
There should riot be abrupt shifts in the baseline.
There should .not be tailing or sharp rise in the fronts.
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Procedure NOK -Ml-PpST
Revision: 1
Date: 06/30/1995
Page 11 d?20-
3.3.2- Review Items
Chroniatograms for -each sample and standard calibrations aie for the evaluation.
These can be found In the front-of the raw data package for each sample. .Hie quantitation
report for' each sample is' also necessary to retrieve the retention 'times since- the
chromatographic profile from a single column can be inconclusive. A copy of the standard
chromatograms from both chromatographic columns -may be very helpful in visiially
'teae^ ."/" "*' . ' ' !'' -
" J ""
3.3.3 Evaluation 'Procedures . . :
i
Note: It is important to- emphastee flat fte evaluation of the chwniatpgtatns; goes' hanc l-in-
' hand with, the retention time'evaluations, /Dunn^-lhe/evafaaticHi'pf any .brie of these JQC
measures, a substantial ''use" of'fhe, other QC;measure is involved..,1; Therefore, It may be
beneficial to carry out these- two -evaluations together-,, '_"''.;" : "":'.:-;:':," ';' . --. ;
* Visually -inspect the primaiy "and the 'secondary column chromatograms -for*
"all peaks ftat appear to be at least' 10 -'percent of the" 'fell ''scale 'defied ion.
t Compare'fhe,retgiitioii tfme of the suspect compound on the primary column
with that of the "Standard. If the retention time--is, close to the
range/ then' check 'the retention time on the secondary 'column. If there is
clear disagreement In the retention time the compound is lij^fly not a .target
compound and should not have been reported. -
' If multicomponent target compounds exhibit marginal pattern-matching
qualify, professional. judgment should be to establish whether the
differences are due to environmental "weathering" (i.e., degradation of tihe
earlier elutmg peaks relative to the later eluting peals). If the presence of a
multicomponent pesticide is sfiongly suggested, results should be reported as
. presumptively present (N).
* If an observed pattern closely matches more than one Aroclor, professional
judgment should be used to decide whether the neighboring Arocfor is a
better match, or if multiple Aroclors are present;
* If GC/MS confirmation was required! but not performed, the reviewer should
report this for TPO action,
Also observe the chromatogram traces for peak resolution between the
adjacent single component peaks. Poor peak-to-peak resolution is indicative
of degrading performance of the gas chromatographic column. The values
obtained from a degrading system are prone to be inaccurate. Generally,
-------
Procedure No.: 'MI-PEST
Revision: 1
Date: 06/30/1995
Page 11 of 20
there should be at least 90 percent valley between the ndghboring peaks.
This criteria is important for detectors such as the electron capture detector
(BCD) that do not.allow for unequivocal identification. Poor peak resolution
between the'adjacent peaks may results .in estimated quantisation of'both for
both compounds.. ' _
, * " 'Inspect the "BCD',.profile -for--broad, wiiesolved. envelops. --These 'arc .
. generally- indicative of outside interference from homologous compounds.
Such envelops .'am mask the target peaks or- interfere, with accurate
quantifation of 'the peafa. , ,, '.-.'' ,*-/,
- : ' - '"'. .Is.'.'"' ' . "' - #.., '
, : _ . _ ซ . Mspeet the'ECD.p&file'fbr abrapt shifts in the baseliae.: .Such- shifts," are -
r.'!.-' _ '..indicative-of problems witli'-ihstacuiqpat\sqmtiviiy "or. lafage in the system,
ITie area counts obtained from shiftal baseline are inaccurate^
, f ' detection of a -TOC Callow concwittation may-be mfcsed:'--{\
" "' ""'".", .-\ ' '' ' " ' . , .
Rapid peak rising or .peak tailing indicate problems with the gas/
.; ' elirofMtojpc^fa^
1 " dee^mposatjoii of Me -stetionairy phase or aeatioji of'active sites,.' Again, a
'visual inspection of the ECD profile will 'yield information on the shape of .
the .peak, ".'... ' '. -.''
1.3.4 Action- . . " """.'.
professional discretioii must be used -when evaluating .and qualifying data .based on the
cfiromatograpMc evaluations. An experienced chemist can generally infer the magnitude
ahd the frequency of the problem from the ECD profile and fingerprinte. If the problem
appears to be systematic, then it should be brought to the laboratory*ฎ attention and
resolved. Intermittent problems may or may not require any-action. The following
guidelines are suggested when acting on ECD. profile observations:
* .Any unaccounted TCL peak (as confirmed by the retention times on both
columns) with area equivalent to or than the lowest reportable limit
for the sample must be brought to the laboratory's attention and resolved.
In the event, the discrepancy cannot be resolved with the laboratory, the
problems should be documented and brought to the attention of the CLP-
TPO, 'the RPM and the SM, The data for unreported TCLs may be
considered unusable until the problems are resolved.
If a, peak resolution problem is evident for the samples, and appears to be
- systematic (i.e., present in all calibration samples, QC samples, and field
samples and increasing as the run progresses, additional QC measures such
-------
Procedure No,: MI-PEST
Revision; 1
Date: 06/30/1995
13 of 20-
as the continuing calibration percent difference (%D), and surrogate standard
recoveries in the vicinity of fee affected, peaks should be 'evaluated to
determine if the peak resolution problem could affect detection .or
quantitation. If determined so, the positive data may be qualified as
, estimated, **J.*' Negative date may also be qualified as estimated, "UJ'Vif
the ability to detect at low. concentrations is also deemed to be jeopardized
.v by poor resolution- of adjacent peaks, _ " '.-..-.'
- Broad envelopes of homologous compounds could interfere with quantity tion
or even detection. If the interference is evident fawn the recoveries; of the
' -: surrogate standards- in the vicinity of the envelop, associated .compounds bay
'also' be totorfeml '.with. Using professional- discretion, \the positive jand
negative date may be considered at estimated, *T* and "UF^iespeclivdy.
If Hie'projectiobjectives- cannot be met with'the estimated' data," alternative
'sample preparation, and cleanup procedures may "need to.be developed land *
'specified. Hie recommended' solution should -be brought to the attentiojn of
Ithe 1PM( Ifae SM and the/EPQ, __.,-'"' ' ' '."- . ! :
"I&crete" shifts in.the baseline "in the middle of .a ran axe indicativfe of
intermittent problems. If the shift is due to leakage br'ehange in the system
pressure, the positive as well as negative data may be considered' estimated
("JV -and- "UJ,. respectively), Tht problem -could be also- due to some
fluctuation in the instrument electonics which" may lead to drastic changis in
the sensitivity of the instrument to detect the compounds. As a rote,
professional-judgment should be exercised in determining the severity or the
problem. For example, the magnitude of a drop in the baseline below
the
zero line may not be estimated and could be very significant. On the other
hand, a drop that yields a baseline still above zero can be put in a
perspective with the original baseline and a general appearance of the entire
RIO profile.
The problems with peak symmetry, are indicative of system degradation, and
should be brought to the attention of the laboratory for a corrective action.
Professional judgment should be used when and If qualifying my due to
unsymmetrical peaks. First 'the problem, should be -defined in terms of
persistence throughout the chromatogram and also from sample to sample.
Additionally, the shapes and area counts for the surrogate standards should
be evaluated' to see if the problem could have affected compound detection
and/or quantitation. Data qualification may-be uncalled for if the standard
area counts are acceptable.
-------
Procedure No.:- MI-PEST
Revision: 1
.Date: 06/30/1995
Ptge 14 qf 20
3-3*5 Reporting
Keeps notes of the problems 'and substantiate them with copies of both chromatograms and
o^her pertinent laboratory paperwork. , Include >these items in the overall report for Level
date valdation. For moee descriptive comments, a -separate sheet nay be used. .
3.4 .
T^he -purpose of laboratory (or field) 'blank ."analysed: is' to determine 'the existence and
-magnitude of contamination problems resulting from laboratory (or. field) activities. ' The
criteria for evaluation of laboratory blanks apply to any blank associated with the' samples
(i s.g. , method blinks, instrument blanks,- and sulfur cleanup blanks) . If problems exist with
aiy type of blank, all associated data must be carefully evaluated to determine whether or
not these is an inherit' variability --m ihe data, or 'if the problem is an, isolated Gccuiaence
not affecting other date. '-.'_/' ' . ' . ,
* * '
laboratory blanks and -field "Wanks have a profound impact on felse positives reported in -
simples; i.e.,. compounds reported as positive detects but not originating, torn the samples "
themselves. Cross contamination from the sampling equipment, incidental contamination
from the field 'conditions or contamination from the laboratory equipment or general
environmental ace likely sources of felse positives in the' samples.
3.41 Acceptance Criteria . , '
Criteria for blank evaluation are specified in the EPA's functional 'guidelines. In addition,
Region" in has some additional requirements modifying the guidance. The acceptance ,
criteria for blanks apply equally to any type of blanks associated with either sampling or
analysis, such as trip blanks, rinsate blanks, field or bottle blanks, laboratory method
blanks. While there arc several criteria for evaluating the -blanks, the only criteria
applicable to Level Ml is the comparison of the blank and ample concentrations. These
criteria are as foEows:
ป No contaminants should be present in the blanks,
* Frequency of Blank analyses:
ซ Method Blanks A method blank analysis must be performed for
each 20 samples of similar matrix In each sample delivery group
(SDG) or whenever a sample extraction procedure is performed.
* Instrument Blanks An acceptable instrument blank must be run at
least once every 12 hours and immediately prior to the analysis of
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Procedure No.: MI-PEST
Revision: 1
Date: 06/30/1995
Page 15 of 20-
either the performance evaluation mixture or Individual Standard
Matures A and B, decoding on the place in the analysis sequence.
* Sulfur Cleanup BlanksA" sulfur cleanup' blank must be analyzed
'whenever .part of a set of samples extracted together requires sulfur
' .-cleanup. If the entire set of- samples associated 'with a method blank
- ' requires' sulfur cleanup, then .the method blank also -serves- the
purpose of a sulfur blank and no separate sulfur blank is required. *
ป
3.4,2 Rgrtew Items*' .',"" " ' - :
.-..." - * ' I-
Data lequirements and data retrieval procedures for blanks are the 'Same as those tea; fee
field samples because the blanks as well as field samples are validated similarly, FondiTs,
mass spectra, chropiatpgrains, -quantitation reports, eto.t are essential for perforating a
validation of the blanks 'first. ' ". . ' ' . ' -
3,4,3 EvoXuaMom Procure ' . - '' ,'
Validate the "blanks', same as the field samples. Detailed validation procedures are descr .bed
above under appropriate sections. Use the validated blank results for a comparison with
the sample results. Mafc certain that the simples and blanks are evaluated on the $ame
basis of sample weight or'volume* dilution factors, "moisture content, eteVTUse the 5 (or
10) times the highest blank concentrations for qualifying the sample date. More
specifically, the blank'data evaluation procedures are as fellows:,
Review the results of all associated blanks, Form I PEST, and Form IV
PEST, and chromatograms to evaluate the presence of TCL pesticides.
* Verify that method blank analysis has been reported per SDG, per matrix,
per concentration level, for each GC system used to analyze samples, and
for each extraction batch.
* Verify that the method blank analyses do not contain any target pesticide or
Aroclor/Toxaphene at greater than its Contract Required Quantitation Limits
(CRQL).
For the surrogates in each method blank, verify that the observed retention
times are within the appropriate retention time windows calculated from the
initial calibration.
* Verify that the instrument blank'analysis has been performed every 12 hours
as part of the continuing calibration and following a sample analysis which
-------
Procedure No.: MI-PEST
Revision: 1
Date; 06/30/1995
16 of 20
contains an analyte(s) at high eoncetttratiQn(s), and that the instrument blanks
do not contain any taiget analytes above one-half the. CRQL, assuming that
the material in the instalment-resulted from Hie extraction of a 1-L water
sample; '.._.'
# * l"
* : Verify that the suHur cleanup blanks were analyzed at tne'iejqpixed frequency
! ' and that * they do not contain any target compound above; the CRQL,
' assuming that the material in die instrument resulted from-(he extraction of a
.1-L'water sample;' If a separate sulfpr cleanup' blank -vvas\;piepattd, one
.; version of Form IV PEST should be completed a$soeiatlng;ซaiitfae
with the 'method blank, and a second 'version -of Form IV;PEST should-toe
completed-listing,, only those samples associated with the separate sulfur
cleanup blank, . , ' ,ป'-"';, ... v -./.';,.'" >.-;'-'-
'3t,4.4 Action : .' . ;..' '"-" -:" ' .
If the appropriate blanks were not. analyzed with the'frequency described in Criteria 3, 4, -
and 5, then the data reviewer should use professional judgment' to determine if the *
associate! sample data should-be qualified. Hie reviewer may. need to obtain additional
information from (he laboratory. The situation should be brought to the attention of the
TJPO. " ' , ' '
Action in the case of unsuitable blank results depends on the circumstances and the origin
of the blank. Detected compound results should be reported unless the concentration of the
compound in the sample is less than or equal to 5 times (5x) the amount in the blank, In
instances where more than one blank is associated with a given sample, qualification should
be based on a comparison with the associated blank having the highest concentration of a
contaminant. The results must not be corrected by subtracting the blank value.
Specific actions are as folows:
* If a target pesticide or Aroclor/Toxaphehe is found in the-^blank but not
found in the sample(s), no qualification is required. If the contaminant(s) is
found at level(s) significantly greater than the CRQL, then this should be
noted in the data review narrative,
* Any pesticide or Aroclor/Toxaphene detected in the sample, that was also
detected in any associated blank, is qualified if the sample concentration is
less than five times' (5x) the blank concentration. The quantitation limit may
also be elevated. Typically, the sample CRQL is elevated to the
concentration found in the sample. The reviewer should use professional
judgment to determine if further elevation of the CRQL is required,
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Procedure No.: MI-PEST
Revision; i
Date: 06/30/1995
Page 17 of 20
"Hie reviewer should note that analyte concentrations calculated for method
blank may not involve the same weights,; volumes, or dilution factors as the
associated samples. These factors must be into consideration when
applylng'fhe "5x" criteria, such that a comparison of the total amount of
contamination is actually made. , '
In addition, there may be instances .when little or no contamination was
present m the associated blanfcs, but qualification of the sample was deemed
necessary. Contamination introduced through dilution is one example.
Although it is not always possible to determine, of this occurring
can be detected when contaminants are found in the diluted sample re iult,
but absent in the undiluted sample result. Since both results are not
' routinely reported, it may be "possible" to verify mis source of contamination.
However,'if the reviewer determines that the contamination is from a so nee
other than'the-, ample, he/she should qualify-. Ihe "data, to-this-ease, the-
**5x"' rale-does not apply; the. sample value should be -reported is a,
nondetected taif et cdmpound, "U." - _, ' .:
* , ' If gross contamination exists (i.e., saturated peaks), all affected compounds
. -in the associated .samples 'should be qualified as unusable (R), due to.
'iriletieience. "Ms should be noted in the date, review- narrative if: the
contamination is suspected, of having an effect on the sample-results. :
* If inordinate amounts of other target pesticides or Aroclors/Toxaphene-are
found at low levels in the blank(s), it 'may be indicative of a problem at the
laboratory and should be noted in the data review narrative.
* If an instalment blank was not analyzed following a sample analysis which"
contained an analyte(s) at high concentration(s)ป sample analysis results after
. the high concentration sample must be evaluated for carryover. Professional
judgment should be used to determine if instrument cross-contamination1 has
effected any positive compound identification(s), and if so* detected
compound results should be qualified. If instrument cross-contamination is
suggested, then this should be noted in the review narrative if the cross-
contamination is suspected of having an effect on the sample results.
The following are_ examples of applying the blank qualification guidelines. Certain
circumstances may warrant deviations from these guidelines:
-------
Procedure No,: MI-PEST
Revision: 1
. Date: 06/30/1995
Page 18 of 20
Example 1: Sample result" is greater than the CRQL, but is less than the 5x
multiple of the blank result.
Blank Result
CRQL' -
Sample Result
Qualified Sample Result
&
1.0
.0.5
4.0
4.01
In this case, -sample -results less than 5.0 (or 5 x 1.0) would be
qualified as nondetected target compounds.
Example 2: Sample result is less 'than the CRQL, and is also less .ten the 5x
multiple of the blank result.,- ' ; ' , .
Blank Result
CRQL" ..
Sample Result
Qualified Sample Result
1.0'
0.5
0.4J
0.4B
Example 3: Sample result is greater than the 5x multiple of the blank result.
55
Blank Result
CRQL
Sample Result
Qualified Sample Result
1.0
0.5
10.0
10.0
In this case, the sample result exceeded the adjusted blank result (Sx
1.0) and the sample result is not qualified.
ป Record blank contaminants on QSFs. "
If the sample concentration do not meet the criteria of 5 (or 10) times the Wank
concentration, the sample results should be considered essentially undetected (or as not
detected substantially above "the levels reported in the blanks); therefore, flagged "B" in
accordance with the Region III data validation guidelines.'
-------
Procedure No,: Ml-PEST
Revision: 1
Date: 06/30/1995
19 of 20'
'3.4.5 Reporting
Form I*s may be used to write* the **B"*' data' qualifier for the data not meeting the Hank
criteria. Additional discrepancies may1 be included in the overall report for the Level Ml
validation. ,',:"' ' .
''3;5, Sample Paperwork \ ' ' . '. , . .-'''"'
The purpose for evaluating the sample paperwork is to determine that the samples being
validated are'indeed "the ones' taken from the ate, and ^ have'not ".been, tempered with.
Accurate sample identity, is of. paramount importance In substantiating the sample data. '
Without unequivocal sample identity and chsun^f-custody.procedures, the sample data may'
hot be defensible 'or enforceable. , ป'" _. _ : ' '
- Under the current "CLP contracts, the original paperwork (I.e., the"purge package oij the
administrative record) is included in the 'data package from the laboratory. If is assumed
. that the'data validator is not privy to the original paperwork; therefore, the evaluation
criteria and procedures described below apply only to the documents that are generally
, ", included to the data validation package. These documents are the chain-of-cttstody fo,nns
and Region in SMpping_Record,
3.5.1 Acceptance Criteria - . ,- ^T
Criteria for acceptability or authenticity of the sampling paperwork, document control! and
chain-of-custody have been established by the National Enforcement investigations Center'
i (NEIC), in support of the CLP. Overall criteria are too numerous and subjective to be
discussed here, but the criteria that apply to data validation are:
i The chain-of-custody form should be properly and completely filled out
! including the sampler signatures, date and time of sampling, sampling station
i identification, analyses .requested, traffic numbers, tag numbers, etc. These
data are minimally required to confirm the authenticity of the ample and its
data,
* The chain-of-custody must be maintained at all times. The custody transfers
between different parties must be signed and dated,
\ ' '5.5.2 Review Items
i . A copy of the chain-of-custody form originated in the field and that returned from the
; laboratory with the data are essential to confirm the identity of the samples. In addition,
-------
Procedure No,: MI-PEST
Revision: 1
Date: 06/30/1995
20 of 20
tfjie Region ffl Shipping Record is to identify the field QC samples. The-chain-Gf-,
custod'y and Shipping Record are generally located in .front of the
3.5.3 Evaluation Procedure . ; ' .
Ensure that 'the chain-of-custody form was and' dated by the samplers, and a time .
apd weie for sample collection. The laboratory '"'of fee ehaui-of-autody
' must have the signature of theJaboratory sample custodian.'' Any on the form should
have been- crossed! out viith a single Mne through the entry. Verily-' fhai alt. collected
have unique station, identification, traffic numbers and tag numbers.
Ensure, that the Region ffl Shipping Report correctly reflects the information on the-chain-.
oi-custody. _ /" --_ ,, - ' "" . . " .-'":.; -,-
< . - - , . .,ป""*' / . - , , - ,,;-';-.-ป*/'
3.5.4 Action. .-.-' ' . ' ";'* " '' '.'
The action to be taken in qualifying the is highly dependent on the of the
problem. Some errors in. paperwork are practically unavoidable,in real situations. An.
effort should be made to reconcile the differences by checking the field
a gainst the sampling paperwork. Occasionally, the samplers may forget to the chain-
of-elistody; however, the field notebooks may- amply describe- me -sampling event
Problems are also inevitable in noting or cross-referencing teg numbers and teaffic
numbers, CaeneraEy, there are alternate sources of infoimation to..substantiate or
refute the problem.
,3.5,5 Reporting
Any discrepancies found In the paperwork must be immediately brought to the attention of
the EPA RJPM or SPO. Clearly define the problems in a memorandum to the responsible
'parties. Attach marked copies of the chak-of-custody forms to substantiate the findings.
-------
Procedure No.: M2-PEST
Revision: 1
' * Date: 06/30/1995
Page! of 3 f:
Appendix 'C-2
Validation of Organic Analyte Data-
' -Manual -Level M2 ' ":
' to manually validate "the pesticide analyte
organic data using the manual innovative data validation approach at Level M2.
' focuses on' .the use of. irijforanatioi .contained on the CLP forms, arid a fewe^ 'of
: ;." dtoDitiatomms- as summarized in 3$ble M2-BB$T4,
x! .vu '. ' - :' .-.W;r'.?*-v*.-1 '"'-'. ^/
*>'>$:..'' - '" ' .--. ' ' .' ' ^>-- :fซf- ''. ..*'".
the app!
/;';;';';Date.validated using te.procedaie axe ccnuideared. usable for.'the-following.typei of-
.'.""',- purfปซs; however, _ the -dat&i^iisets: must, decide -on t case-by-case basis' whether the
:' .procedure is suitable foriheif .intended data uses. The suggested data are: ,:
'..' ' - *. ' Oversight of activities led by other parties . ' -17,"
*'
. * Comparison to -action levels
Initial site investigation _ .
ป Contamination sources .
* Nature and extent of contamination
Preliminary risk assessment
* Risk assessment with known high levels of toxics
ป Feasibility study
* Preliminary design
* Treatability study
Initial cleanup verification
-------
Procedure No.: M2-PEST
Revision:' 1
Page 2 of 31"
'- .. mm
GM R^S-HKTIGIDE-FOLYCfflLORINATED
.Acdon LeVd-
ContiEuing Calibration (RPD) *';*
Laboratory Blank '
(%R, BUD)
Field Quality Control (dup., blnk., PE amp*.)
Sample Paperwork
Holding Time
Retention Time
Surrogate Recovery
Dilution Factor
Moisture Content
Pesticide Cleanup Checks
Chromatograms
Raw Data
Ml,
X
-------
Procedure No,: M2-PEST
Revision: 1
'06/30/1995
Page 3 Of 31-
2. Quality Control Measures Checked
Wile M2-PEST-1 highlights the quality control (QC) evaluated under this date
validation procedure. '
. . " -.' '-. ' ;' 3. Procedure '- \
"Hie fofldmng*sil>secfioiis''de^OTlbe"ftff eajeh of ttd'*QC indicate*'the criteria,
location and retrieval of QC data, evaluation of-the QC data, actions taken In the event the
QC acceptance criteria are exceeded, and documentation of the QC violations in a
standadizedteoottforfn. , ... . ,
, ' * _ f m <
" ' '" , " *" , "-*" *".".*.
The pesticides data requirements to be checlced are listed below: ^ '
, **f '*""*" f"* ' '**-.ซ f
3.1 Action level NottficaJfon . ,//'^' ;
3.2 Techmcal Holding times (CCSC^nttactoalholdijig'ti.ines.only)
3.3 GC/KD Instalment Performance Cheek '
3.4 Initial,CaMteation (CCS). ' ' . ;^
3.5 Contimung CaHbration (CCS)
3,6 ' Blanks.
3,7 Surrogate Spikes (CCS) .
3". 8 Matrix Spikes/Matrix Spike Dupicates
3.9 Pesticide Cleanup Chosks -
3,10 Reported Contact Required Quantitation Limits (CRQLs)
Two fortos have been developed to assist in the performance and documentation of
implementing Level M2. The first form, M2-PEST-QUAL, summarizes holding time,
calibrations, blanks, surrogates, and internal standards. The form, M2-PEST-SPK,
summarizes surrogate and matrix spike quality control -checks. These forms are presented
on the following as Tables M2-PEST-2 and M2-PEST-3.
Reporting requirements for Level M2 are as follows:
-------
Procedure No.; M2-PEST
Revision; i
06/30/1995.
4 of 31
Hand flic Pom I's, including:
, Data validation
_ number
Sampling,
Provide .. . " '
. - A statni^l^ define ibe level of the ซtota-iซฅlewป i.e., M2
Major and miaor problems assockted with the analysis
-~ Highlight issues that may have affected detection limits ,
ItteJtode the
; ' .Iist
Support documentation including forms that support assigning data
'
_ .
Samples % should be listed OB the appropriate
' : * '
Data qualifiers in this review are as follows: ,
Codes Relating to (Confidence Concerning or Absence -of
Compounds): -. ! .
-" ^"^
* ^i
V ป Not detected. Hie number ^proximate sample
o>acoitraion to be detected.
PO CODE) = Ccmfirmed
B * Not substantially above the level in laboratory or
blanks.
R = Unreliable result. Analyte may or may not be present in the sample.
Supporting necessary to confirm result,
N = Tentative identification. Consider present. Special methods may be
to confirm its presence or in future sampling efforts.
Codes Related to Quantltation (can be for both positive results and sample
quantitation limits):
J = Analyte value may not be or
-------
Method 608/8030
Cause No:__
SDO No-.', _'
Pneediw H0.S M2-PEST
Revision: 1
' DutK peOO/1995
j - TABLE WB-FESM
FESTICrDE/PCBS QUALIFIER SUMMARY (CAI,!B5UTIONS, BLANKS, HOLDING TIME, SURROGATES, INTERNAL
! STANDARDS . - f
Dste Analyzed:
fefaltJK
'jMMMOl'lb-
. Me&o:
Earsction Date;
Cotemeu Prisaary
"CwnfMwl: .
. Sample Idsjflificn
- . ..- , ,,, *
.'.' =:"?: ' ,-; ".- '
'.. ..' >f, .i.v.--,"-,-"._ ; '_
"'ซ";ฃ-, ".-;..!>'<*V
'>v- / ;, ., ^ /-
.":.' '- -. . * '..
-.--;,'',"" '
Hold Time
Oul, days
fiflt
- . ;. . *' * .'.', " ' '
_j&ML_
* ป f ซ
Lsst [ND Standard before Ansi^sb
I '
*v" " *
?
. "
^ ***/ซ>
, - ' _",
^ <'
?'
i -.vf
.;"-v;5i
.i/-,fS
>i5^
*l":Kf*S
; ' ^' >v
"*" s;'S-
4 "
g "
i^r
<^S||;
:*ฃ&$
V'tv '.'
__AL_ f
{
s
-.-.
j* .
, -ป
,
, ,;":-s-;ซS':i .-"'
.;..i;, ซ. > CriKmtfouft. ' -* ". '" " ":':f?~^
Ub-Cd. ;
ซ
jfe*rfiMC' ' '
J^i-BHC - "
-ririfrPti? : ''''. '.'
ซuwซ-BIiB2iUWซซ^
lt( iHiS^M^s^iwr
t ซf^ffi^B j i
HeutachloT woxide *
Endosniifars J
BfWrin
4 4*-DDE
Etiiirin
Endosulfen II
4".4'-pDD
Endosxil fan KUlftle-
4.4MJDT
Meihoxwhlor
Epdrtu Kiwloniir
itt!flfott'^nI0fllCliB'Ri6
jggnnH-cMpRiMie
nr AX s p ft ts ftft
Aroetor-1016 ffCB-1016'i
AmetocJlZt fPCB-O">H_
^ftEctor-1232 (PCB-t 23|L
Arockir-124? (fCQ-teW '
Amclor- 1248JFCB- 1 24|)
Arocior- 1 254 (fCp- 1254} '
Aitwior* 1 260^ CPCB- 1 260)
DitMiyfcMorenetaefDBa Surr.
8l2w*^l,w Ml
ats/mosilb
Tiwe-"
\t """**
1
*
,$$ป, '' \ '"'-' : .'" ' ' *-^:"^S
" 4 '
.' '*."-
, '-. *^' '
. .
*
' I 4tL^
J]^5.*'*
'',^"^*4
.' '.'' ' 4
'.. * -,,
_v
J
i." k *, ***
; ' -
--,
'.
K
?a?Nis*%
j; V-'-; -'
tV>" .'
W:.\ " ' .
- . . .
,;,ซ
%
, ^v
t "
ซ
i.
ssESers
-' - v
.* r
* .
*
1
1
Det*cted eoriipounds
1Jitdeiซeted compounds
*D < IS
*D < 20
and %D < 20
or ซD < 20
-------
Method
Cttt No:
SBG N6t
Pwwwlute No.:' M2-PEST
1
;
Atฎ QUA1JW
&ซ^^^ซa
SarojiSe UesJifisr:
^
,
.
Surrogsts R.e*overiซ, %R
Aqueซ33
CM-lSt
-. - ' " .
,- ^
\ -
1 ; '-.
- ** ".
. . .- .
f
-.
Soil
\ *> . - ฐ
. , _ .... .
\'
-
*.
* ' >" .*
)"^%,V-
- " '-. v*. '
. '" '
"
^^flteปf*Q_
< ~
-:
, - .
,>
. - .-* -
4 * -
*
Ceปpoซ}i:
Matrix Spike, Rccor try,
%R .
Acted
Matrix Dupicatซ,
RซOTW._%R
Actual
MSMSD
PrwdsMJn. RPB
Quidiflere
|4-/-ป
AQUEOUS SAMPLES ^^
jmwa-lWC ^LiwIiiK)
HepUcMor
Aldria
DkHiin
Endrin
4,4'-DDT
56-123
40-131
40-120
52-126
$6-121
3H27
5ซ-1B
40-131
40-120
52-126
$6-121
3*-n7
14
20
22
!t
21
3?
SOIL SAMPLES
gซmim*-BHC (Ufl4*n*|
HepiMhlor
Atdrin
Dwldrin
Eadria
4,4 '-DDT
48-127
3S-130
34-132
31-134
42-139
23-134
46-!2?
35-130
34-132
31434
42439
23-134
50
31
43
31
45
50
==8SE
1
-------
Procedure No.: M2-PEST
Revision: 1
06/30/1995
Page? of 31,,
K " = Aualyte present, Eeported value may be biased high. - Actual value is
expected lower.
JL =* Analyte present Reported value may be' low. Actual value is
expected to be higher.
UJ " = Not ducted, (pantitation Emit jnay be inaccurate or imprecise.
- ' -,"'.** \
HJL ซ. ' '
Other Codes . _ - ' .
Q '.../.= NO analytical-result. ," -* '. " . ' ""':,, . -
t f '
* = Results reported.from diluted analysis. .' ./
3.1' Action Level Notification " /'.'.
Hie purpose behind'action-level, notification is to tide EPA'ItemedialProject Officer
(RPM) or the Site Project Officer _(SPO) aware of the potential human health risk, at the
site. In accordance with the Region ffl Hazardous Waste Division- policy, the EPA RPM
or SPO must be promptly notified of any conteminant the level
or the 10-day health advisory limit The data for contaminants exceeding "the action levels
must be validate! as a top priority and reported to the RPM or SPO, Validation of the rest
of the data may then be completed normally.
3,1.1 Acceptance Criteria for Action Level Nefificotum
EPA's Office of Sold Waste and Emergency Response has. esfebHshed 10-day advisory
" Emits or the action levels for several organic compounds and elements of special health risk
concerns based on the Safe Drinking Water Act, The pesticide organic compounds and
their 10-day health advisory limits apply only to aqueous samples and are listed in Table
M2-PEST-4, The criteria for action level notification are as follows:
ป The contaminant concentration must be equal to or above the established 10-
day health advisory limits.
Data for contaminants exceeding the action levels must be validated as a top
priority. ' '
* The foEowing EPA personnel must be notified of the action level
exeeedances:
-------
BPA or SPO
BPA Section Chiefs: .
- ' i Site, Investigation (SI)
- . Remedial
- . Bnfoieeiaait-
- -. RCRA. . . '
Procedure, No*: M2-PEST
Revision: i
'
' Page8"of31
.- " , Brifcttwneat ' , '
Sttperftad , . "
, - , ..RCRA "' .
f i
''",", ; , *Xlr ** . i ,
The remaining data validation. should be completed per normal procedures.
Any special instructions from the Hazardous Waste Division should be
followed. " . ." . -
Records should be kept of the date review, action level notification and any
' follow up instructions and actions. '
. 1Uปle M2-PEST-4 ' : ^
AND POLYCHLOMNATH) AND ACTION
DEVILS
Compound
Chlordane
HeptacMor
Methoxychlor
' , Action
Level*
63
10
2,000
Compound
Endrin
Xindane
Toxaphene
Action
Level*
5
1,200
m
*A11 units ajre ug/1.
3.1,2 Data Requirements and Retrieval of Data
All data required to perform Level M2 validation, as in the following sections, are
necessary for carrying out action level notification. The, location of the and their
retrieval procedures are discussed below.
-------
Procedure No.: M2-PEST
Revision: 1
Date: -06/30/1995
Page 9 of 31-
3.1,J Evaluation Procedure'
The evaluation process preceding action level notification will priinadly consist of
comparing the results on Form I's with the action levels in Table M2-PESTซ4.
Following the identification of the contaminants exceeding the-action* levels, focused
validation should be .performed using the criteria, and procedures described in the
appropriate sections below, _ *:..' _ - _ . _".'-'.^':^;:''.'-..''.
3.1,4 Action ' ' , " ':"/^i-'~''-..
The action resulting from focused data validation will be the notification of action' level
orcdsdance to the porsonnel identified above in Section 3.1,1. ' ' .
...;_-.: . - ,'. , :,;;i
J.1.5 '.;.'.'' ".'. - ' ' ; '.-:;.-ป-
:& -
, Copies of Form I's can be used to highlight the contaminants above the action levels. The
findings of the focused validation can be summarized in a memorandum, and the data'
qualifiers resulting from focused validation may be written on the Form Fs. - The marked
up forms should be clarified, that they represent validation of only, the contaminants
exceeding the action levels, and not all data,
3.2 Technical Holding TJmes _ . '. -^ .
The objective is to Meertain the validity of'results based on fee holding time of the sample"
from time of collection to time of sample extraction'and analysis.
3.2.1 Acceptance Criteria
Technical requinements for sample holding times have only bean established for water
matrices. The holding times for soils are currently under investigation. When the results
are available they will be incorporated into the data evaluation process. In addition, results
of holding time studies will be incorporated into the data review criteria as the studies are
conducted and Approved, The maximum holding time, as stated in the current 40 CFR Part
136, for pesticides and Aroclors in cooled (@ 4ฐC) water samples is 7 days from sample
collection to extraction and 40 days from sample extraction to analysis. It is recommended
that pesticides and Aroclors in soil samples be extracted within 7 days of sample collection.
The contractual holding times, which differ from the technical holding times, that
extraction of water samples by separatory funnel must be completed within* 5 of
validated time of sample receipt (VTSR), extraction of water samples by continuous liquid-
liquid extraction procedures must be started within 5 days of VTSR, and soil/sediment
samples are to be extracted within 10 days of VTSR, Also, contractually both water and
-------
Procedure No.:
Revision: I
Date: 06/30/1995
Page 10 of 31
soE sample extracts- must be analyzed within 40 days of extraction. However, the
contractual delivery due date is 14, days or 35 days after receipt in the laboratory of
the last sample In the SDG, depending on the contract.
3.2.2 'Revtew .'..':.'... . . .;.'-.-..
Form I BBSf, EPA Sample *Mffic.ป^ortt:.aod/or chak-of-custody.-. . .. -;,,_. .
3.2.3 '
Technical holding times for. ample extraction are established by comparing the sample'
collection -dale on, the EPA Sample Traffic Report with the of extraction on Form 1
PEST. To determine if the samples were analyzed- within the holding time after extraction,
compare the dates of ซteaction,oii.FofniI"lBSr. , " '.-'','",..' "^;':"-
Verify that the traffic report indicates that the samples wore received intact and iced . , If the
samples were not iced or there were my problems with, the samples upon receipt, then,
dtoepanties in Che sample condition ittuld affect the data. .' >*- ' VN... :
3.2,4 Artfoii " : -\ *' . ,'-. ';;;.'-:-
1. If technical holding are exceeded, qualify 'all dieted, ccmpfimd results as
estimated "J" and sample quantitaiion limits as -estimated **UJ," except for PCBs
which ate not expected to degrade significantly during storage.
2. If technical holding times are grossly exceeded,* either on the first analysis or upon
reanalysis, the reviewer must use professional judgment to determine the reliability
of the and the effect of additional storage on the Jesuits. The reviewer
may determine that detected compound results or the associated quantitation Emits
are approximates and should be qualified with "If> or **UJ," raqซtively. The
reviewer may determine that nondeteeted target compound data are unusable (R).
3, Due to limited information concerning holding 'times for soil samples, water holding
time criteria should be applied,
4, The reviewer should also be aware of the scenario in which the laboratory has
exceeded the technical holding times, but met contractual holding times. In this
case, the data reviewer should notify the Regional TPQ (where samples were
collected) and/or RSCC that . shipment delays have occurm! so that the field
problem can be corrected. The reviewer may this information on to the
laboratory's TPG," but should explain that contractually the laboratory met the
requirements.
-------
Procedure No.: AC-PEST
Revision: 1
'
Page 11 of 31-
3.3 GC/ECD Instrument Performance Check
Performance checks on the gas chromatogra])h. with electron capture (GC/BCD)
system UK performed to adequate resolution and instrument sensitivity. These
criteria are not sample specific. Conformance Is using standard
'' '
Resolution Cheek Mixture
a.
The Resblutipn Check Mature must be analyzed at the beginning of every
initial calibration sequence, on eath'GC column, and instrument used for
analysis.-- . Tbe -Resolution Check Mature the.lbllowifig 'pesticides
..'*- ' ' " *
and -
.
:Bridosulfei: I
4,4'-DDE
Endosulfan sulfate
Endrin iaetone -
Mefiioxyefalor
TettacMoro-m-xylene
Decachlorobiphenyl
b,
TJie dq>th of the valky betw^ two adjacent in the Resolution Check
Mktofe must be than or equal to 6CLO percent of the of the
shorter peak.
Performance Evaluation Mixtures
a. The Performance Evaluation Mixture (PEM) must be analyzed at the
beginning (following the resolution check mixture) and at the end of the
initial calibration sequence. The PEM must also be analyzed at the
beginning of every- other 12-hour analytical period, The PEM contains the
following pesticides and surrogates.
* " gamtna-BHC
ป alpha-BHC
ป 4,4J-DDT
ป beta-BHC
-------
Procedure No.:
. Revision: 1
Date:
Page 12 of 31
* Bndtin
Methoxychlor .
* Tdrachloro-m-xylme
b. The resolution of adjacent peaks for the PEM injectioiis in .each; .calibration
- ' (initial ami continuing) mist be 100 percent for both GC coluiims.' , - .
c. ' \ The- absofaiterietentfefl- times- of etefr of- tiie'-slngle. aw^piffl^jp^ikiite* and
- surrogates In all PEM analyses must be witWn the specdfic^ietention time
: windows centered around the mean retention times detertiaii^d from file
' . thae-point initial 'caUbraiion using, thekdiwdM.Sd^^lMllrw.-, A-list
., of '
-. , -. .
"Pot example, for t given pesticide, the- mean.
determined torn' the initial calibration .and found to be,12.69;.jiikiites. The
retention time window for this pesticide' is. ฑ0,05 Auiw^j;!pttPdtew, the_
, "-" ' "*" ~' "'.* i" ' '
dl. Hie nbljve percent difference pPD) betwem tte;afailatel amount tad the
brae amount for each of the single component pesticides and surrogates in
the "PEM. analyses must be less than or equal to 25. Q percent . . ' ' .
e. The percent breakdown is the amount of decomposition that 4(4'-DDT and
Endrm undergo what analyzed on the GC column. For Endrin, the percent
breakdown is' determined by the presence of Bidrin aldehyde and/or Bndrin
kewne in the GC chromatogram. -For 4,4'-DDT, the peroat breaWown is
determined from the presence of 4,4'-DDD and/0r 4ป4'-DDE in the GC
chromatogram. 'The equations used to verify these calculations are provided
' in Attachment 1, Equations A and B,
i. The percent breakdown for both 4,4'-DDT and Bndrin in each PEM
must be less than or equal to 20.0 percent for both GC columns.
. , ii. The combined percent breakdown for 4,4*-DDT and Endrin in each
PEM must be less than or equal to 30.0 percent for both GC
columns,
3.3.2 Review Items .
Form VI PEST-4, Form VD PEST-1 Form Vffl PEST, and chromatograms.
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Procedure No.:-- M2-PEST
Revision; 1
Page 13 of 31
3.3,3 Evaluation Procedure *
1, Resolution Cheek Mixture "
a. ' Yerify firofli Acf/ifem Ym PEST flat the 'mixture was
analyzed at the bepmiliig of the initial calibration sequence on each GC
cotenii il^'iiuitzSBi^itiised for analyas. ~ -"';';-"-'
b. Cheek- the fesofaticn and Form VI PEST-4 to verify
the resoluticm criterion between two adjacent _ for the required
compouBds'is less'thaii or equal to 60 percent. ' ' ,
', -' " " ~
2, Performance EyaluaticS"
/ , .
Veiirr ..from- that the Evaluation Mktuie
*" j " ii;-iysfe-w*%l'**^ฃfe: ' j ' *i! - :
was analyzed it the;prol>er:%equency and position sequence.
' " -
a, .. Check the PEM data from the initial and continuing calibrations 'to verify
that the'resolution between adjacent is. 100 percent on both GC
columns.-.'vi*" v:vl- - ./ , -,'--,
' b. Check the PEM data from the initial and continuing calibrations and Form
"VH PEST-i to verify flat the absolute retention 'for lie pesticides in
each analysis are within die calculated retention time windows based on the
mean RT from the three-point initial calibration using equations and
- examples found in Attachment 1, Table 1.
d, Verify that the relative percent difference (RPD) between the calculated
amount and the true amount for each of the and surrogates is less
or equal to 25.0 percent "
e. Verify that fee individual breakdowns for 4,4'-DDT and Endrin are less than
or equal to 20.0 percent, and that the combined breakdown is less than or
equal to 30.0 percent.
3.3.4 Action
Resolution Check Mixture: If resolution criteria are not met the quantitative results
may not be accurate due to inadequate resolution. Detected target compounds that
were not adequately resolved should be qualified with "J." Qualitative
identifications may be questionable -if coelution exists. Nondeteets with
retention times in the region of coelution may not be valid, 'depending on the extent
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. Procedure No.;
Revision: 1
Date: 06/30/1995
Page 14 of 31
of -the problem. Professional judgment should be used to determine the need to"
data is unusable- (8). , " "
2. Performance Evaluation Mixture Retention limes: Retention time windows ore
used in qualitative identification. If the retention times of the pesticides' ia the PEM
. do. not fall within the retention time -windows, the associated : sample results should
. be carefully evaluated. All samples injected after the last in-coatrol standard are
, , pot^i^afly "affected.; 'It 'should be rioted for TPQ action if toe PBMiซteiticMi:ttme
"
.. .
a.' For the affected samples, check to see if the sample chromatograms coafain
- any peaks that are close to the expected retention time window of the
pesticide .of itttfflpst; :';lf no peaks are' present either' wil^^^ose to lie ,
retention time wiadow of the deviant target pestidde compotJhd^
. 'is usually no effect on the data* (i.e. , nondetected values can be;coasidered .
. valid); - 'Safjple;'! data' tint, aie . potentially affected 'by standwfc" not -naeetiiig '
: " the retention tune windows should be noted k the data review narrative. '
b. If the affected' sample chromatograms contain -peals. -which .'may' be of'
'coiuiem'.
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Procedure No.: M2-PEST
Revision: 1
Date: 06/30/1995
Page 15 of 31
c. If the reviewer "cannot do anything with .the data to resolve the problem of
concern* all positive results and quantitation limits should be qualified **R,f ' '
3, Performance Evaluation Mixture Resolution: If PEM resolution criteria are not met
then the quantitative results may not be accurate due to resolution.
Positive for cx>mpounds that woe 'not should be
qualified with "I,**. Qualitative; identifications may be questionable If coelution
exists. NoadetectedtaJ^-compoimdsthatelutein the re
not oe valid" depd^mg^otfr'tBe"-"wiw^"'of' fc'.eoetatioii^pft^lemr^Ite^
judgment dioiliibe"-teed;^i|wJ%-d*i as inmsable (R). .'"
4.- If RPD criteria, axe nofioe^jitflify all associated positive during
the analytical sequence' -.withW" and ' for
"
5. 4f4
a. - If 4s4f-DOTbiปMon:"is Crater than 20.0
i ' aU'picMifhe for DOT as "L" low. If DDT
was not detected, but DDD and DDE 2re delected, then qualify the
quantitation limit for DDT -as 'unusable (R),
ii. Qualify- positive for DDD and/or- DDE as" presumptively
present at an quantity (N).
b. If Endiin breaMown is grater than 20.0-perce&t:
i. Qualify att poative for Bidrin with **J," If Endrai was not
detected, but Endrin aldehyde and Endrin tetone are detected, .then
qualify the quantitetion limit for Endrin as unusable (R).
ii. Qualify' positive results for Endrin ketone as presumptively present at
an approximated quantity (N).
c. If the combined 4,4*-DDT and Endrin breakdown is greater 'than 30.0
percent:
i, QaaHfy all positive for DDT and with **J. " If Endrin
was not detected, but Endiin aldehyde and Endrin ketone are
detected, then qualify the quantitation limit for Endrin as unusable
(R). If DDT was not detected, but DDD and DDE are detected, then
qualify the quantitation limit for DDT as unusable (R).
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No.:
Revision: 1'
Dale;
Page 16 of 31
ii. Qualify positive for Bndrin tetone as presumptively present at
an, estimated quantity (N). Qualify positive results for DDD and/or
DDE as presumptively present at an approximated quantity (N),
i *
6. Potential cur the sample resulting from the initial calibration problems
' , .' should be noted intjted^nwj^'nanative, - _. . . .-,.-
3.4 irftial/CalibnilfoiL -.''. , _(.- - ' " ,' .,.' ,"'"'
* '* ""'"*", " " .ฐ '." ^
Compliance requireraeiits for satisfactory initial calibration ace established to ensure that
the instrument is capable of producing acceptable qualitative and quantitative data for
pesticide and Aroclor target compounds. Initial calibration demonstrates that the
instrument is capable of acceptable performance aithe beginning of the analytical
and of producing a linear rcalibratioa curve.
3,4,1 Acceptance Crtte A- :\^' .
1. .. Mdiyidual Staadaid
-a, Individual Stunted Mixtures A and B (containing all of the single
component and surrogates) must be analyzed at low, midpoint,
mid high levels during the initial calibration, on GC column and
instrument used for analysis. ' "-'',
b. The resolution between any two adjacent peaks in the midpoint coneenttation
of Individual Standard Mixtures A and B in the initial calibration must be
greater than or equal to ,90.0 percent on both columns,
c. The absolute times of each of the single component pesticides and
surrogates are determined from three-point initial calibration using the
Individual Standard Mixtures. A Est of .the retention time windows are
included in Attachment 1, Table 1.
d. At least one chromatograni from each of the Individual Standard Mixtures A
and B must yield peaks that give recorder deflections between 50 to
. 100 percent of full scale.
e, The concentrations of (he low, medium, and high level standards containing
all of the single component pesticides and surrogates (Individual Standard
Mixtures -A and B) must meet the following criteria on both GC columns,
The low point corresponds to the CRQL for each analyte, The midpoint
concentration must be four times the low point. The high point must be at
least 16 times the low, point, but a higher concentration may be chosen.
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Procedure No,: M2-PEST
Revision: 1
06/30/1995
17 of-31
f. The Percent Rditive Standard Deviation (%RSD) of the calibration
for 'of the single component pesticides and in the initial
* calibration on both columns for-Individual Standard Mixtures A and B must
be less than or equal to 20.0 percent, except as noted' Mow. For the two
- ' surrogates, the %RSD must be less than or equal to 30.0 percent. Up to
two single component target pesticides (other than the surrogates) per
- ,' - column way exceed flic '20,0 percent limit .but It* .XB^^ii^;'.be..le8s than
' -'or eqw4,.to^36.0.peBeentป. CtitadBtion.ir.incindftW 1,
Equation D.' '" " . , . ;:;
Mote; Either peak area or peak height may be wed to calculate the calibration
_ that are, in turn, used to calculate 'StSD. However; the .type 'of
.peak measurement used to calculate each calibration factor for a given
' ' " compound must be consistent. For example, if peak area is usol to calculate
* , ' ***-,, ^ a j-*, jriw..,^
the low point .calibiation &ctor for endrin, -:ttซl',|hej.iiM-^ซl high-point
calibration factors for endrin must also be calculated using peak
' '
a. ' The MuM^mponent compounds '(the 7 Aroclor .and Tcmpieae) must
* ' each be analyzed separately at a single concentration level during the initial
calibration sequence. The analysis of the multi-component target compounds
must also contain the pesticide surrogates, ''.'-.""
b. For each multi-component analyte, the retention times aft determined for
three to five peaks. A retention time window* of ฑ0.07 minutes Is used to
determine retention time windows for all multi-component analyte peaks,
fc
c. Calibration factor data must be determined for from the
multii-oomponeot analysis,
3.4.2 Review Items
Form VI PBST-1, 2, 3, and 4, Form VH PEST-1, Form Vffl PEST, and chromatograms.
3.4.3 Evaluation Procedures
1 . Individual Standard Mixtures
a. Verify from the Form VHI PEST that the Individual
Mixtures A and B were analyzed at the proper frequency -on each
GC column and instrument used for analysis.
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Procedure No.: M2-PEST
Revision: 1
Dote:
Page 18 of 31
2. Multi-Component Target Compounds
a.' Verify from the Form Vffl PEST that each of .the multi-
compoaent target coBDpoirnds were ^analyzed 'at.-the required
fhqaepcyi.. * ./." .
b. Check the data_for the. multi-component target" compounds and
^Fonn PBST. VI-3 to verify that a least fltree^peakS'-^ete used for.
cal ibration and that retention time 'and' cai ibration, factor data are
available for-'each peak. - ' ; ' r'A
3.4.4 Action ;y '^\;:.-~- x.!;.-' /,. 'r, :,.';; " .
1. - If the initial calibration sequence was cot followed as required, professional
judgment mast be' "to "-evaluate the effect of the non^rapliance am the ample:
data.' If the' requirements for the initial calibration sequence were not met, then this
should, be noted for TPO action. If tie nonncoinpliaiice has a potential effect on the
data, then the data should be qualified according to the professional judgment of the
. reviewed and flris shpiiU be noted' in toe data review, narrative.
2. . If resolution criteria are not met, then the quantitative results may not be accurate
due to peak overlap and lack of adequate resolution. Positive sample for
compounds .that weaป-not adequately resolved shouM be qualified with "J."
Qualitative identifications may be questionable if coelution exists. Nondetected
target compounds that diute in the region of coelution may not be valid depending
on the extent of the codution problem. Professional judgment should be used to
qualify data as unusable (R).
3, If the %RSD linearity criteria are not met for the compound(s) being quantified,
qualify all associated positive quantitative results with "J" and the sample
quantitatiofl limits for nondetected target compounds with "UJ,1
tป
4. Potential effects on the sample data due to problems with calibration should be
noted in the data review narrative. If the data reviewer has knowledge that the
laboratory has repeatedly Mled to comply wife the requirements for frequency,
linearity, retention time, or resolution, the data reviewer should notify the IPO,
3.5. Continuing'Calibration
Compliance requirements for satisfactory instrument calibration are" established to ensure
that the instrument is capable of producing acceptable qualitative and quantitative data.
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Procedure No.;- M2-PBST
Revision; 1
' G6730/1995
Page 19 of 31-
Continuing calibration checks and documents satisfactory performance of the instrument
over specific time periods during analysis,." To Verify the eaffitetioa and evaluate
instrument performance, continuing calibration Is performed, consisting of the analyses of
instrument blanks, the PEM, and the midpoint concentration of Individual Standard
Mixtures A and B. .'" ' . ''.-: :-y ,-,
3.5.7 -Criteria,. . ' . ;" ^ .^^jf:--1
1, An instrument blank' and the PEM must bracket one 'end of a 12-hour period during
which samples axe analyzed, and a second instrument blank and the midpoint
concentration of Individual Standard Mixtures A and B must bracket the other aid
" i of .the 12-four period. ''"'" v 'r-^&v://
2, The resolution -between "any two adjacent peaks in the midpoint ^concentration of
Individual Standard Mixtures A and B must be greater thaiif-;0r equal to.
9G.Q: percent -.''':'''.< " -'-:>-T>^4/' -. '
3. The absolute retention time for each single component pesticide and in the
' midpoint concentration of Individual A and B must be within the
retention time windows determined from the initial calibration, - -'' "
4. The" RPD between. the calculated amount and the true amoustTfo? each of .the
pesticides and surrogates in the midpoint concentration of die Individual Standard
Statures A~and B mast not exceed 25.0 percent.
3.5,2 Renew Items.
Form VH PEST-1 and 2ป Form "VIE PEST, and chromatograins.
3.5.3 Evaluation Procedure .
1. Check the Form Vffl PEST to verify that the instrument blanks, PEMs, and
Individual Standard Mixtures were analyzed at the proper frequency and that no
more than 12 hours was elapsed between continuing calibration in an
ongoing analytical sequence.
2. Check the data for the midpoint concentration of Individual Standard Mixtures A
and B to verify that the resolution between any two adjacent peaks is greater than or
equal to 90,0 percent,
3, Check the date for each of the single component pesticides and surrogates in the
midpoint concentration of Individual Standard Mixtures A and B and Form VII
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Procedure No.: M2-PEST
Revision: 1
date: G6/3Q/1995
Page 20 of 31
PEST-2 to verify tot the absolute retention times are. witMn the appropriate ,
retention time windows. " , ,
4. Check the data from the midpoint concentration of Individual Standard Mixtures A
and B and Form VII PEST-2 to verify that the RPD between the calculated amount
and the true -amount for. each of the pesticides and surrogates 'is less than ฉr equal to
25.0percent," ,:-..V,:.V-:.'." - . ' '. .."">>,. ';" ' '
'3.5.4 Actiom .'- * ,.\.-v" ;;-i, V . ' ..'- "
' 'V- ,' '>..-'',,'-' r ' " -^V' '
1. If the continuing calibration sequence was not followed as .-tequixed, then
professional judgment must be used to -evaluate the effect of the noncompliance oil
the sample data,-_ If the requirements for tfee'continuing calibration sequence were
not met, then this should,be noted fax TPO action. _ If the noncompliance has a
. potential on the; data, then the data should be qiiaMed according to the
professional judgment of the reviewer and this should be noted in the data review
narrative. . - - ... Y-" '." '...'.'*'
2. If resolution criteria are not met than the quantitative may not be accurate
due to inadequate resolution. Positive sample results for compounds that were not
adequately resolved should be qualified with " J." Qualitative identification may be
questionable if coelution exists. - Nondetected target compounds that elute 'in the
region of coelution may not. be valid depending, on the extent oF~tiie coelution
problem. Professional Judgment should be used to qualify data as unusable (R).
3. Retention time windows are used in qualitative identification. If the stoidards do
not fall within the retention time windows, die associated sample results should be
carefully evaluated. All samples injected after the last in-eontrol standard are
potentially effected.
a. For the affected samples, check to see if the sample chromatograms contain
any' that are close to the expected retention, time window of the
pesticide of interest. If no peaks are present either within or close to the
retention time window of the deviant target pesticide compound, then
nondetected values can be considered valid. Sample data that is potentially
affected by fee standards not meeting the retention time windows should be
noted in the data review narrative. If the retention time window criteria are
. grossly exceeded, then this should be noted for TPO action,
b. If the affected sample chromatograms contain peaks wMch may be of
concern (i.e., above the CRQL and either close to or within the expected
retention time window of the pesticide of interest), men the reviewer should
-------
. ' - , Procedure No.: M2-PEST
Revision: 1
Page 21 of 31 -
follow the guidelines provided in Section 3,3 to determine toe extent of the
effect on the data.
If ihe'RPD 25 for the compound(s) quantified, qualify
all associated positive quantitative results with "I" and the quantitation
'5." . Potential, effects on .the .sample 4ata due,to problems wi& calibration should be
-. . noted in flic data xeviewr narrative;" If the reviewer _ his IcnowJedge that'the
': ' ' laboratory has repeatedly failed to comply with the requirements for frequency,
'" linearity, retention-time, resolution, or DDT/Bndrin breakdown* the. date reviewer
, notify the TPO.- ' .-.-/..'
: 3.6 'Blanks..'' -' -;-v.. -.: '; ' . ' '...;-...
' Hie purpose of laboratory (or field) blank analyses is to determine die- and
magnitude of contamination problems resulting from laboratory {or-field) activities. The-
criteria for evaluation of laboratory blanks apply to any blank associated with the samples
(e.g., method blanks, instrument blanks, and sulfur cleanup blanks). If problems with any
blank exist, all associated must be carefully evaluated to determine whether or not
there is an inherent variability In the data, or if the problem is an occurrence not
Effecting other date, ' - . .~;--
3.6.1 Acceptance Cnteria
L No contaminants should be present in' the blanks.
2, Frequency;
a. Method BlanksA method blink analysis must be performed for
20* samples of similar mabrix in each sample delivery group (SDO) or
whenever a sample extraction procedure is performed,
b.' Instrument BlanksAn acceptable instrument blank mist be run at .once-
every' 12 hours and immediately prior to the analysis of either the
performance evaluation mixture or Individual Standard Mixtures A and B,
depending on the place in the analysis sequence.
c. Sulfur Cleanup BlanksA sulfur cleanup blank must be analyzed whenever
part of a set of samples extracted together requires sulfur cleanup. If the
entire set of samples associated with a method blank requires sulfur cleanup,
then the method blank also serves the purpose of a sulfur blank and no
separate sulfur blank is required.
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Procedure No.:
Revision: 1
22 of 31
3.6,2 Review
Form I PEST, Form IV PEST, and
'3.0.3 Evaluation Proct&un -- ,
1. Review flie "of dl blanks, Form 1 PEST,- ?*ปป IV FBST, -and
chiomatogram tb..evalua&^^ - ..'/'.' '
.2, Verify that method blank' analysis- has been reported per ,SD0, -per matxix, per
concentration level, for each GC system used to and for each
extraction batch, _.-.. , . , .-.;.. .-. ,
3. Verify that the method blank analyses do not contain any or
Aroclor/Toxaphene at greater tea- its Contract Required Quantisation Limits
'
4. For the surrogates in each method blank, verify that the observed retention times;
are within 'the appropriate retention time windows' calculated from the initial
calibration, . - .. - - - , . -
5.' Verify that fte iastnimeat blank analysis has been performed every; 12. hoars as part
of the continuing calibration and following a sample analysis which contains an
analyte(s) at high concentration^), and that the instrument blank do not contain any
target aaalytes above one-half 'the CEQL, ' assuming that fiie .material in the
instrument resulted from fee attraction of a 1-L water sample.
6. Verify that -the sulfur -cleanup blanks were analyzed at the required frequency and
that they do not contain any target compound above the CRQL, assuming that the
material in the instrument resulted from the extraction of a 1-L water sample. If a
separate sulfur cleanup blank was prepared, one veraon of Form IV PEST should
be completed associating all fhe "samples with the method blank, and a second
version of Form IV PEST should be completed listing only those associated
with the separate sulfur cleanup blank.
3+6.4 Action
If the appropriate blanks were not analyzed with the frequency described in Criteria 3, 4,
and 5, then the data reviewer should use professional Judgment to determine if the
associated sample data should be qualified. The reviewer may to obtain additional
information from the laboratory. The situation should be brought to the attention of the
TPO. ' .
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Procedure No,: IkC-PEST
Revision: i
Page 23 of 31-.
Action in the case of unsuitable blank results depends on the circumstances and the origin
.of the blank. Detected compound results should be imported and cpiaifiecl "B* if the
concentration 'of the compound in the sample is, less than or equal to- 5 times (5x) the
amount in the blank. In instances where more than one blank is associated with a given
ample, qualification should be teed, on a comparison with the associated blank having the
highest concentration of a contaminant The results must met be corrected by subtracting
'the blank- "'value. . ; *-- -','";*::':,; "' - '' -''y,.?
-". ".. ' ; ', ~;S^:"'- ' . . ".- ,;- <.- " .
Specific actions axe as ftUows:'- ''' . - ' ' -"'.''" '''"."' f'"
1. If a target pestidde or Aroclor/Toxaphene is found in the blank but not found in the
. ttiBfie(s)ป no qudificatiJj^'is inquired. If the. oonteminanl(s) is found at level($)
thrifts CRQLป; thw-'tMs" should be noted in fte data
' 'narrative. ."." ^'". : - ': ! - ."
2. Any pesticide or Aroclor/Toxaphene detected in the sample, that was also detected -
' ' in' any1 associated blank, is qualified if the sample concentration is less ten five.
, times (5x) the blank concentration, > The quantitation limit may also 'be elevated:
~T^IcaEyป, the"" ample ;CRQL 'is elevated to Ac ccraeetttratioii found in flie"~sample.
The reviewer should use professional judgment to determine If further elevation of
the CRQL is required. ' ' .' '
The reviewer should note that analyte wacentmtioM ซIcukted- for method blank
may not involve the weights, volumes,, or dEtttion fectare m the
samples. These factora must be taken into -consideration when applying the "5xf*
criteria, such that a comparison of the total amount of contamination is actually
made.
In addition, there may be instances when little or no contamination was present in
the associated blanks, but qualification of the sample was deemed necessary.
Contamination introduced through dilution is one example. Although it is not
always possible to. determine, instances of this occurring can .be when
contaminants are found in the diluted sample result, but absent in the undiluted
sample result. Since both results are not routinely reported, it may be possible 'to
verify this source of contamination. However, if the reviewer determines that the
contamination is from a source other than the sample, he/she should qualify the
data. In this case, the "5x" rule does not apply; the sample . value should be
reported and qualified "B* and a note should be added to the narrative.
3. If gross contamination exists (i.e., saturated peaks), all affected compounds in the
associated samples should be qualified as unusable (R), due to interference. This
should be noted in the data review narrative if the contamination is suspected of
having an effect on the sample-results,
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Procedure No,:
Revision: 1
Page 24 of 31
4. ' If inordinate of other or Aroclors/Toxaphene are found at
low levels in the blanfc(s), it may be indicative of a problem at the laboratory and
should be noted in the data review narrative.
5. If an instrument blank was not following a sample analysis which
"., - contained an analyte(s) at Mgifa concentration(s), tie
_ high concentration be for carryover, "Professional judgment
should be to determine if cross^^ntaminatiori has effected 'any
fwsitive compound identification(s)ป and- if so, be
qualified. If instrument crossn^ntaminadon is suggested, then this .should bซ
in the data review if the cross-contamination is of'having an
on . " -.-. **^
, . . . . . , ,
following are of applying the blank qualification guidelines. Certain
wiiemat from guidelines: '. ,, i, \ ^ . . /
Example 1:* 'Sample is the CRQL,, but is less than the 5x
multiple of the blank result. . :
. Blank Result ' 1.0 '
CRQL ' 0.5
Sample Result ' ' 4.0
Qualified Sample Result 4.0B
Bi this case, ample results less than $.0 (or 5 x 1.0) would be
qualified as nondetected target compounds.
Example 2: Sample result is less than- the CRQL, and is also less than the Sx
multiple of the blank result.
Blank Result 1.0
CRQL 0.5
Sample Result 0.4J
Qualified Sample Result 0.4B
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Procedure No.: M2-PEST
Revision: 1
25 of 31.
Example 3: Sample fault is greater than the Sx multiple of the result.
'. 5s
- ;': Elude Result 1.0
; - , -/ .CRQL - -0.5 .
' 10,0
In Ihls case, the result exceeded the blank (Sx,
' nsolt is' not qualified, -
Laboratory perfonnan<^ oa^Mdmdual samples is established by means of spiking
prior to extraction1 amf ซ|toyria!:%);?'Atene'simj^te recoveries,. All are
spiked with surrogate compounds prior to sample extraction. The evaluation of the
, recovery results of these surrogate spikes is not. necessarily straightforward. The sample
itself may produce due to Such as interferences and high concentrations of
target and/or nontarget analytes. Since the effects of the sample matrix are frequently
outside the control of the laboratory and may present relatively unique problems, the
evaluation and review of data on specific sample results is frequently subjective and
demands analytical and judgment. 'Accordingly, this
consists primarily of guidelines, in some with optional approaches suggested.
3,7.1 Acceptance Cr&eria '
1. Two surrogate spites, tetraeMoro-m-xylene and decachloxobiiphenyl, arc to
all samples, MdivMual, Standard Mixtures, PEMs, blanks, and .anafrlx to
measure recovery in/sample and blank matrices,
2. The advisory limits for recovery of the surrogates teteacWoro-m-xylene (TCX) and
decachlorobiphenyl (DCB) are 60 to 150 percent for both water and soil samples.
3. The retention times of both of the surrogates in the PEM-, Individual
Mixtures, and samples must be within the calculated retention time windows. TGX
must be within ฑ0.05 minutes, and DCB must be within ฑ0.10 minutes of the
retention time determined from the initial calibration.
.3.7.2 Review Items
Form n PEST, Form VM PEST, and chromatograms.
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Procedure No.: M2-PEST
Revision: 1
Date:
Page 26 of 31
J.7iJ Procedures
1. .Verify tot the neeweries
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Procedure No.: M2-PBST
Revision: 1
27 of 31.
sightly outside its retention window. If this is the case, in addition to
surrogate recovery for quantitative bias, the overriding
consideration is to investigate the qualitative validity of the analysis. If the
surrogate is not present, qualify all nondeteeted target compounds as
unusable (R). '.'. - '*'.
2. If surrogate re^tkjn tim^
of the retentioa tirafi limits, . qualilicatioE of the data is left up to the professional
judgment of the leviewer:'- Itefitf to'Seefion 3.3;4.2'for'inKtte'|piidance..' .
3. _ Extreme or repeated analytical problems with, surrogate recoveries should be noted
. ' for WO action* i;--,>V.> :' . . . . "..'.:.:,'' >' ,: '
. ' ' .. ;; "'ซ'.} >*c -," "" ~ ป**,'. p " : i^ v '' r' .
4, Potential effects of the data resulting from surrogate iwoveries not meeting the
advisory linuis &oi^ b& ';"-.''
3,ฎ Matrix Spikes/Matrix Spike Duplicates ' ' ';.:,,,;
Data for matrix spikes (MS) and matrix spike duplicates (MSD) are generate! to determijie
long-term precision and accuracy of the analytical method cm various "matrices. These
alone cannot be used to evaluate the precision and accuracy of individual samples.
However, when exercising professional judgment, MS/MSB data should tie used in
conjunction with information 'on other deficiencies. '
3.S.1 Acceptance GHerta
1. Matrix spikes (MS) and matrix spite duplicate (MSD) samples are analyzed at a
frequency of at lest one MS and MSD per 20 samples of each matrix.
2. Matrix spike recoveries should be witMn the advisory limits provided on Form ffl
PEST-1 and PESTrl and in Attachment 1, Table 2. _ -
3. Relative percent difference (RPD) between MS and MSD recoveries must be witMn
the advisory limits provided on Form ffl PEST-1 and PEST-2 and in Attachment 1 ป
Table 2.
3,8,2 Review Items
Form M PEST-1 and PEST-2, and chromatograms
3.5.3 Evaluation Procedures
1. Verify that MS and MSD samples were analyzed at fee required frequency and that
results are provided for sample matrix,
-------
Procedure No.:
Revision; 1
Date:
Page 28 of 31
2. Inspect results for the MS/MSD Recovery on Form ffl PEST-1 and PEST-2 and
verify that the results-for reeowy tad RPD are within the advisory limits.
. 4. Check that the* matrix spite recoveries and RPD were calculated correctly.
'5. Compare %RSD results of npnspited compounds the original result, MS,
-- ' and MSD.. '"' ...-'.^'l'j&\. ; ". ' . ''
** "ป .V ' * r % '
3.8.4 Action'': ' .: ./;/";: .- _-/..,,,;
1, 'No action- is taken on MS/MSD data alone. However, using informed professional
judgment tbe data reviewea: may use tite MS- and MSD in conjunction with
" other QC .cntoaa, $od' jteteonipie- die need far some qualificalzoii- of' de data.
"- . V-':. ,;<'"'&*&?:'-'' .. - ' . .
2. ' The data' reviewer should first try to to what the of the
MS/MS0 affect the 'associated sample data,', ~. This determination should be made.
with regard to;the-MSA^D sai^te itself, as wdl as qjซffic inalyjto foraH sample"
wife tie " '
3. In those Instances wfae it ran be detenmed that the iraulte of ttie MS/MSD afect
only the sample spiked, qualification should be limited 'to this- .sample alone.
However, it may be determined through the MS/MSD that a laboratory is
having a problem in the analysis of one or more analytes, which affects
all For example, if fee recoveries for MS ano* MSD arc
consistently low for both water and' soil samples, this could be indicative of a
systematic problem in toe laboiatoiy and reeoYeries shoald be examined in aM
associated samples.
4. The reviewer must use professional judgment to the need for qualification
of positive results of nonspifced compounds,
NOTE: ' If a field blank was used for the MS/MSD, a to that effect
must be included for the TPO.
3.9 Pesticide Cleanup Cheeks
Pesticide cleanup procedures are utilized to remove matrix interferences from sample
extracts prior to analysis. Hie use of the Florisil cartridge cleanup procedrae significantly
reduces matrix interferences caused by polar compounds. Gel permeation chromatography
(GPC) is used to remove high molecular weight contaminants that can interfere with the
analysis of analytes. Pesticide cleanup procedures are checked by spiking the
-------
PioeecteeNo.: M2-PEST
Revision; 1
Page 29 of 31-
columns and cartridges, and verifying the recovery of pesticides through the
cleanup procedure.
3,9,1 Acceptance Criteria . ." ' .
I. Florisil CartiMgtfCteaittJp " . " "/''" \ ' .
a, HorisM cartridges- must be used for the cleanup of all sample es
, b. ~ Every lot number of FlorisiJ cartridges for sample clranup must be
diedced' .toy' 'spMng^ with 2,4,5-bichlotopbeiiol' and '''die midpoint'
coricedttaitfcm of In&vidtial Standard Mixture A; ': ',, '-'
The lot 'of Modal cartridges is if the fwwaSei for aU of the
'pesticides and surrogates in Individual Standard Mixture A are within 80 to
120 powait* if .tie xeoovery of 2,4,5-tridilQKfiliaiol is fhari 5 percent,
and if no peaks intetferiiig with fte target analytes are detected.
2. GdBennefrikto'CfacMn^ . .. :
a. GPC is used for- the cleanup of all soil sample extracts and for water sample
extracts that contain, high molecular weight components fiat interfere with
the analysis of the target aaalytes.
b. At least once every 7 days, the calbration of the GPC units must be checked
by spiMng. with two check mixtures: the matrix spIMng solution and a
nrataie of 0.2 ug/mi Anoclors 1016 and 1260.
cu The GPC calibration is acceptable if the recovery of the in the
matrix spiMag solution are within 80' to 110 percent, and the Aroclor
patterns should mateh those generated for previously run standarfs.
d. A GPC blank must be analyzed after each GPC calibration and is acceptable
if the blank does not exceed one-half the CRQL for any targe* analytes.
3.9.2 Review Items
Form DC PEST-1 and 2 and chromatograms
3.9.3 Equation Procedure
1. Florisil Cartridge Check .
-------
Procedure No,;
Revision: 1
Date: 06/30/1995
"Page 30 of 31
Check the date front thePlorLtil cartridge solution and the Form DC PBST-
l and recalculate of the percent recoveries to verify flat the percent recoveries
of the pesticides and surrogates in Individual Standard Mixture A me within 80 to
120 percent, tite recovery of 2,4,5-tritihlGroplienol is less titan- 5 percent, aiid no,
interfering peaks are pcesebt Compare the raw data to the reported and
verify that no calculation or transcription errors' have ceramet!,
2. CM'Penn^ctt'Ciirofflatogeaphy (CSC) . .v*
Cbeetthe datt.ฃnm Hue GPC' calibration check analyses and the 'Form' K HEST-2
and recalculate some of the 'percent recoveries to verify that the percent recoveries
of the pesticides in the, matrix spike solution are within SO to 110 percent and that
the Aroclor patterns are sirnilar to those of jjrevious stands
that no traii^riptioii errors have occurred, , : _., t
3.9.4 Action '...';- . .
1. If FtaM Cartridge Chedc; criteria are not met, the aw 'data. snowM be' oamiiitti '
lor the presence of polar interferences and professional judgment should be to
qualifying file data. If a laboratory chooses to analyze samples under an
unacceptable MoiM Cartridge Check, then the TPO should, be notified.
2. If Gel Penaeation Criteaia arc not met, the raw data should be exeunined for the
ppesenซ of "high molecular weight coatonMaiits and professional judgment should
be used in qualifying the data. If a laboratory chooses to analyze samples under
Gel Permeation Criteria, then the TPO should be notified.
3. If zero recovery was obtained' for the pesticide compounds and surrogates during
either check, then fee nondetected target compounds may be suspect and the
may be qualified'unusable (R).
4. If high recoveries (i.e, greater than 120 percent) were obtained for the pesticides
and surrogates during after check, use professional judgment to qualify detected
target compounds as biased high (K). Nondetected target compounds do not require
qualification,
5. Potential effects on toe sample data result from the pesticide cleanup analyses not
yielding acceptable results should be noted in the data review narrative.
3,10 Reported CRQLS
The objective is to ensure that contract required quantitation limits (CRQLs) are accurate.
-------
Procedure No.: M2-PBST
Revision: 1
31 of 31 -
3.10.1 Acceptance Criteria
The adjustment of the CRQL, must be calculated according to the provided in
Attachment' 1, Equations N and O. . ,
3.10.2 Bevieto Hans' - . .
Fonail PESTi FoOT'X/PBST^l amtPEST-2^andchromaiognii!s.;
\ ,
3.10.3
1. Verify that the CRQLs have been adjusted to reflect all sample dilution,
concentrationSj splits, cleanup activities and dry weight factors that are not
accounted for by the method.
-.'-'. / ' ' " -' ,
3,10.4- Action-, :' .'.,--"'. ''..- ' '
1. If there are any discrepancies found, the laboratory may be contacted by .the
designated representative to obtain additional, information that could resolve any
differences.. If' a dteBjMncy 'remains unresolved, the reviewer" must "dซde which
value is the value. Undo- these tiraimstances, the iwtewer may determine if
qualification of the data is warranted. A description of the reasons for
qualification and the qualification that is applied to the data should be documented
in the data review narrative.
-------
-------
JProcedure No,: M2-PEST
Revision: 1
'
1 of 6
1 to Appendix C-2
and
- for
~ '-
tihe 11.2^ IL3, and fl.4 to
ensure cxsrrect calculation of DT and Endrin br^kdown. The brrakdown of DDT and Endrin
Jfl both of the PEM be less than 20,0 and the combined of
'
.DOT ป 100 . (A)
' ' ' M mg- of D&T h^ected, . > -
in ng (Endrin + Endrin ketone) x 100
qf tang
Combined % BreaMown ** % DDT *- ft Breakdown Endrin (Q
All peaks in both the inJTOtions of the Performance Evaluation Mixture must be 100 percent
resolved' on both" columns. The relative percent difference of the calculated amount and the
true 'amount for each of flic stogie component pesticides and surrogates in the PEMs must be
less than or equal to 25,0 percent using equation D,
Where:
* F""* " Ccafcl x 100 (D)
turn
True concentration of each analyte
Calculated concentration of each analyte from the analysis of the
standard
-------
Procedure No.: M2-PEST
Revision; 1
' Pager 2 of .6
Initial Calibration
Retention time windows for analyte and swrogate are calculated using Table 1. Windows
aw around the mean absolute time for the analytfr during the
For example, for a given the-mean retention time is first
froin the initial calibration and found to be 12,69 minutes. The.retention time
window for this pesticide is ฑ0.05 minutes. Therefore, the calculated retention time window
would' tram 12.64 to, 12.74 minutes. './.="'
'.'.''.'.--"'.. Table 1 ' '" ' .. ,'/
' ' WINDOWS 1TOR IKlldDE TARGET <ปMPO1MK
; Pesticide Compounds ' ;
alpiia-BHC, .'* /-;,' '."."'
"- .- '.-.:
gamnia-BHC ' " '
Mta-BHC '. -
Heptacblor..1' . , . '
"'- '/_.'
aJ^ba-Chloidane ~ - l . . '. ' - '
gamiaa-ChtanJane -
Heptechlor epoxide
Dieldrin "
fiidrin
Bidrin aldehyde
Bndrin ketone
DDD
DDE
DDT
Ettdosulfan I
Endosulfen D
Bidosulfan sulfate
MethoxycMor
Aroclors
Toxaphene
TetracMoro-m-xylene
DecacMorobiphenyl
Time WIndo ws fa Miontes'
" -ฑ005-
. ;ฑป.G5 . ' '
. . ' ' ฑ0.05
, ฑQM
. " ' ' .. ฑQ.*QS- '
' ' ฑo.Q5 ;
ฑ0.07 ,
ฑ0,07
,ฑ0.07 "-^
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
ฑ0.07
. ฑ0.07
ฑ0.05
ฑ0,10
The %RSD of the calibration factors for single component target compound must be
than of equal to 20.0 percent. The %RSD for the two surrogates must be than or equal to
30.0 percent. Up to two single component terget compounds per column may exceed the 20,0
-------
ProceduteJSTo,: M2-PEST
Revision: 1
.Date: 06/30/1995
Btge: 3 of 6
percent limit for %ESDป but those compounds must have a S&RSD of less than or equal to
30.0 percent. Calibration factors are calculated using equations G and H and the. %RSD is
calculated using equations E and F.
" ftjHD _,
Mean ' _ . ,. ' , , .
wtee: " .. , "'.-.''"'''.
ป , ; ' ; _ , :
3D (Xf - Jff ^ \
- I - - \*f!L
'
.../ . , /"',,
- ^ = kdivMwtl value to calculate the ".-
x <* the of a Mues .
n- =' the total nraitar of values ' '
(V tf tke
~.-.~-.-~g.- *-""- ....... '"- ...... ซ~ -
J*aw wt/ecfea
n
Where: .
CF ' = -Mean caMbration factor of n values
CFj = i* cdibration factor'
n = Total number of values
Continuing Calibration
The retention time (RT) for each target compound and surrogate must be within RT window as
calculated above using the mean absolute RT estabEshed during the three-point initial
'calibration. The relative percent difference of the calculated amount and the true amount for
each of the compounds in the mid-point concentration of the Individual Standard Mixture^ must
be less than or equal to 25.0 percent using equation I.
-------
Procedure No.:
Revision: I
Date:
Page:' 4 of ,6
JHRD =
100
Whore;
" eoneaatratiofl of each analyte ,
C^ " = Calculated concentration of each analyte from the analysis of the
standard ..-"-
, Surrogate .
The advisory Bmite few recovery of tetraidiloio-m-xylafie,(TC3Q and decaciilorohipiie&yl (DCB)
ore 60 to 'ISO percent for both water and soil samples. . The surrogate percent recovery is
calculated using equation J. The retention of both be within the
calculated 'retention' time- windows, 'Leป, TCX be within ฑ0.05 -minutes of the
time determined from the initial calibration and DCB must be within ฑ0.10
of the mean retention time determined from the initial calibration. . ,
d
Percent Recovery * - x 100
Whore;
Qa = Quantity determined by analysis
Qt = Quantity addol to ample/blank
CD
Matrix Spikes/Matrix Spike Duplicate
The matrix spike/matrix duplicate recovery and RPD requirements are listed in Table 2,
-The matrix recoveries and SPD are calculated using equations K and L.
Table 2
CONTRACTUAL
Compound
gamma-BHC (Lindane)
Heptachlor
Aidrin
Dieldrin
Endrin
4,4f-DDT '
% Recovery
Water
56423
40-131
40-120 -
52-126
56-121
38-127
RHD
Water
15
20 -
22
18
21
2?
% Recovery
Sou
46-12?
35-130
34-132
31-134
42-139
23-134
Soil
50
31
43.
38
45
50
-------
Procedure No,: AC-PEST
- Revision:. I,
Date: 06ao/1995
.. ' 5 of,6
; Sptoe Recovery - ^^-^ x 100
Where: .. ,
* SSR = Spike sample result ' : ;-
' -SA-' ปSpite '..' 7 ' ;'.-''.
JtfP- -igซ-lgP>| ,100 (L)
H2 (MSR -
Where;
MSR ซ
MSDR ~ Matrix spike duplicate recovery
Hie vertical tan in the formula above indicate the absolute value of the
difference, hence RPD is always expressed as a positive value.
. Ptestidde Cleanup Check
Every lot number of FlorisU cartridges used for sample cleanup must be by spiking
with 2,4,5-trichlorophenol and the midpoint concentration of Individual Standard Mixture A.
The recoveries for all of the pesticides and surrogates in Individual Standard Mixture A 'must
be within 80 to 120 percent, the recovery off 2,4,5-trichlorophraiol must be less than 5
percent, and no peaks must interfere with the target anatytes. Percent recovery is determined
.using equation M.
Percent Recovery - -ซx 100 (M)
Vซ
Where:
_ Qd = Quantity determined by analysis
Q. = Quantity added to sample/blank
The gel permeation chrornatography (GPC) apparatus must be calibrated every 7 days. The
calibration is acceptable if the recovery of each single component analyte is within 80 to 110
percent and the Aroclor patterns match patterns previously generated by standards!
-------
Procedure No.: M2-PEST
Revision:- 1
Date;
6 of.6
, Reported CEQLs
The CRQL of the compoiiซt_iwtiddซ is odculaied using equations N and Oป as
appropriate, . .
CRQL for waters: "
;>
'/AivfeCtp, ป Rtfumncฎ QtfiLjr^ __ . " (N)
"".'*"''
Df ซ . ' Mซiซ factor , ,, ;
CRQL for soiis/sedimeiits (dry weight basis): ' ' .
CRQlx, ' (O)
100
-------
' .
of
-------
-------
Procedure No.: IM-14NGRG
Revision: -2
06/30/95
Page; 1 of 26' .
OF ANALYIE .
' DATA ' . .'
.. :'. ' ' ...
. . 1... AND An^^m.^^^^-j:-:-^ ^-'\
This procedure provides instnsctions to manually validate the target aialyte list (TAL) '
melais and cyanide data using ft manual innovative data validatioa apjjroach that is based on"
the BPA*s National" ttyncftkin^Guidk&tafis fox Dati. B0riewv?luiฃ.BPA' K^w--ffi*s.'
Modifications to the National FunctioEal Guidelines for Data Review,' Specifically, ttie
approach is on the use of quality control (QQ Monnation -contamed-on,-^
laborator>' QC summary forms, 'and does not udiizetfie raw dala. The mformation tfiai is
obtained from the QC: summary forms is indicated .on Table IM-J-J>IG4RG-^.;;:;This
procedure is applicable to the TAL metel and cyanide data obtained using the-^
' Laferamtocy Pwฎmiป of'Wo* (C3LP SOW)V v" ',."- 4'^;' ;:.'' .;./..-;P ;";; ''.' ";' "'
Dala validated wag this procedure are considered usable for the following types of
purposes; however, the data users .must' decide on a case-by-case basis whether the
procedure is suitable for their intended data uses. Hie suggested data are: .
ป Ovcrsi^tit of activities led by other -parties " _---
Comparison to action levels
* Initial site investigation
* Contamination sources ,
Nature and extent of contamination
PreMmnary risk assessment
Risk assessment with known high levels of toxics
Feasibility study
Preliminary design
Treatability study
ป Initial cleanup verification
IM-l-WORO
-------
Mo,;
2
2 of 26"
2. .
IH-1-WQRO-QC the U^Kj>:V-'"-; ;:'"-: : ';'''' '":-.'' - \
Data validation is performed prinmrily with respect to the technical
however, there are certain contractual criteria on a participating
laboratory's with the terms and -of the of
the laboratory. * The term "CCS" next to a itep indicates that - there is a
contractual criteria in addition to the ' It is a
validator to point out to- tfie OOP.
Officer (ITO) for action, The data: are as '
' " ' '
* Tcx:hmraJ Holdrng/Iimes (CCS - ContractuaJ holding tiraes ortly)
:ป ,% -* , i " '
ป CMteatliin
*
* Initial and Continuing Calibration (CCS)
* dDL
* Blanks -
* Initial (CCS)
* Continuing Calibration (CCS)
* (CCS)
" ICP Interference Oปck Sample (CCS)
ป Laboratory Control (CCS) ,
* (CCS)
IM-l-INORG
-------
Procedure No.: M-1-INORG
Revision: 2
Date: 06/30/95
3 of 26'
QC mm JM-I
CUP ปAS
Action Level Notificaiioa
Holding Times
Imiia! Calibration
Initial Calibration Verificalion '
Ccaitinaiiig Calibration Verification
Instrument Blanks
Labomtory Bknk
ICP Interfemice Gbeck
Laboratory Coairol Sample
Duplicate Precision
Matrix Spike Recovery
Fmnaoe QC (MSA)
ICP CMluliaa
Field Duplicates
Reporting Omit VeriJtoitiซ
Paperwork
Raw Data
ttl-l-WQEO
-------
Procedure No.: M-l-MORG
Revision: 2
Date:
Page: 4 of 26
Matrix Spike Sample-(CCS) .
GiapMte Furnace Atomic Absorption QC (CCS)
Method of Standuil Addition (MSA)
IQP -Serial Mutton (CCS)
f.",'*> 1. .'ซ'. _ . .
i<$ฃ\. ; '.' '. f KeM Buplicato Of.indudedl)'
* . Itepartfiig limit Verification (IDLs, linear range, dilution factors and
^ , moisture content) .'.-'
' SampleFaperwotit ." . ^-*; ' , "-"-,"
\ V' ;/; ,/;', ~ .
Several forms have beea developed to in the performance evaluation and in keeping ^
track of the data quality qualifiers. The first form, IM-14NQRG-BT, stimmarizes the
'hpjtdmg times. Tie .second J^rai, M-1-INORC3-CAL allows icKajMtttioa of the'
calibration .and blank- QC violations. The third form, IM-1-INORG-SPK is uscxl for the
spile recoveries, duplicate precision, and control sample analyses data. UK fourth form,
IM-1-INORG-QL is used for summarizing all qualifiers for the samples.. The EPA Region
in Inorganic Regional Data Assessment form is used by the data validator to summarize
contractual dcfidซic!ซ for the fataatory's CLP Technical Picgec4^0ffiปr (EPO), All
. fonns are appended at the back of this SOP. ' '
A memorandum describing those dements that were butsidc of QC criteria, the
actions which wore and the impact on data usability must be prepared with
substantiating documentation. Hie report-and the supporting documentation should include
, the foEowkg: -
1. "Sand annotated Form Is with
a, data validation qualifiers
b, sample identification number
c, sampling location
2. A narrative description with
a. a statement that defines the level of the date review, i.e., IM-1
b. major and minor problems associated with the analysis
c. Issues that may have affected detection limits
1M-MMOKO
-------
Procedure No,: IM-1-INGRG '
Revision: 2
Date: CM/30/95
Page; 5 of 26'
3. . "Hie foflowing attodufteals
a. list of data validation qualifiers
b. documentation which includes tens that support the assigned' data
. qualifiers. > Samples affected; by noncompliant quality control
, measure should be listed on forms.
. ... ซ. . .data of disiQdy forays) .. ;. ' .... -..,; , .
, - . , , . - . . ,, ,,
. ".': ,!'; '
The codes described below are those -r^ommended in the EPA's national Functional
and "the Regioci HTs'tnodificBtkiiui.1 " "
^ -*;^-.V. . "-..-;.-. 5
" ; ซ/ amiytes): .- - " , :^ . ' ,
'' '
associated number indicates
tfnitioa necessary fo.bedetected.' :''"'
Confirmed idratilicatiort. '
** * *
B = vNot detected substantially above tie level reported In laboratory
or field blanks. , <""
R- * " Unreliable result Analyte may m may mi be present .in tite
sample. Supporting data necessary to confirm result. .
Codes RehUing to
(can be used for botfi positive results and sample limits):
J - * Analyte present Reported value may not be accurate or precise.
K = Analyte present. Reported value may be biased Mgh, Actual
value is expected lower.
L = Analyte present Reported value may be biased low. Actual
value is expected to be higher,
UJ = Not detected, quantitation limit may be inaccurate or imprecise. '
UL = Not detected, quantitation Emit is probably higher.
IM-l-WOM
-------
. No.: IM-MttQRG
RevMon: 2
6 of 26
Other Oite . -
Q SB NO analytical result.
* = Results reported from diluted analysis.
He following subsections describe for each of the QC the acceptance
location and retrieval of QCdaSa, evaluation of the QC data, actions taken in the event the
QC 'acceptance- criteria are and documentation -of the QC .violations in a
The purpose behind action level notification is to the EPA Project Officer
(RPM) or tile Site Project Officd (SPO) aware of the potential human health risk at the
site.' In accordance iWHi,-HB5 Kt^tcss JLUL Hsz3jntous. iriiSte IkivisiOB-policy>p.tiifr EPA RJKMJ
of"SPO must be pfoinptly 00fiฃied<'pf any contaminant exceeding the established action teyel
>?ฐฎi* Mie 'H^dav healiii '^iciviiSOify ^lifnitif' ^me ฐCMJKH j^w c?oioit^yFitiiiBiite cscccsediiiiir fliฉ 0001311 l^v^is
must be validated as; a top priority and reported to the RPM or SPO, as soon as possible.
^ Validation of the rest of the data may then be completed within the normal time frame.
2.3 J
EPA's Office of Sold Waste and Emergency has JLG-day advisory
limits and actioa levels for- several organic compounds and of health risk
concerns on the Safe' Drinking Water Act. The analytes and their IG-day
health advisory limits ate isted in'Table M-1-INORG-AL. The criteia-fiir action tevd
noMcmtion ate as follows;' ' '
The contemtaamt concentratioa must be equal to or above Ac 10-
day health, advisory limits,
* Dab for contaminants exceeding the actioa levels mast be validated as a top
priority,
ป The following EPA- personnel must be notified of the action level
exeeedances:
* EPA KPM or SPO
-
- ป The remaining data validation should be completed per normal procedures.
IH-l-INOftQ
-------
Procedure No,: 1M-14NORG
Revision:' 2
. Date:-
.' . - 7 of 24
Any special instructions from the Hazardous Waste Division should be
followed. ' ' -
Records should be kept of the review, action level notification and any
follow up instructions and actions. / ' , *
',, -.-. : .
Compound, """".-,
Arsenic. -. ' - '.-.; ;, i\-.-
i
Obmniiiim '-" ' ' - '
, -' .. :' .."'
ฑ-%S*:- ;-
:>. ^50 : .''.
i; --1000-'- \
-^1000 ;.<;
;7 ,r*"^"V; ,
CtedmiBni' " ''-'' :"--
" ! *
*L5d:"' " ' -'"
--.'- .,-:-r.-Kv::
y~ Action
,^:-:40
w-i^ -
;V-: -200- '
b Lead also Ms an action level of 5CK) mg/kg (ppmw) for sol ~ - ':, \ .
2.3.2 -Hofti mquu-ememis ,entl Retrieval of Daia, -^
* * "*,^
All forms required to perform Level IM-1 validation, 'as detailed in the following sections
necessary for canning out action lewd notification. _ , , ' " '
2.3.3 Evaluation
The evaluation praew .pecottag action level notification will primarily consist of
comparing -the results on Form Is with the action levels in "Mite M-l-MORG-
AL. Following fee identification of the contaminants the action levels, focused
date validation should be. performed using .the criteria, and procedures described in the
appropriate sections below,
2.3.4 . Action
The action resulting from focused data validation will be the notification of action level
exeeedance to the personnel identified above in Section 2.3.1. Copies of Form Is can be
used to highlight the contaminants above the action levels.. The findings, of the focused
validation can be summarized in a memorandum, and 'the data qualifiers resulting from
focused validation may be written on the Form Is, The marked up .forms should that
they represent validation of only the contaminants exceeding the action levels, and not all
data.
1M-I-ZNQRO
-------
Procedure Noป; 1H-MNORG
Revision: 2
8 of 24
2.4 HOLDING TIMES-
The primary objective is to ascertain the validity of results based on the holding time of 'the
sample from ig|g:.:iM[r;gQllQptiQi|- to time of sample extraction and analysis. 'Hie secondary
' objective is also to verify compliance with the contractual extraction and analysis holding
' - times ftoM the y^jjR^lt_t|ifl6rjtf.SKPi:^te, psceipt. -COS'Rj it the laboratory .
; ' 2.4*1
/" Technical requirements for sample holding times have only been established for water
. matrices. The following holding times (from the time of collection) and
preservation requirements were established under 40 CFR 136 (Clean Water Act) and arc
;*; found. ;:in ,Volame;49ปt :NuDd)ซr-^H)9/of -the Federal Uegbtef, jปge43260r issued on
^ //October 26,- 19841"'- : " ,*" "";/"'? "*"*5.*"" _ ^ *-','' : ,-< ป/^ .''"/"".'". ''
. :' Metals: '"' '. ;'6.'iKซflis;^p^orfปd'topH <: 2"-
' " ; pesoved to pfi < 2
topH->12
Contractual holding times have .been established by the CLP for the water and soil/sediment
samples. He times are counted from the time of sample receipt at the laboratory, and are
as follows: ''. . _ ,.,.''
180 days
ซ Memary: 26 days
ซ Cyanide: 12 days
Generally, the holding times are calculated using the dates only and not the times,
2,4.2 Data Requirements and Retrieval of Data
' , * IT
Forms 1, 13, 14, and EPA Traffic Reports and Sample Shipping Logs.
2.4.3 EvoiuQtwm Pmcedum
Technical holding times are established by comparing the sampling date on the EPA
Sample Traffic Report with the of sample preparation/exttaction and analysis found
on the extraction and instrument run logs (Forms 13 and 14, respectively).
Technical Holding Time (days) = Analysis Date - Sampling Date
Contractual' holding times are established by comparing the sample receipt date on Form Is
with the sample prepmtion/extetction and analysis on the extraction and, run logs
' (Forms 13 and 14, respectively). ,
IM-MNORfl
-------
Procedure No.: 1M-1-MORG
Revision; 2.
ง6/30/95
Page: '9 of 24
Contractual Holding Hme (days) ซ= Analysis Date - Receipt Date
2.4.4 Action '. ' ". . ' . .
Tne following actions are requited only for the violations of the technical holding times, If
contractual holding times are exceeded, the TPO must be notified of the violation.
1, Jt 40uQ&lati&A
qualify all results > Instrument Detection Limit (DDL) as' biased low (L) and the
results < IDL is estimated detection limits biased tow (UL).
2., If holding times are exceeded by two times (2X) the criteria for mercury and
cyanide, qualify the non-detected results (tesults < DDL) as unusable (R). ฐ
ซi **" "\ "'"'* * ' '''""'
ซ ' ' - ซ."."ซ ""."-_
3. If there are gross violations of the holding times for the metals, use professional
. judgment to determine the reEability of the data. . A low bias would be expected for
significantly longer holding times, and the reviewer may reject the non-detected
data (results < DHL) as unusable (ft). .
*ป'
- \ ** * > ' ' "
4. Although the technical holding times for soil samples have not been established,
apply the water holding time criteria to the soil samples. If the soil sample are
qualified using the water holding time criteria, this must te clearly documented in
the narrative report.
2.5 CALIBRATION '
Requirements for satisfactory instrument calibration are established to ensure that the
instrument is capable of producing acceptable quantitative date. Initial calibration
demonstrates that the tastnimeiit Is capable of # cceptable performance at the beginning of
the analysis run, and oontinuiiig calibration verification documents that the initial
'calibration is still valid.
Standards at concentrations near the lower limit of detection sure required to be ran to
determine the Imearity of the instrument,
2.5,1 Acceptance Criteria
1. Initial Calibration. Instruments must be calibrated dally and each time the
instrument is set up. Specific requirements for type of analysis are is follows:
ป ICP Analysis
ป A blank and at one -standard must be' in establishing the
analytical curve.
-------
Procedure No.: 1M-MNGRG
Revision; -2
Page: 10 of 24
Atomic Absorption Analysis (AA)
A blank and at least .t&ee standards, one of which must be at the
Contract Required Detection Omit (CRDL),, must_ be used in
establishing the analytical curve. ".
, , <>.. .. . - . - - ,
* A blank and at least four standards most be used IB establishing the
, analytical cunfoj-. .': . -.' .. ; . - _."_'.
* ' The correlation coefficient must be sas 0.995. (This is a technical
, . * -, critefotttfflid/i|ot ft contiactittl 000*) l , . ..,..-
' "'' "
.
at least thiee standards must be used in establishing the
'''
_
The correlation coefficieait must be S* 0.995. (This is a technical "
criterioQ and not a contractual one.) , ' '
ซ AnalyMs results -muEt Ml wifliin flic ซป&ol limits of 90 "to llOperoeot
Reecwoy (%R) of tibe true value for, all- amdytes ซซyt' mercury and
cyanide. ' _
* Analysis results for' mercury must fell within the control Emits of 80 to
Analysis results for cyanide must Ml witMn the control limits of 85 to
3. CRDL Standards for ICP (CM) and AA.fCRA).
* A CM must be 'run at a concentration of 2X CRDL, or 2X the IDL,
whichever is greater, for each ICP analyte (except Al, Ba, Caป Fe, Mg, Na
and K) at the beginning and end of each sample run or a minimEm of twice
per 8 hours.
A CRA must be ran at a concentration equal to the CRDL, or the IDL,
whichever is greater, at the beginning of sample ran.
IM-I-WO8O
-------
'Procedure No,:' M-l-MORG
MevMon: 2
'
11 of 26 '
_ The CRDL standard be 90410% of the true
values.
2*5,2 Data Requirements md Retrieval of Data . ;. - "": -.
1, 2Aป 2B arid 14. -' " .'!'- ' ' ":-".' >*HI1iv:^-. :'
* '' ' '
1. Verify that the instrument was calibrated daily and each time the instrument was set
" up using the correct number of staridarfs and blank.' : . , ' .'' " "
_ _
_2. ^ Recalculate one or mine "of flic 1C? and Ctry
' GFAA, etc,) , using the following equation and verify that the mSaloilated value
' . with the laboratory reported values cm Form 2A. Due to |K>^able rounding
* di^rq)anciesj allow results to Ml within 1 percent of the contract windows (e.g.,
80 tt> 111 ' ' '''
x IIDO
Tree
Found = Concentration (in ug/L) of each anaiyte measured in the of
the ICV or CCV solution , /
True = Concentration (in ug/L) of each anaiyte in the ICV or CCV source
3. Verify from the run log (Form 14) tot the CRAs mid CRIs were run at toe
required frequency, ' ,
4. Verify from Form 2B that the CWs were at 2X C1DL, or 2X IDL, whichever was
and the CRAs were at the CRDL, or the IDL, whichever was greater,
2.5.4 Action
I, If the minimum number of standards as defined above were not for initial
calibration, use professional judgment in qualifying the data. However, if the
instrument' was not calibrated daily and each 'time it was set up, qualify the as
unusable (R). Document the noncompliance with the calibration requirements in the-
"narrative and document on the EPA Region in Inorganic Regional Data Assessment
Form.
1M-HNQRQ-
-------
2.
Procedure No.: JM-1-IN0RG
Revision; 2
Date:
Page: 12 of 26
" If the. ICV or CCV %'R fill? outside the waidowns, ising the following.
guidelines for Qualifying 'flic data.
QraUfior
Cyanide'
.> IDL
90-110
None-
75-8?'
70-84':'.
<75ฐ
<70
3,
If the ICV. or
of 75"'
> IDL
- . .
toeaa^pten^c ^dbws^'liutwItMn the
. ซ >l5-"(N)("ซ> .20
results < IDL are acceptable. Results > 'IDL should be qualified as biased
Mgh (K). ' ; '. ':, ' s ' '''
ff the ICV or CCV %R is <75 {eedent (m^als) or <70jwoeiit (CN) or
< 65 percent (Hg), ipalify al j^ative results' as uauaybte (R)".
Please be advised, -then are no National Functional Guidelines to qualify the data
based on the CKDL analyses; however, EPA Region ffl his developed specific
to qualify the date.' , .
ซ If the 'recovery for the CM or CIA Is > 110% and the reported sample
results are >BDL, tot < 2X C1DL, qualify the data as biased high (K).
ซ If the recovery for the CM or GRA is between 50-89%, qualify results >
IDL, but < 2X CKDL as biased low.- Qualify results < DDL as low
'(UL).
ซ If the recovery for an dement is <50%, qualify the results > IDL, but <
2X CKDL as extremely low (L). Quaffify < IDL as unusable
(R);
IM-i-INORO
-------
Procedure No,: M-l-MORG
RevMoa: 2
'' 13 of 26
Blank results are to- determine the and . magnitude of
problems. Hie criteria for evaluation of blanks applies to any blank with the
samples. ' If problems wife aay, blank exist, all data with tfee Case must be
'ouD^Mly e^uatM'to'.ieiecniiiw-:'i^rtiar or -not is, an ,} ', ' ' .. "*y ~\ ';. ' ' '" ''-' -''
' vBtidriliJy in the dote:- for the Case, or if the problem is an isolated occurrence not affecting
'y-' - " ' " "-' '
n QfififaminHTifs should ha in the hlank^s) at concentrations, > HJL.
' " " :-' ''"' ' '*""' ' '
'J.C3 'fimeime " * ' ' '/
. ' ' - . ,";'"' "- 1
Review the on the Blank Summary (Form 3) for all blanks. Note that the
instalment blanks two purposes: One, to determine any sample -carryover, and
second, to determine the shift in the instrument baseline. It is common that the instrument
baseline may shift upward or downward from the calibration point (zero
concentration standard) during a sample run. This shift is not necessarily indicative of any
carryover from the previous sample. Negative blank results ace common indicating a shift
in the baseline. Professional Judgment should be used when qualifying data on the
instrument .blanks.
2.6.4 Action
Action in the case of unsuitable blank results depends on the circumstances and origin of
the blank.
ซ Sample results > IDL but < five tiroes the amount in any blank should be
qualified as (B).
* Any blank with a negative result whose absolute value is > CRDL must be
carefuEy evaluated to determine its effect on the sample date.'
ซ Qualify the field blanks in a manner similar to that for samples. A field
blank may not be used to qualify another field blank,
1M-1-INORO
-------
Procedure No.: M-l-MORG
RevMon; 2 .
Due:
14 of 26'
* When multiple' field blanks are in a SDG, use the highest
concentration for each in the field and laboratory blanks when
qualifying the sample data,
Note! The blank analyses may not involve the weights, volumes, or dilution
as the associated samples, in particular, soil sample results reported oil Form 1 .will not be'
on the same basis (unitsf dilution) as the calibration blank data reported on Form 3. *
" ' " . ''',.< f V ~~ > ' ' " '"* ;4-'jฃ,,' i S.= -a a* '
'5.7. IGPIMCiRHBRENGE^I^MXSAMEtE .-. '.'-'' ;';**;"
He ICP Interference Check Sample (ICS) verifies the contract laboratory's
_
1. . An ICS must be rw at the beginning and- end of ^tch simple analysis rua (or a
* minimum of twice per S-hour woddug shift, whicheves- is frequent).
. - .' ./"..". \ ' ' ' ''.?$:<.: _.-_ ' ; -
2, ' Results in" the ICS solution AS must Ml within the control limits of ฑ
' 2Qpapeentฉฃ ihe'tnie' value.- , - " . _ - '"-"'', '"
BaM Requirements and Retrieval of Dalu - - -
Forms 1 and 4
2,7.3 Evaluation Pmcetfatm
1, ' Verify at random -the reported %Rs for the Solution AB using fee and found
values. Use the following equation:
%R . AB x
Trae Solution AB
where:
Found Solution AB = Conantatioa (in jag/1) of analyte measured in the
analysis of solution AB t ,
True Solution AB = Conceitotion (in jttg/1) of each analyte in solution AB
2, Check the results with an absolute value > IDL for those analytes which are not
. _ present in the ICS solution.
IM-HNORO
-------
Procedure No.: M-1-INOEG
Revision: 2
15 of 26
2.7.4 Aetton
L For samples with concentrations of aluminum, calcium, iron, and magnesium which
are comparable to or > their respective levels in the Interference Check Sample: . '
* "
If the ICS recovery for an is > 120 and the results .
',",.; are < IDL, this data is accepMile for UK, " . ; _ , . ,
^ 'the '
we ."> IDL, qodfy'ffc effected date ป biased Mgk(K).. '-"..
sample results are > .IDLป qualify the affected data as biased low (L). " . -:
' ' ' ' ""' ""' '
' If stDi>le;iiesซlts'':aie < IDL, and the ICS woivery'-for. flat enalyte fells
. . within the range t>f 50 to 79 percent, the possibility of false negatives may
exist. Qualify the data for as detection limits biased low
(OB). ' .' .-- - ",.. '- ' ...-.
'ป.-*" ,
*. If ICS recovery results for an element is < 50 percent, qualify results >
IDL as biased low (L)t and results < IDL as unusable (R).
2." . If results. > JDL -at obปrvcd_for elements which are not pre^it in the ICS
solution, the possibility of false positives exists. An evaluation of the associated
sample date for the affected elements should be made. 'For samples with
comparable or higher' levels of totefaeats and with analyte eonceatratioiis that
approximate those levds found in the ICS (false positives), qualify sample results
. > DDL as biased high (K).
3. If negafiYe results axe observed for elements that are not in the EPA ICS
solutions, and their absolute value is > "IDL, the possibility of negatives in the
samples may exist If the absolute value of the negative results is > 'DDL, an
evaluation of the associated sample data should be made. For samples with
comparable or higher levels of mterferents, qualify results for the affected analytes
< BDL as biased low (UL), qualify results for the affected analytes > BDL as
biased low (L).
4. In general, the sample data ran be accepted if 'the concentrations of .aluminum,
" calcium, iron, and magnesium in the sample are found to be < or equal to their
respective concentrations in the ICS, Jf these elements are at concentrations
> the level in (he ICS, or other dements are present at concentrations > the level
' in the ICS, or other elements are present in the sample at > 10 mg/L, the reviewer
should investigate the possibility of other interfereEce effects by using the Table
found in the most recent version . of, the SOW. 'These analyte concentration
IM-MNOtO
-------
Procedure Noป: M-l-MOKG
RevBioa: 2
Date:
16 of 26
equivalents presented in the: table should be considered only as values,
the value of any analytical system is instrument specific. Therefore,
estimate the concentration produced by an interfering element. If the estimate is
>2X CRBL and also > 10 percent of the reported concentration of the affected
element, qualify the affected results 'as biased high (K). . '
2.8 LABORATORY CONTROL SAMPLE _ * .' ;-'':-*v-. -.k''*-' '
The, laboratory control fflmple^(LCS)serฅes as a, monitor of the oveiail performance erf ail
steps in the analysis, indiiding the sample pieparation. '' ^ v5'Y' " .' * '
2,8.1 Acceptance Qtietta:: , ",. ;' ;-,/-ivt", .-,/'
' . ;" . ' ";' . - ' . - vV^: ^"V/O '
1. Ail aqueous* LCS results mmt fall within fee'control 1Mb of 80 to 120 %R, except
Sbmd Ag wlikiiliaซiป"iปiifircilM ' . ., ,,- ': /'riV'Y'.'V/??;- .
' : -v-'.^' -v-^' :'-. ' ' ' '.. ,;fe:v::"f-v
2. All solid LCS ..mutts ^ must fail within the control . by -, the EPAซ
'' '
2,8.2 'Data Requirements and Retrieval of Data ' . / ' . ,
Forms 1 and 7.
2,8.3 Evakmtom Pivceium ^ '
1. "Smew Form- VH and voify that results fall wiflun the omtool limits.
2. landotaly verify the reported recoveries on Form VH using the foUowing equation:
LCS %R - "X 100
LCS True . ,
where:
LCS Found = Concentration (in |ig/l for aqueous; mg/i|ป for solicQ of each
anaiyte measurrf in the analysis of LCS solution
LCS 'True = , Concentration (in jxg/1 for aqueous; rag/kg for sold) of each.
analyte in the LCS source
2.8.4 AcOan
1. Aqueous LCS:
1M-1-WOKO
-------
Procedure No.:. IM-i-MORG
Revision: 2
-
17 of 26
If the LCS recovery for any analyte falls within the range of 50 to
79 qualify, mute. > IDL as biased lew (L). If the 'LCS recovery is
> 120 percent, qualify > IDL as high (K). ป '-..
If results are < IDL and the LCS recovery is > 120 percent, the are
acceptable*", .'.V.-.';" ' '.."-"., .' ;*
If sesills/ftte^;'j^tee' of 50 to
affected analytes as bkisซj. low (UL).
If LCS recovery results are < 50 percent, qualify > IDL 'as
-tow (L)Vand'iefldfs"^ 'IDLas"uniisablf (R). . , "; ;-;,;.;:;-' -/' -
~*
.. ^/:,S/
-.-f :-'-'-.'f---.'-w-
"
,
IDL as biased low (L). If the
. LCS iwovery -is 'atoe the upper control limit, qualify ^ie results >' IDL as
Uaaeil '"
If the LCS results are lower the control limits, qualify all sample
<
ซ If the LCS' results arc higher than the control limits and the sample results
- are < IDL, the data are acceptable.
2.9 DUPLICATE SAMPLE ANALYSIS '
Duplicate analyses are used to' determine the laboratory precision for each sample matrix.
'2.9.1 Acceptance Criteria
I. Samples identified as field blanks cannot be used for sample analysis.
2. A control limit of ฑ20 percent (35 percent for soil) for the Relative Percent
Difference (KPD) shall be for ample values >5X CKDL,
3. A control limit of ฑ CRDL (ฑ2X CRDL for soil) be for values
< five times CRDL, mcluding the when only one of the duplicate .
values is < five times CMDL.
1M-MNO&O
-------
Procedure No,: IM-14NORG
Revision: 2
' ' Date:. 06/30/95
' Page: IS of 26
2,9.2 . Data Requirements and Retrieval of Data
Forms 1 and 6.
2.9.3
' "1. ... Review Form 6 and verily that results fail within the control Hmits. ,
y.-f.. ' -:- -v:; "..;" -,-" 'X ^*i*^;.i^\ซiifey - ., .' .:,:,-.-" '--,"'
-", V ' . ',,--' "*'" .->>ซ Vs- *' ' . .;
'<".2-.;' Recalculate one/'Or more-WB-usieg" the following equation to verify that results
' ''*
,--,^,,%m/:^xm
' {'4^-."li?^^<-:ซ.;
- ,-.. .. <..,^ii.i.-.- "S4ปtf,^ - '
." P ' ** "S*c^'ซiiil'Wie't ZDL, for that analyte in all samples
, of the matrix as estimated 0), and results < DDL as estimated (UJ).
2. If the fide! blank was for duplicale analysis, aU QC data must be*
carefully checked and professional judgement exorcised when evaluating the date.
Document Ma !nfonnaticป on the EPA Region in fcorgamc Hegfonal Btta
Assessment Form,
2.10 MATUX ANALYSIS
The matrix spike sample analysis provides information about the effect of each sample
mattix on the digestion and measurement methodology.
2.20.1 Acceptance Criteria,
1. Samples identified as field blanks cannot be used for spiked sample analysis.
IM-J-INORG
-------
Procedure No.: IM-1-INORQ
Revision: 2
19 of 26 , -
2. Spite recovery (%R) must; -be within tie limits of 75 to 125 percent However,
spike recovery limits do not apply when, sample concentration the
' concentration by a factor of four or more.
3. If the matrix spike recovery limits are not met and the, sample concentration does
not exceed 4X the spik^ added, a posHHgestion be performed for the
,:, * IQP, CN and flame AA analyses. His criteria does not apply to sUver. , The post
' . _ digestion spike must be performed at 2X the sample concentration;or 2X CRDL, '
'
1.1012 Data'MegminmfMis emi' Retrieval of Data
Fonnsl. and-SA
'
I. ^ Review FO'rm 5 A and verify tint results fall within the
, _. ;--:-: ;..ซ- ' . ;^^
2. Recalculate one or more %R using the following equation to verif>' Uiat msults woe
, correctly rqpoit^.^on. Form 5A. ' -.
%R -
SA . . .
where:
SSR - Spited ample result
SR = Sample result
SA = Spike added
3. Verify that tfiefidld blank was not for spike' analysis,
4, Verify mat i post-digestion spite was performed when required, and at specified1
spike concentrations.
2.20.4
1. If the spike recovery is > 125 percent and the reported sample results are < DDL,
the data is acceptable for use.
2, If the spike recovery is > 125 percent and the are > IDL, qualify
the data for- these as biased high (K).
IM-MNOEQ
-------
' . . No,: M-l-MQRG
2
Date:
Page: 20 of 26"
3. IF the Kcovery is <75;i*reeiit and the sample results are > BDL, qualify the
data for these samples as biased low (L).
4. Iff, the spite recovery Mis within the- range of 30' to 74 percent and the sample
results me < DDL, qualify the data for these samples as detection limits low
COL). ' ; .,-$ ' ' .'-' -: -
5* If spike recovea^ i^ulte fell < 30 parent and the sample result are < IDL,
; ' qualiiy the data for these temples .is unusable (R). If the results are > IDL,
qualify fee date w;feaซd-ftrtiaซ%'Iow-^L). " ,":."'*'
, - :'. V:'"' .:; .. ' :-,-./. ''
6. If the field blank was used for matrix spike analysis, all other QGdata must be
' carefully checked and professional judgement exercised when evaluating the date.
' Report this Mormation on the 1^^
farm. '" ''^v.^S-' v. ' - '' .-';* i ..-' "
' "' " ''
. .
7. If a post-digestion t spike^is not performed when required, or the recoveries fall
. outside the matrix spiferecweiy limits, d
digestion recovery data are rioi used for data quiinfication as acceptable recovery
''' ' ""'"' "
2.11 ATOMIC^ASORPHON QC. , '
Duplicate injections and post-digestion/artalytical spikes are required for each element and
sample analyzed by the furnace atomic absorption technique. Additionally} a reanalysis by.
the method of standard addition (MSA) is required for samples meeting certain conditions
specified to the most recent version of the SOW, Hie -postsligestion/analytical spUce
recoveries for the GFAA metals are reported on Form 14 under the %R column. "The
correlation coefficient (r) can be found on Form 8 for samples requiring MSA. The flag'
*+" is placed on Form Is for samples and analytes with'r <0.995.
2.11.1 Acceptance Criteria'
1. The post-digestion/andytical spite recovery- for the GFAA metals must be within
85-115%..
ซ
3. The correlation coefficient (r) for the samples requiring reanalysis by the MSA must
be 0.995 or better using the ordinary squares linear regression. (A formuk for
linear regression can be found in the SOW, or some computer software applications
have the linear regression function built-in.)
IM4-JNOW3
-------
Procedure No.: IM-1-MORQ
Revision: 2
Date:
Page: 21 of 26
2.11.2 Data- Requirement and- of Data
" Foims, 1, B and 14.
'2.11.3 Evaluation
1. ' Evaluate tie %Rs from Form 14 'for- a comparison with the analytical
. -. imwoty, R^iiitepeat of 85-115%. , ' ".".' '-"" '*-/.
2. , Verify toy random' recaleulatiofi that the -r values reported on Form 8 are accurate
and equal to or -greater tira 0.995. ' ; - - . .~- ,-"..- ;' .'
2.11.4 Acimn ' <\ . '^;r '.*'." .;.' . -'' .^wv -V-- .''? .-'
* ป ' * ' " . " . * " _Hjr -*" " * *
h, , * A, ซ * ,, * " "^^ ' **,ซ*'
1. ' *_ ^ the analytical spike recxwery is less 'ten 85%t tat tha?5 40%, qualify
' > DDL as biased low, (I.), and results < IDL ป biased low (IJL),
2. If te anaiytical spike reawery is greater tlian 115%f qualify results > !DL as'
biased W^ ;(K)j saniple;iwults ''< WL me ' ' '
3. If the analytical, spike recovery is less than 10% and the results are < IDL,
should be qualified usable (R). Sample results > IDL should be qualified biased
extememly low (L). . . - -x" -"
4, If the MSA coraeMon coefficient is < 0.995, qualify the data as (J).
2.12 ICP SERIAL BffiUTION - ,
The serial dilution determines whether significant physical or chemical interferences
due to sample matrix,
2,12,1 Evaluation Criteria
If 'the anadyte concentration is sufficiently high (concentration in the original sample is
minimally a "factor of 50 above fee IDL), .an analysis of a 5-fold dilution must within
10 percent Difference (%D) of the original results.
2.12.2 Data Requirements and Retrieval of Data, .
Forms 1 and 9,
1M-1-INORG
-------
Procedure No,: M-l-MORG
Revision: 2
Date:
Page: 22 of 26.
2.12,3 EvobtaMom -Procedure
1. Recalculate at random the %Ds using file following equation to verify the dilution
analysis results reported on Form 9. ' -
. ' ' ' "" '^''-llซi - ' ;: "'" ''.-'
- -X :,;^6B -Jฑฑฑ x 100, .. ';> :'-:..'
.. -.",'- ">-.- * ป . . ... -. '
., -.jft-t ,
wncre; ' - = , ',."."-"""'.
I "ซ" ,'Mtiffll sample, zesqit;' - ' '
S = Serial dUution resist .instrument reading X 5)
'2. Determine whetfnr\ffioi^i>f^^hซ*,iiitacfaBD^, - GeoeraUysl:a diluM sample
should offer lesser interference.; hence, more accurate and higher reported values.
However, it is ate possible to obtain lower values Sir the diluted sample, indicating
a potential for negative mterfeieace. The apparent negative ihteference may be
related to sample concaateatioris in the less accurate _regioas,;-,of 'the ICP
instrumentation i.e., near the IDL m the upper limit of the linear range. Carefully
fence is real. - ' ' ''
2.12.4 AcAtm ': :^
1. Whoi the dinted sample are cratade the range of 90-110%' of the odfpnai
sample result, .qualify.the assoda^ data as 'estimated CD-
2. If evidence of negative interference is feuad, use professional judgement to qualify
the date.
2.13 'HELD DUPLICATES .
Field duplicate samples may be taken and analyzed as a indication of overall precision.
These analyses measure both field and lab precision; therefore, the may have more
variability tiian laboratory duplicates which measure only -laboratory performance. It is
also expected that soil duplicate results will have greater variance than water matrices due
to difficulties' associated with collection identical field samples.
2.13.1 Acceptance Cnterm
There are no review criteria for field duplicate analyses comparability.
-------
Procedure No,; ttf-1-WGRQ
RevMon: 2
_ I*age: 23 of 26
2,13.2 Data, Requirements and Retrieval of Data
Form L .
'2J33
-,- ?--- ;-' ;v -'.
Samples which ace field dupli^tes should be identified using EPA Sample Traffic Reports
or sample field sheets. The should compare the reported for each
" ' '' ''' ' '
-
Any evaluation of the field should be provided with the At the
reviewer's discretion, a ~ table; listing the RPDs between the original and the
ampte may be prepared.' '.'.'- . ._ "
2.14 .REPORTWC'LIMrr '^ " .
Reporting Emit verification is performed to verify that the CRDLs were net; to ensure that
the reported quantitation results were accurate, and to ensure that the ICP data were not
reported beyond the upper finear range of the Instrument.
The positive results themselves are not verified for accuracy, as tMs would require the use
.of raw date. However, the undetected values are for proper application of dilution
factors and moisture content normalization. Indirectly, a check on the reporting limits
would suggest that the sample results have been properly adjusted for the dilution factors
and moisture content
2*14.1 Acceptance Criteria
Minimally, the laboratory should meet the basic CRDLs specified in the most
version of SOW, TMs implies that the laboratory's IDLs must be equal to or less the
CKPLs. The laboratory has a choice of using the ICP or AA instrumentation for analyses
of metals; however, the sample results for As, Pb, Se and Tl must be greater man 5X IDL,
Otherwise, AA instrumentation must be -used.
ICP data must not be reported beyond the established linear without sample dilution,
The linear range for each ICP metal is 'established on a quarterly basis,
-------
: IM-1-INGRG
Revisi0a: 2
Date.
:* 24 of,26'
Furthermore, the dilution factor aad correction, must be made to the
. results, as This may the reporting Emit above the
CRDLs for some analytes, . .'-
; , * ' 2.14.2 Data Requirements and Retrieval of Data .'
.:..|4V'" '.- Forms 1, 10and 12.' ', ,;. :- . '' . ' ','. , > .";.."-.
'v^lf.. '"/'',- ,' ''."-'':';''" " ' -' 1 -; " - v
'.\'k^-': 2ป143 .-. . ': . - -I _' - . :...
' '. '-.. i - 1. ' - Verify from Form 10*that the IDLs for ami
'.'. ''"", . .ฃ)ฃ CKDLs it a ndttbnniii*' "Eta* may be seven! Penan'"IGi-'ibf-IbblCP*' AA4 Bfe '
' f * S# *..'ซ.,> 9" ' 1 "^"^9
': .''". 2. " ฅeaff' ftk the liaear'jai^ป;iป the; ICP tie reports!;ซ" Bo^m;12ป" tad ao
''".; -''.' _k; ; undiluted sample dak' axe Reported above tfcw anges..":'"." '-'-'^\^
'; / 3. "' Verify <ป Ac tem Is'that tee CTDla adji^l.'lw any' ffltqtipo ,
: . '" anil mtMsftae eonleot, as applicable, '-..'' : /^\ ;-
' .4.- Verify that the sample ate >5X ICP IDL, if 1C? analysis results are used
fear As, Hf Se, or Pb. ,.'..'"'.
2.144 . "^
If there are any i^lJnd, fee may be by the
' representative to obtain additional information that could resolve any differences. If a
discwpancy unresolved, the reviewer may quaMcaticm of tlw data is
warranted..
.2.15 - ' .
The puipose for evaluating the paperwork is to that the samples being
validated are tite from the site, and have not been tampered with.
Accurate sample identity is of importance in the sample data.
Without unequivocal identity and eham-of-custody procedures, the sample data may
not be defensible or enforceable.
Under the current CLP contracts, the paperwork (i.e., the pmge or the
administrative fecdrd) is included in the the toboiatory. It is assumed
that the validator is not privy to the paperwork; the evaluation
criteria and procedures below apply only to toe documents that are generally
IM-i-WORO
-------
. ' . , Procedure No.: IM-1-1NQRG -
Revision: 2
25 of 26 ..
included in the date validation package. These documents are the chain-of-custody forms .
in Shipping Recoid. . * '
1.15.1 Criteria .. ~ '''.'.'
Criteria for acceptability 'or authenticity of the sampling paperwork, document control and
chain-of-custody have been established by the National Enforcement Investigations Center
(MEIQ, to . support ,lhe CLP,; .Overall criteria are too numerous and subjective to -tie
discussed hei^ but fe '. -:; ' .
* ' Hie chaijn-of-ciistody form should be properly and completely filled out
including the sampler dgnatures, date and time -of sampling, sampling station
identification, analyses requested, traffic numbers, tag numbers, etc, .These
data are minimally iiequired to confirm the authenticity of the sample and its
' ' ' '
... .. , . .
* Hie chain-of-custody must be maintained at all times. . The custcsdy transfers .
between different parties must be signed and dated; ;" ' . , :'":; ' ' "
* '*,'. * ' . ' , >- - _ ^ t nj
2.15:2 Data Reqmremenis a?td Retrieval of Data " .-. -,"V'.
\ , '
A. copy of the chain-of-custody form is essential to' confirm the identity of the samples.
The Region in Shipping Record is required to identify the field QC samples. The chain-
of-custody form and Shipping Record are generally located in front of the data package.
2.15.3 Evaluation JRrece
-------
Procedure No.:' IM-1~ZNORG
2
Date:
26 of 26
numtas. Generally, MB of to or
refute the problem.
Any found in the be brought to the of
the EPA RPM or SPO. Clearly the in & to die
parties. Attach copies of the chain-of-custody to the '
IM-l-INQItO
-------
No.; :
SDQ MO.J ''I-:
Site; ' -.v ..;.:.. \
Procedure No,: IM-1-INOR6.
Revision: 2
Date: 06/30/1995
.
Sampk
a^fe-iCiaoi^g
Hg (28 Days)
CN (14
Date
.on.
Reed.
Lat
IP
I'ttPMtriV '
Date
Prep,
Anal
Hold.
Time,
Days
Qual,
Date
Prep,
Anal
Hold.
Time,
Days
Qual.
7 /
/ /'
7 '/
.., -
T.1-
/
'.."/ 7
17
/ J
.-A
-1 /
/ /'";;
/7
/ /
ilia
v/,V
7/
-r
-------
CMC No.:
Procedure Ho.: tQf-l-IMGEG
2
'SDGNo,; . . ' Revisrf^
Data Reviewer/Date: _. . / Bate: Oft/^n/
Site:
Table M-l-HOtG-CM,, TAL and and Summary
ICP InstnJmen t ID;
jfatnunent Cafibrstet? _
ICP Ditto
' ICP Dale Haded:
""ฃ," H " * . -^
. lastnuoeate CMibrafajd?
AA'Itate Staffed: ,*:_V
' AA IDite Bated; '
_.*!ฃ
' "V-"/^"
; "j^fe!^^
_J^
,,i , ,: ,,. .,,,.
*** .,*i'.
-"--.-
' : ^ * "
: r ''.^^^...^^
"}. >"v , ' .
' >' ' -.. .,-
JJ^^ff""- - " ' ..'-'
.StB^pfo
11.
,12, , , ".. , .
,tt : : ,: ป,,ป,
14. , ".. ."/
is, . . . ; -. " - .
I6t'- ;':- , -*' "li- ' " ' "
_ jy;v. %>->_.-; --j: ,
' 1% : ' ' '",' ' '
19. ' . /; ,
ป,, .-. . . ;.
- ... - ' ,., ; ,v--.
:. * _ ;-v ,"r ^ ' ^> -
Armlyte {Cril^)
JUnatett '.'' Al
-AwtoM^ , 8b'
Assenic , .' Al
Barium * ' Ba
Beryllium ' Be
ttdniiitti '. -CM
Calcium Ca
CfcKปw!um Cr
Cobalt On
Copper Cu
Iron Fe
Lead Pb
Mt|facsiuiB Mg
Maojanesc Ma
Mercury HJJ
Nickel NI
Potassium K
Selenium Se
Silver Ag
Sodium N*
Tballiutn 11
Vanadium V
Zinc Zn
Cyanide CN
<"ic^^ป
*' ."*.."'- Tj'n
'., >*.'.? *fS
-~ ', ,",.
"" L1***' '
-
"* r" l " ' *'v
."' ' '' '.
<%:-:
%ft '
*> < SI
.
r* - <>
'QML
-" v "
' '.
.
-
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*"*:* ' ".!-
:;;;. f
"* ,
,
nBetf"
if -Mป ' '.
-
-------
Case No,:.
Sim No.:"
Data Reviewer/Date;..
Site;
Mo.: IM-l-INO&G
ferislen: 2
. _ Bate: 06/30/1995
m~i~HQRS~Sff.. TM.M*AซซซQซซ*MMi4iSpito, lhป^fcป
*
,
AhntaMt' A3
j^tt^^^>ป Sti
Awฃฃฃi*'ฃ"
*^^*^i"
1 .'ปe '
Oi**ป:i*,oa"
ctf^'S&'or.
'''chM^a^Ck
:oSft'%ป"
Oa^wV'v Cd '
'iMS'-^' '-"iC
taHt-C^'-l*
liMHJtt.
Ha
itoMil^ Bjf'
MbluJ Ml "
HioDpI PH
Fet*8ซiซak K
fc
SSJw Ag
N*
n
VซMซffaซ V
Ztac' A
CpaMe * Ol
Msirii
Es^ftR
'ปซ$
' - ,t
**" ' ^
** *
^
t * ป '
^" '. "ป *ซ *
'<:v~,' ' "'-'
i - ''""
'- *, *
"
,
RPD
ซ%ig> ^"WftWTtfc
jgj I^Ojp *'
\; -S,
'.' ''. :<;".
- ~'~ :
' -:;~-\'"
." ;""C-'"'' ''
. ,-" ' '/ "
-. _ .
. \.
"' , "
' Quals.
, ,
,:;^1,;;
'ji^k'.Cv
" ^\^'^'
f,*ป^f ;*~ ,
/'"f^f-"
1'. '","*' '
''.- . *
ICTS<
.
'f.'-* v
'^V'"'- "
' ,
* * ".
;J-T';-v-"
,'ซ,!. *, > ',
^-^."f. ,
i1:^:-'-
, ^ ,v V
'".-:'>--:-
* ป
sr.0tt .
Qaalf."
f.jป
te and ICP Sedai Oaufioa QjialiJy Coat
Post f%KL/AML
ICP
ff.US%
^*----
,
' AA .
BHDStt
, , .
' ; ป;
. ; ^.*
, - ,-ป
;
. .' *
.-Oiifc..
p
roS Summary
US Recovery
O4mป>
ปซ?-;:.
?3Sv. '
#&'.? -
.i-'-
. "vi- *"/;*.
" '-' ;
^k
- ^*^
f
53^.. f:
vl^r? --". -
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i
QuaU.
.
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>:-t;': . v
a
, ' . .
. "-. "
* ,
'-> .-
.'; ",. -ซr-
> -.* _ *
.
* T^ซre we no criteri* U the present time to ejyalify the ICP metals or Cytmde based on the post -digestion spike tecovcries,
*' 'The preeisioa RPD far soil amplei is 35.
1 Tbe-rซO|e of 88-120% R S wsed for Uie aqueous LCSs, Solid LOS samples feavt specifif ซeemt!yj25Sf_!2ฃฃ?* 'i*3^6'
-------
CM
SCO No.:
eNo,s
i
Data Reviewer/Date: ".' '. " __ ..,.:...., <_!J _:_/:: "..-":-, _'. . /.-./.--,
Site:
';
,
#
XM-1-IBOBG-QL. of
Sample
Number
.; -
Rcocedore So.: Hf-Ir-HOif
ievlsloa: 2
Hate: 06/30/1995
Qualifiers' ' 1
-,,-''', 1
Al
Sb
As
B&
,
-
Be
Cd-
f
*
Ca
- .
Cr
.t
*
Co.
i
'Cu
'
, -. ,
#-'
F^
ป ซ ' '"
^
ft
* '*>:
,
*.. ','
" -':*.
. , '-
. . "
.Pb
" <: ',-.
.";?
1
jS|
tltfe"-
1
m*
i
s .
.':','.
i^--
'."" '^7
' .
'*
;Mg
,f.^v
y^j
fe
4*Ha*jซ^fe
91
11
1
'*
*>
-,. .1
fe
,y;
"Ma
- ^
Js, %/
jfatitlti
^R^8
^1
?"-. ;
/>
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V-y
^ff'l*^^'
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iS^"^
f:r
K'
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$$
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m
.':'''*,
,-;
-
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4:l;
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'*
,-Se
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,;*;
sp
US
'
"'
s'
r^i'Vt-
ซWf-,
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fttl
;/' ;
Ag
Y:.^
^i5
H' . -
- -
".-
;| '.
V
i
Na
'
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Tt
V
i .
ZtI3
-
1
CM
1
'
.
1
I
1
I
I
-------
ป
SDGN.
Ho; M-
Revision: 2
Date: 06/30/1995
*ฃ>'.
'"' *'*/' *
' "*x ฐ' .,
Case No.
SDO No.
SOW No.- ___
IPO: Action
Holding Timers
Calibrations
Di^fiiMto Aaalyds
Table
IPA B-egloa m
biorganie Regional Data Assessment
Site _..
Nuwber of 'Stiaplea/Matrix ,
Review* 0f not CRL) _
Reviewer*! .^..^^..^^
FYI. .
ICP
AA
MSA ' .'
Sand Dilation , "
Field Duplicates
R^ortmg Limit Veriicntioa
Sample Paperwork '
O =
M =
Z =
X =
Action Items:
Data had no problems/or qualified due" to minor problems.
Data qualilled dปe to m^or problems,
Data unacxjeptable,
Problems, but do not affect data.
Areas of Concern:
Notable Performance:
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------- |