Document 2JzYBeZkKr0JqManbVvgYK4m5
____________S4EH/ESC ~W.7D^v.7D*P^.AbctTonj
Analysis (Type of Report]
REPORT NO.: MSL-S489 ESC-UAG-86-24
JOB/PROJECT NO.:
DATE: Harch 5, 1986 1/>
i TITLE: ANALYSIS OF TOTAL PCB CONGENERS IN KRUMMRICH SOIL SAMPLES
3 AUTHORS: B.M. Hughes, D. McKenzie and C. Trang
5
ABSTRACT:
Krummrlch Plant Soil samples were analyzed for total PCB congener concentrations using capillary GC/EC analysis techniques. Eleven samples contained total PCB congeners at levels less than SO ug/g. One sample contained a total concentration greater than SO ug/g.
J* v!> i3
ii
IS
N lOMfAl
TECHNICAL APPROVAL:
P.L. Sherman Environmental Sciences Center Senior Research Group Leader
APPROVED BY:
Environmental Sciences Center Quality Assurance Specialist
3 Z-APPROVAL DATE:______ - / -
HONS 023945
COMPANY CONFIDENTIAL
This document it the property ol Monsanto Company end the recipient is responsible for its safekeeping and disposition. It contains CONFIDENTIAL INFORMATION which must not be reproduced, revealed to unauthorised persons or sent outside the Company, without proper authorization.
DISTRIBUTION
COPY NUMBER
J. Gloeckner - 1740 2. B.H. Hughes - U4E 3. D. McKenzie - U4F . C. Trang - U4F S H.M. Mees - U4D (. P.L. Sherman - U1F 7-9 Reports Library - R2C 10 Chesterfield Information Center - AA3A
ABSTRACT ONLY H.A. Woltermann - U4E
This report he* been assigned to you. When it is no longer needed, you are responsible for returning it to:
i____
If you transfer it ;o anyone else, please let your librarian know, so the records can be changed.
a.|*es:ci tacv. i.soi
HONS 0239*6
Tine Stamp . <860305.1601> ANALYSIS REPOST
L0C NUMBER: U-86-02-18-01 U-86-02-24-01
DATE: March 4, 1986 PROJECT NO: 760.28-6207
TO: Jim Cloecknar/Krunnrlch Plant
FROM:
Environmental Science* Center Monsanto Conpeny 800 0. Lindbergh Blvd. St. Louie, Mo. 83167
Phone No: (314) 694-1464
Title: Analyele of Totel PCB Congener* in Kruanrich Soil Senplee.
ABSTRACT
inaerich Plant eoil sample* vers analyzed for total PCB congener
concentrations using capillary CC/EC analysis techniques. Eleven saaples contained total PCB congeners at levels less than 50 ug/g. One sanple con tained a total concentration greater than 50 ug/g.
INTRODUCTION
Twelve soil saaples were analyzed for total PCB congener concentration*. The** analyses are required a* a part of the Kruanrich Plant cleanup of an area where chenlcal* had previously bean storad.
SUMMARY
Table 1 suaaarlzes the results of caplllsry CC/EC analyses of 12 soil ex tracts. Not* that on* aaapl* contained a total PCB concentration greater than SO ug/g and the remaining 11 samples contained PCBs less than 50 ug/g. Table 2 suaaarlzes quality control experiments conducted on blank soils and samples 1SP-004-C and B-5,0-7.5'. See PCEX21 and PCEX03 for the details of how th* samples were extracted and cleaned up prior to CC/EC analysis. Refer to Standard Analyels Methods ECAN02 for the details of hov the cleaned up extracts were analyzed. This information is Included in a later section of this report.
The patterns of PCB congeners found In these soil samples were similar to
Aroelor 1254 and Aroclor 1262 patterna. However they ware not identical.
In * previous project for the Kruanrich Plant (Project Number 760.28-6204),
similar results were obtained for soil samples which were analyzed using CC/EC
end CC/MS extract analysis methods. In that study, the PCB congener patterns
were also not identical to Aroclor 1262. Therefor* w* have chosen to report
data based upon this less expensive, yet technically equivalent CC/EC analysis
method for this present study.
HONS 0239V/
QC results Quality control raaulta ara shown In Tablaa 1 and 2. These tablet ahov good racovarlaa of surrogate compounds which vara added to each aaapla bafora extraction. Thia information Indicates how well each toil aaapla waa extracted. Duplicate analyses of Log #0007S, 1SF-003-C, B-2,0-15' and B-3, 0-7' ara also ahown in Table 1. Table 2 auaaarlzaa racovarlaa of Aroclor 1254 which waa added to Blank Soil staples, ISP-004-C and B-5,0-7.5'. These data show that good FCB congener recoveries would be expected using these methods for the analysis of toils froa the Kruaarlch Plant.
DETAILS Standard Sampling Method Ho(a): Saaplaa supplied by the Kruaarlch Plant. Standard Extraction Method No(t): PCEX03 and PCEX21 (Sea PCFS03 and PCFS21
for flow sheets describing chase aethods.) Standard Analysis Method No(s): ECAM02 Final Report File Ho(s): A2071S Table File Ro(a): B2071S. C2071S Also Included in this report are:
1) Suanariee of Standard Extraction and Analysis Methods used for this project.
2) Analysis Request lnforaatlon recorded at aaapla login. 3) A copy of the ESC/UAC Good Laboratory Practices Manual.
ANALYST(S): B. Mason Hughes, David McKenxle and Chi Trang
HONS 023948
TABLE 1. Sumaery of rCB Concentrations In Soil Saaples.
ESC Project Ho: 760.28 - 6207
Date: March 1, 1984
Saapla I.D. Surrogate Recoverlea(IRecovery)
pcs(a)
CL5-benzene 2,4,6-CL3-blphenyl
Concentration (ug/g)
Method Blank
Soli Blank Log #00078
* (DUP) 1SP-003-C
(DUP) ISP-004-C
1SP-005-C 3SP-004-C
B-10-15'
Blank Soil
B-2 . 0-15' (DUP)
B-3 , 0-7* * (DUP)
B-5 , 0-7.5' B-6 , 0-15'
B-7 , 0-15'
B-B . 0-15'
105 97
.
69 55 88 58 80 111 103 127 101 101 100 117 117 85 86
103 93
94 82 85 83 81 110 86 108 89 95 100 102 105 80 79
A1248 A1254 A1260 A1262 Total
ND(b) ND(b) ND(b) ND(b) ND(b)
a
55.00 - 145.00 200.00
50.00
* 163.00 213.00
" ND(b) *
a
2.50 2.50 2.00 2.00
a 2.87 2.87
ND(b)
a
2.40 2.40
a 6.20 6.20
a a a ND(b) ND(b)
aa a -
a 1.00 1.00 a a a 1.00 1.00
a a a 4.00 4.00 a 3.50 3.50
a a a ND(b) ND(b)
" ND(b)
a
a
ND(b)
aa
a
a a
Method Blank
101
92
Footnote*: a.
b.
Aroclor 1254 and Aroclor 1262 standard foraulatlona ware used to calibrate the capillary GC/BC raaponae for PCB conganera. How ever the pattern of congeners in these soil saaples ware not Identical to these foraulatlona. Sea text for wore details.
ND- None Detected (<1.0 ug/g)
TABLE FILE NO: B20718:MH
HONS 023949
TABLE 2. Suaaary of Aroclor 1254 Spiking Concantratlona and tacovariaa In Quality Control Sxparlaanta for Soli Sanplaa.
BSC Frojact Ho: 7*0..28 - 8207
Date: March 3, 1966
Staple I.D.
Surrogate Recoveries (%Recovery)
Aroclor 1254
CL5-bamana 2,4,6-CL3-Blphanyl
Soil Blank(L. Splka) 87 (H. Splka) 106
1SP-004-C (L. Splka) * (H. Splka)
94
69
84 103
83 87
Ajaount Added Recovery
<us/s>
<%>
1.00 10.00
70 91
1.00 10.00
100 84
Soil Blank(L. Splka) 101 * <H. Splka) 114
86 98
1.00 10.00
100 120
B-S.O-l.S'a. Splka) 103 * <H. Splka) 102
91 95
1.00 10.00
110 114
TABLE FILS NO: C2071S:MH
HONS 023950
Tha following pagaa daacrlba standard Extraction Methods and Standard Anslpsls Methods usad for this project.
HOMS 023951
ESC Standard Extraction Method (SEN) TITLE: PCBa in Non-EC Active Matrices
ESC Standard Extraction Method Mo: FCEX21
MATRI(X), (CES):
Soils and other non-EC active solids and aolvanta
TYPICAL SAMPLE SIZE <E>
TYPICAL EXTRACT VOLUME <1>
TYPICAL ANALYTES: Aroclors 1232, 1242, 1248, 1254, 1280, 1282, trlchloro blphenyl lsoaers through octachlorobiphenyl iaoaera
0.5 - 5.0
10
ESC Standard Analysis Method Nos: ECAM01, ECAN02
INTERFERENCES: Any electron capturing species in the retention tine region of trlchloroblphenyl lsoaers through octachloroblphenyl Iaoaera that is non acid hydrolyzable
TYPICAL SURROGATES
TYPICAL RECOVERIES <)
pentchlorobtrtfn* 2,4,6-trlchloro
blphenyl
50 - 120 50 - 120
APPARATUS AMO MATERIALS: Burdick and Jackaon banxana or haxana for saaple extraction or dilution. Pierce vtale. Sulfuric acid at varying concentrations.
Ultrasonic bath. Disposable glassware.
(Sea flow sheet for this extraction nethod in PCFS21.)
LIMITATIONS: Method appllee only to uatrlces which do not contain interfering electron cepturlng species in the trlchloroblphenyl through octachlorobiphenyl isoaer retention ties region.
SAFETY PRECAUTIONS: See PCB handling protocols in laboratory safety Manual.
DATES OF METHOD CREATION AND UPDATES: 12/17/84
HONS 023952
FLOW SHEET PCFS21 FOR ESC EXTRACTION METHOD FCEX21
SAMPLE ID:
EXTRACTION DATE and TIME: SAMPLE COLOR AND DESCRIPTION
VEICH OUT SAMPLE INTO A 14 OR 40 aL PIERCE VIAL
[] .
MRC EXTRACT LOO NO: .............
SAMPLE WEIGHT
SURROGATE SPIKE OF SAMPU
. (]
ADD 10.0 aL BENZENE TO SAMPLE.
. []
ULTRASONICATE SAMPLE FOR 1/Z HOUR IN A SOUND BATH.
[] . .
PLACE 2 aL OF THE EXTRACT INTO A 7 aL VIAL
ADD 2 aL ............. SULFURICACID AND SHAKE
.
() . .
[) .
.
ALLOW PHASES TO SEPARATE REMOVE 1 aL FOR ANALYSIS.
. l)
EXTRACT NO: ............... DATE/TINE COMPLETED ANALYST: ...................... ESC JOB NO:
10.0 aL FINAL VOLUME..............................
HONS 023953
CSC Standard Extraction Method (SIM) TITLE: PCS* In Non-EC Active Matrices
ESC Standard Extraction Method No: PCEX03
MATRI(X),(CES):
Soli* and other non-EC active aollda,aolventa and olla.
TYPICAL SAMPLE SIZE
<S>
TYPICAL EXTRACT VOLUME
<-l)
0.5 - 5.0
10
TYPICAL ANALYTES: Aroclora 1232, 1242, 124S, 1234, 1260, 1262, trlchloroblphanyl leoaere through octachloroblphanyl laoaara
ESC Standard Analysts Mathod Noa: ECAN01, ECAN02
INTERFERENCES: Any electron capturing spocles In the retention tin# region of trlchloroblphanyl laoaara through octachloroblphenyl laoaara which are not reaoved by tha three-phaee alllcagal column.
TYPICAL SURROGATES
TYPICAL RECOVERIES (t)
pentachlorobenzene 2,4,6-trlchloro-
biphenyl
50 - 120 50 - 120
APPARATUS AND MATERIALS: Burdick and Jaekaon hexane for aaaple extraction or dilution. Sadlua eulfate far drying tha cample matrix. Silica gal coluana lapragnatad with potaaalua paraanganata, aulfurlc acid,
and potaaalua hydrexlda.
Nitrogen for extract volume reduction. Olapoaable glaaavare.
(See flow aheet for thla extraction aethad In PCFS03.)
LIMITATIONS: Method applloe only to aatrlcea which do not contain lnterfarrlng electron capturing apeclaa In tha trlchloroblphanyl through octachloroblphanyl laoaer retention tine region when electron capture analytical aethods are uaed. Thla llaltatlon does not apply to aaaa apactroaatrlc aethoda.
SAFETY PRECAUTIONS: See PCS handling protocola In laboratory aafaty manual.
DATES OF METHOD CREATION AND UPDATES: 2/13/84, 9/23/84
MOMS 023954
TLOV SHEET PCTS03 POE ESC EXTRACTION METHOD PCEX03
SAMPLE ID: ................................................................................... MRC EXTRACT # .................................................................................. LOG NO: .............
EXTRACTION DATE nd TIME: ......................................................................................
WEICH OUT SAMPLE INTO
A 16 aL VIAL
I)
SURROGATE SPIKE OF SAMPLE
. ! (]
FINAL HEIGHT........................ INITIAL HEICHT.................... SAMPLE HEIGHT ....................
DRY SAMPLE IF NEEDED BY .
ADDING ABOUT 0.1 |
[J
N SO TO VIAL
.
24
. .[|
RINSE COLUMN HITH 2 X 20 aL HEXANE
DILUTE SAMPLE IN VIAL
HITH HEXANE AND PLACE ONTO CLEAN-UP COLUMN.
[j
. .
QUANTITATIVELY RINSE
VIAL ONTO COLUMN HITH 4 X 1 aL RINSES.
. .
(] .
.
.
ELUTE SAMPLE INTO SO aL .
CENTRIFUCB TUBE HITH [ ]
40 aL HEXANE.
.
.
.
NITROGEN BLOU DOHN TO .
_ _ __ aL
[]
EXTRACT NO: ..................................... DATE/TIME COMPLETED....................................... ANALYST: .................................................... ESC JOB NO: ........................................................
CLEAN-UP
COLUMN DESCRIPTION 25 aL DISPO PI PET
|............. |
l
||
|| | j..................... 4
ca Na SO 24
ca 1* POTASSIUM
||
PERMANGANATE
||
SILICA CEL
|............ |
|............. |
I ca SILICA CEL
||
| |...................... 4 ca ACID SILICA
||
CEL
|............ |
I............. I
1 ca SILICA CEL
II | |..................... 4 ca BASE SILICA
I1
CEL
\/ \/
GLASS HOOL
MOMS 023955
ESC Standard Analysis Mathod (SAM) TITLE: Aroelor Toraulatlona In Solvent*
ESC Standard Analysis Method Ho: ECAN02
ANALYTICAL INSTRUMENT AND MODE OF OPERATION: HP-5880 Capillary CC/EC Inter faced to an HP3357-LAS Laboratory Data Systea
TYPICAL ANALYTE
TYPICAL INSTRUMENT LEVEL OF DETECTION (LOD)
(ug/al)
Aroelor fornulatlons 1232, 1242, 1248, 1254, 1260, and 1262
0.1
TYPICAL PRECISION 10X LOD
<%)
30
TYPICAL ACCURACY
9 10X LOD
(>
30
INTERFERENCES AND LIMITATIONS: Any alactron capturing apaelaa In the reten tion tine region of trlchloroblphenyl through octachloroblphenyl laoaara ara potential lnterferancaa. Exact retention tinea of aoet likely PCS laoaara can be obtained froa tha analytic of Aroelor 124S, Aroelor 1254 or Aroelor 1260 foraulatlona.
CHROMATOGRAPHIC COLUMN: 30-aetar fused alllca J6W DB-5 (0.25 uM) with wide bore (0.32na).
COLUMN TEMPERATURE PROGRAM: 130(l)/4/300
INJECTION TYPE: Splltlaaa
CALIBRATION AND STANDARDIZATION: Uaa Internal atandard quantitation technique and eallbrate lnatruaene raaponaa factora froa authentic Aroelor fornulatlon atandarda. Use a alnlaun of 10 PCB laoaara for the deterainatlon of foraulatlon Identity and quantity.
CALCULATIONS:
Fornulatlon eoneantratlon (laoner RRF)(laoner area/internal atandard area)
where: RRF la the relative response factor for the appropriate PCB laoaer In a given fornulatlon. Formulation concentra tion la obtained froa the average of at least 10 such cal culations.
SAFETY PRECAUTIONS: Sea PCB handling protocols In laboratory safety aanual.
DATE OF METHOD CREATION: 10/25/83, 2/3/84 Tine Stamp - <860227,1513>
HONS 023956
for
Th this
following pages project.
describe
Analytical
Request
Inforest Ion
generated
HONS 02395 7
tine Scaup - <860304.0958>
MONSANTO COMPANY/ENVIRONMENTAL SCIENCES CENTER
ANALYSIS REQUEST
DATE: 2-18-86
LOG NO: U-86-02-18-01
REQUESTER: KRUMMRICH
PROJECT NO:
760.28-6207
REPORT RESULTS TO: F1LES/KEES, Sharaan, Hughaa, McKenzie
ANALYSIS REQUESTS SENT TO: FILES. Maaa, Sharuan, Hughaa, McKanxla SAMPLE PICKUP BY: McKanzla
SAMPLE LOCATION: U-420
SAMPLE DESCRIPTION FOR 6 SAMPLES
BSC
SAMPLE IDENTIFICATION
NUMBER OF BOTTUS
NUMBER(S)
Method Blank Blank Soil Blank Soil + LS Blank Soil HS Log No. 00078, 81-4-1466 B-l, 0-15' Coapoalta, 81-4-1466 1SP-003-C, 81-4-1466 1SF-004-C. 81-4-1466
1SP-005-C, 81-4-1466 3SP-004-C, 81-4-1466
1 X 4 oz 1 X 4 oz 1 X 4 os 1 X 4 oz
1 X 4 oz 1 X 4 oz
PCB-1549 PCB-1550 PCB-1551-LS PCB-1552-HS PCB-1553, PCB-1554-DUP PCB-1S62 PCB-1555, PCB-15J6-DUP PCB-1557, PCB-15S8-L5 PCB-1559-HS PCB-1360 PCB-1561
Ncta - LS lafara to a low laval native spike, HS refers to a high laval natlva aplka, and DUP rafara to duplicate analyses.
RECORDED BY: McKanzla
REQUIRED ANALYSES: PCBa
ANALYTICAL TECHNIQUES: TECHNIQUE (IN)
DATE COMPUTED
TECHNIQUE(EN)
date
COMPUTED
x CC/EC (18)
3/3/86
QUALITATIVE: X
SEMIQUANTITATIVE:
QUANTITATIVE: x
REQUIRED QA/QC: SEE COOD LABORATORY PRACTICES MANUAL
COMPLETION DATE REQUESTED:
1 Vaak
COMMENTS:
SAMPU DISPOSITION: HOLD FOR 30 DAYS SAFETY PRECAUTIONS: SEE SAFE LABORATORY PRACTICES MANUAL
HONS 023958
Tlae Scaup - <860304.0958>
MONSANTO COMPANY/ENVIRONMEMTAL SCIENCES CENTER
ANALYSIS REQUEST
DATE: 2/24/86
LOG NO: U-86-02-24-01
REQUESTER: Kruawrlch/Cloaknar
PROJECT NO: 760.28 - 6207
REPORT RESULTS TO: F1LES/MEES, Sharaan, Hughaa. KcKanzla. Tran*
ANALYSIS REQUESTS SENT TO: FILES, Maaa, Shaman, Hughaa, McKenzla
SAMPLE PICKUP BY: McKanzla
SAMPLE LOCATION: U-420
SAMPLE DESCRIPTION FOR 6
SAMPLE IDENTIFICATION
NUMBER OF BOTTLES
SAMPLES ESC
NUMBER(S)
Blank soil Bialik aoll + LS Blank toll + HS B-2, 0 - 15' B-J, 0 - 7' B-5, 0 - 7.5'
B-6, 0 15' B-7. 0 - 15' 8-8, 0 IS' Method Blank
1 x 4 oz 1 x 4 os 1 x 4 oz
1 x 4 oz 1 x 4 OS 1 x 4 oz
PCB-1363 PCB-1364 PCB-1565
PCB-1S66, PCB-1567-DUP PCB-1568, PCB-1S69-DUP PC8-1J70, PCB-1571-LS, PCB-1572-HS PCB-1573 PCS-1574
PCB-1575 PCB-1576
Nota DUP rafara to dupllcata analyaaa, LS rafara to a low laval nativa aplka, and US rafara to a high laval nativa aplka.
RECORDED BY: McKanzla
REQUIRED ANALYSES: PCBa
ANALYTICAL TECHNIQUES: TECHNIQUE (EM)
DATS COMPLETED
TECHNIQUE(EN)
DATE COMPUTED
x CC/EC (18)
3/3/86
QUALITATIVE:
SEMIQUANT1TAT1VE:
QUANTITATIVE:
REQUIRED QA/QC: SEE GOOD LABORATORY PRACTICES MANUAL
COMPLETION DATE REQUESTED: ASAP
COMMENTS: SAMPLE DISPOSITION:
HOLD FOR 30 DAYS
SAFETY PRECAUTIONS: SEE SAFE LABORATORY PRACTICES MANUAL
HONS 023959
lh following it copy of the ESC/DAO Good Uborctor* Frcctlcci Manual.
HONS 023960
Copy Number:
GOOD LABORATORY PRACTICES MANUAL
Ultratrace Analyala Croup March 1984
Bopcnil J. IroW * Croup Leader, Ultratrace Analyala
R. A. Uoltanann Mana|ar, Eavlronnental Sclencea Cental
laaued to: Bate: ____
JR3/J0B A
Zavlroanantal Scleocee Canter Dayton Laboratory
Dayton, Ohio 45407
HONS 023961
TABU OF CONTENTS
I Objective* II Scop* III Analyala
A. Method* >. QA/QC Progra*
1. Sanpl* Preparation QA/QC a. Method Blank* b. Replicate* c. Spike*
2. Inatruaental Analyala QA/QC a. Inatruaentatlon b. Blank* e. (hiantltatlon Internal Standard d. Standard*
C. D*|ieea of Quantitation 1. Qualitative Analyala a. Tentative b. Confined 2. Seal-Quantitative Analyala 3. Quantitative Analyala
D. Quality Criteria and keaedlal Action 1. Quality Criteria a. Blank* b. kecoverle* c. Preclelon d. Halt of Detaetlon a. Accuracy 2. keaedlal Action
IV Data V Saapl* Dlapoaal
FIGURES
ZiEVX*
1 Kxaaplaof CC/MS Logbook page 2 Exaoplt of CC/EC Logbook page 3 Example of Dlac/Tapa Logbook page
!u I 1 j ! 2 2 2 2 2 3 3 g *
^
A 7 7 7 7 7 B 8 8 8 8 9 9 9 9 10
SSB*
5 6 11
HONS 023962
I. Objective*
Th Mia objective* of tho Ultratrace Analyst* Croup quality aeaurance/quality control prograa oral 1) to aaaura that our laboratory generates high quality rcaulta; and 2) to Mlntalo the nccaaaary rtcorda that docuaent laboratory parfonanca.
II. Scop*
Tha acopa of thla annual lncludaa arena of GLF not apaclfleally addraaaad In tha ESC aactloa nanual and axpanda upon cartala araaa vhera QA/QC practlcaa differ froa thoae daacrlbad la the aactloa. Mnual. It la Intended to be uaad along with tha aactloa naaual to provide a coaplata picture of tha CLP within tha Ultratrace Analyala Croup.
III. Analyala
Tha generation of analytical raaulta within tha Ultratrace Analyala Croup routinely lavolvea two proceaaaai aaapla preparation aad lnstrxmntal aaalyal Staple preparation lnvolvee one or aora of a variety of ttchnlquea Including extraction, dilution, acid/base waahaa, coliao ebroaatography, concentration and nuaerou* other technlquaa to render tha aaapla la a *ultable condition for lnatruaental analyala. Inatruaantal analyala taken the aultably prepared aaapla and Introduce* It Into an analytical lnetruaent to aeaaure the dealred paraaeter(a). goth of theea procaaaca can be deacrlbed by clearly defined and aeparabla nethoda called aaaple preparation aethoda (SPMa) and lnatruaental analyala nethodc (lAMa). SPMa and lAHa My be coablned In nuaeroue waya (depending upon the nature of the eaaplea and the needa of the cuetOMr) to produce a aucce**ful analytical protocol. For example, aeveral different SPMa My be uaed to produce aaaplea that era (ultable for aMlyala by a alngle IAM. The Manure* Incorporated Into each of theae experlaental proccaae* to enaure that an aaaeaaacnt of the quality of tha raaulta can be aad* conatltut* the QA/QC prograa for a project. The following aubaectlon* deacrlbe the eleaenta of the analyala proceaa:
A. Method*
Method* are the written docuaentatlon that deacrlbe the analytical proceaa. They contain aufflclent detail auch that a coapetent aclentlat or technician can readily perform the required analyaea. Tha uaual practice la to have method* that deacrlbe the aaaple preparation proceaa (SPMa) and aethoda that deacrlbe the lnatrumental aMlyala procaa* (lAHa). Each method developed within the Ultratrace Analyala Croup* la aaalgned a method number a* deacrlbed In the ESC Section Manual.
Method* are obtained froa verlou* eource* Including ln-bouae develop aent, aodlflcatlon/adaptation of literature nethoda, or apeciflc protocol method* dictated by government agenclea. Method* My be formally validated by a aerie* of experlaenta that deacrlbe a daaalcal validation protocol or My be lea* vlgoroualy proven owing to factor* auch aa frequency or u*e, customer needs and
HONS 0239*3
1
cost/tlalng restriction!. Jo soy csss s QA/QC progrsa Is applied to tbs enalyals process to provide a aessure of tbs quality of tbs results, teless a QA/QC progrsa Is prescribed by a required . protocol (e.g., ETA Dio*in In Soil protocol), certain alnlaun QA/QC asssuras (depending upon the analysis type) are Incorporated Into all Ultrstrace Analysis projects. The following subsection describe* th* Ultrstrace QA/QC progrsa:
QA/QC Progrsa
An effective QA/QC progrsa Incorporates axperlacnts that provide lnforaatlon relative to each of the following questions:
(1) Are there any lapurltiss, background or cootaalnatlon that will Influence the results)
(2) How reproducible are the results?
(3) Bow well can th* analyte be recovered froa the saepl* atrlx?
(A) What 1* th* Halt of detection for th* analysis?
(5) What la th* dynaalc rang* of th* analysis?
(6) What Is th* accuracy of th* analysis?
All of these questions are addressed by properly selecting/applying th* us* of blanks, replicate*, spikes and standards In a QA/QC progrsa. Th* discussion of th* use of these QA/QC techniques as they apply to Ultrstrace Analysis Croup activities la beat done by considering th* saaple preparation and lnstriaental analysis processes separately.
1. Saapls Preparation QA/QC
a. Method blanks - Representative glassware, solvents and rsagsnts ara used with saaple aetrlce* which are slallar to those for which results are being reported, yet do not contain th* analytes of Interest. Method blanks are analysed at a frequency equal to 10X of th* analysed saaple* for saaple sets which are Multiples of 10. At least on* Method blank la analysed for saapls sets containing between 1 and 9 saapls*.
b. Replicate* - If sufficient saaple aaounts have been suboltted for analysis, repllcata frequency Is tha saa* as th* Method blank frequency. If at all possible, replicate* should be obtained froa th* saae saaple bottle In order to alnlals* saaple lnhoaogenelty probleaa due to saapls* being taken st slightly different tlaes.
e. Spikes - If sufficient saapls Is available for each saaple type, eh* saaple 1* split and spiked st t levels with
2 HONS 02390b
th native (unlabelad) analyte(s). Tha levels are typically 2* (low) and 20* (high) tha anticipated detection Halt and eerve aa a technique for astlaatlng the Halt of detection for each aatrlx. These low end high spikes are conducted at a frequency equel to the Method Blank frequency. Obviously spiking with the native enalyte cannot be done for wldeacan enalyele since this presupposes knowledge of the Identity of the analyte(e) In the saaple.
Other spiking techniques are uaed to evaluete the sxtractlon/recovery efficiencies for the enalyte(e) of lntereet. Ideally extractlon/recovery efficiencies are determined for each saaple, since. In principle, eech saaple nay represent a different aatrlx. This can be done very easily when tha detection technique Is Bass spectrometry If an lsotoplcally labeled version of the enalyte(s) Is available. Docuaentatlon of extraction/recovery efficiencies Is not required for each eaaple If the saaple aatrlx for s set of eaaples Is constant. However, for a saaple set for which the similarity of saaples Is not known, and for which adequate eeaple la available, each saaple aust be split sod eplked with a known aaount of tha analyte(a) of Interest to deteralne extraction efficiency. If adequate saaple site Is not available or the Identity of the analyta(e) Is not known before the fact (l.e., wldescan analysis), surrogate spiking coopounds aay be used to assess extraction efficiencies In each saaple without actually spiking each saaple with the analyte(s) of Interest. The choice of the surrogate spiking conpound la tailored for each analyte. This surrogate aust be choseo so that It Is either chealcally Identical to the analyte of lntereet (for exaaple using lsotoplcally labeled analogues of the analytes), or Is closely slallar In terns of llquld/llquld partition properties, cbealcal reaction properties, colunn elution properties or other aatrlx Isola tion properties which sre used to Isolate the analyte(s) froa tha saaple aatrlx. Another property of the surrogate spiking compound la that it not be present In the saaple being analysed.
Instnsental Analysis QA/QC
The final step In obtaining analytical results Involves the use of an appropriate lnstruaental technique to produce the analytical data. Several QA/QC practices aust be Incorporated In this process to ensure validity of the data.
S. Instrumentation
Careful docuaentatlon of Instrument usage, calibration, and nalnteoance Is essential for the generation of high quality results. Each major Instrument within the Oltratrace Analysis Group will be the assigned responsibility of s professional employee designated as the Instriaent Steward. The Instrvent Steward la responsible for making sure that logbooks are avail able and properly coapleted by lnstriaient users. It Is the
3 HONS 023965
reaponalbillty of each Individual ualnf the equipment to record all tba pertinent data required In the logbook. An example of a page from a CC/MS logbook la given In figure 1 and that of a GC/EC logbook la given In Figure 2.
Inatruaenta will be calibrated according to the lnatruent nanufacturera' apeclflcatloaa or according to the nethod being uaed with the lnatnaent. A log of lnatruent calibration will be nelatalned with the loatrimnt.
The Inatruaent Steward will be raaponalble for enaurlng that preventative and corrective nalntenanca prograna are carried out on all lnatrvaente under hla/ber reaponalbillty. If a apeclflc problem la noted bp an lnetriaeent uaer. It ahould be noted In the logbook and the Inatruaent Steward notified ao that appropriate corrective action can be taken.
b. Blank*
A advent blank will be analyzed at a frequency equal to the method blank. The method blank can eerva aa the aolvent blank provided It la clean In the area of the analyte(a) of Interact. Thlt practice eliminate* the poaalblllty of background Inetruaental contamination.
c. Quantitation Internal Standard
A quantitation Internal atandard will be added to each cample following cample preparation but prior to lnatrumental analyala. Thlc compound will cerve for determining relative reaponae factor* and for correcting for variation* In aample Injection volume* and evaporation of aolvant*.
d. Standard*
Standard* are colutlona of the analyta(a) of lntereat uaed to determine the reaponae of the detector over the range of analyte concentration* found In the aample*. For Quantitative analyaea, aufflclent atandard* and replication of atandard* will be run to demonatrat* linearity and predeloo of the detector reaponae over the range of analyte concentration*. Should aample concen tration* fall outalde the demonatrated linear range, either additional atandard* are prepared to expand the range, or appropriate dllutloa/concentratlon of the aample 1* done to place It In the proper range.
Degree* of Quantitation
The Information provided for any particular analyala la tailored to the needa of the cuatomer. In actual practice thee* neede vary acroe* the broad continuum from the groaaly qualitative to the preclaely quantitative. It la informative to examine what 1* Involved In providing the varying degree* of quantitation required by our cuatonera.
HONS 0239bb
4
HP 5985A
kMtt,
MR..
*?<__
MuimU
RNlMIINimNliM Ml___ .... - --
Em M* 11 MSr Itaa
-
Is UwiifUMiM
>o-M lit m. Mil iftr* mm uk- X ii
1 1; l 1 l
tt* r* 11
ft o
fi
femj Bit %
mi> fell
i L-0 V -
ii *! If
t**, *>
> i
n n
ife
u**'!* M
Jii a i V
it IVS *< v.
IS >!**< i t Ill Cm Oft- mV -
-
it
9
i. Mrf tOB *
t.i
T
nr
,
Mlpm
r* i i K f
1 li1
- - n IS* ri r rt
i
%*
u tfM r~
* ftri krM 7
l1
M
*
1 r
IHI
in M M
n M tf
n*. #V H
'i
r r~
HtklNt MlMill M*
l i
__.
i.* it
It IS)
tml
A k V &
T
U,
-
f
J l
*W
*4*
\%
A*
M r
lot
? 1.
** 1 _
i .... r
it
1
i
MT-i
Iff-
u
*
* CM **
1 1
J* l/ft *
k
1
1
si n r s .1*
M irt M f i1 1 1 1 i if* #* 4- 4 t
P1CVM t. Ixiifli of CC/m Loftboofc HI*.
HONS 0239*7
bum___ -
hpsmo ec/.
- ,, - _............................-- WMHuiMbi
. . ----------------------------- buiui-- . ----------
bn--
..............Mt UUt
ricow 2. Kxapl of CC/BC U|kMk Ml*
HONS 023968
Qualitative Analysis
Qualitative enelyele lnpllei no quantitation at all but rathtr aaafca only the Identity of tba coapound(a) present. CC/MS la particularly applleabla to thla typo of analyala problas. Two typoo of Identifications can b aade:
a. Tentative
A tentative Identification la Bade on tha baela of the analyat'a judgement of a natch between the aaaa epectrua froa the aeaple and a aaaa epectrua froa a reference library. Thle la often done for the large nuaber of coapounda found In a wldeecan organic analyala.
b. Confined
A confined Identification requlrea that the chromato graphic retention tlae and the aaaa epectrua of the unknown compound natch tboae of a known atandard of the tentatively Identified coapound. Thla la often done in wldeecen analyeee when atandarda can be obtained for tentatively Identified compounde that are of concern.
The normal QA/QC requlreaenta for qualitative analyala are (1) analyala of a blank, (2) analyala of duplicate aaaplea and (3) one of a calibration coapound (ueually Decafluorotrlphenylpboapblne, DPT?*) to aaaure that tha aaaa apectroaeter will produce aaaa apeetra that can be coapared with library apectra.
Seal-Quantitative Analyala
Seal-Quantitative Analyala axtenda the Information provided by e qualitative analyala to Include none eatlaata of the aaount of analyta(a) prevent. The aetbod of aeal-quentltatlon Involute the coaparleon of detector reeponae of the enalyte(e) with that of an Internal standard. The outlasted concentration la obtained by aesialng a unit response factor between the analyte(a) and the Internal etsndard(e). An Indication of recovery from the aeaple aatrlx la obtained froa the recovery of the surrogate Internal standard(a).
Quantitative Analysis
Quantitative Analysis provides for the accurate aeaeseaent of the aaount of analyta(a) present In a aeaple. To be able to do quanti tative analysis one Bust know the Identity of the analyte ao that standards can be prepared for spiking and for the generation of calibration curves. The aetbod of quantitation Is bated on a three-point calibration curve ualng standards of the analyte(a) of Interest over the range of concentrations la the aaaplea. A out point calibration method can be used (at with the laboratory data
7 MOWS 023969
system) provided thee linearity bee been deaonetrated over the concentration rang* of the taaplee nelng standards of the analyte(s) at three concentrations In the range. This calibration carve Is then used to provide concentrations of the analyte(s) la the saaples vis an external standards aethod or aora preferably vie an internal standards aethod. For the Internal standards netted, the quantita tion Internal standard la added to each of the standards (Just as vlth tha saaples) prior to Instnaental analysis and rslstlvs response factors are deteralned.
For quantitative analysis tha asss spectroaeter la operated as a gas chromatographic detector. Tha KS Is therefore tuned and operated In a Banner specified In the approved aethod rather than using a calibra tion compound as required for qualitative analyses.
Quality Criteria and Reacdlsl Action
The Inclusion of QA/QC measures Into an analysis program has little aesnlng unless the results era Interpreted snd appropriate action Is taken vhen necessary. The ability to do this assuaes sons set of criteria that will trigger s response or remedial action. The following subsections describe the criteria that are used In the Ultratrsce Analysis Group to evaluate vhen quality control data Indicate a need for corrective acasures snd vhst rsaedlal action will be taken.
1. Quality Crltsrla
The overriding quality criterion above all others lai Do the results asst the needs of the customer. This determination will be aade Jointly between tha customer and the analyst. The analyst oust exercise caution in not allowing the custoaer to overstate, misinter pret or unintentionally alsrepresent the data. In addition to this prime quality criterion, the following conditions aust be asti
a. Blanks - In the event that a blank producss a positive value, It aay oot be used as s valid blank If It exceeds 10X of any reported value for s sample.
b. Recoveries - Recoveries for all surrogate snd native spikes aust lie In the range of J0t<Recovery<150T.
c. Precision Precision will be calculated based on the recoveries of surrogate Internal standards. Average recoveries will be calculated with i standard deviation for each sample set. Repli cate analyses snd low snd high native spike recoveries aay also be used to provide additional lnforastlon/Insight Into the precision of the analysis.
HONS 023970 8
d. Halt of Detection - The Halt of detection (LOD) will nonull7 be eteted a*i the velne of the low level native eplke If It le recovered and quantifiable. Should tha low laval aatlva eplke not be recovered, the LOD will be etated ae 4 tha valua of tha high level native eplke If It le recovered and quantifiable. Should neither eplke be recovered, a declalon aunt ba aada regarding the advleabllltp of reproceeelng tha eaaple. Should all eaaplea contain auch large quantifier of the analpte(a) that the levela of the low and high eplkee are lnelgnlflcant (<10t) bp coaparleon, the value of the LOD becoaea leaa laportant and la alnplp atated aa the LOD for the lnetnaental analpala proceaa determined bp the analpala of atandarda and tha abllltp to recover the eurrogate aplkea.
a. Accuracy - The accuracp of the analpaea la beat deternlaed bp analpalng aome eanple which contalna the analpta at acme predetermined level (e.g., an MBS etandardlaed eaaple). If thla tppa of atandard la not available than tha low level and high level eplkee een be need ae e aeaeure of tha accuracp of tha analpaea. Reaulte auat fall within a range of 752 to 1202 of the excepted value for the analpaea to bo cooelderad valid.
If the above qualltp criteria are not met the enalpet will luedlatalp aaaeaa tha need for aod extent of remedial action that map be neceaaarp.
2. Remedial Action
.
The flrat eourae of action will be for tha anelpat and/or group leader to contact the cuatoaer and dlacuea the reaulte pointing out tha llaltatlona of the data Indicated bp the qualltp control reaulta. At thla point tha ovarrldlng qualltp criterion of cuatoaer oeede will be addreeaed flrat. le could ba that tha cuatoaer'a naeda are net without aeetlng one or aore of the othar criteria. In auch a caee no remedial action le neceeearp. It could eleo be that tha cuatoaer hae auch a daaand for tlghtneaa In tha reaulte that hla naada are not net even though the other qualltp crltarla ara. Thla would trigger further analpaea with tighter qualltp control deelgned around the reaulte obtained (e.g., repllcatlona of poeltlve* to better aatabllah precleloo or aplkee of non-detected aaaplee to better cetabllah the limit of detection).
In conaultetlon with the cuatoaer additional experlmenta will be deelgned Including the appropriate qualltp control to ultlmatelp provide the reaulta of auffldent qualltp to meet the cuatoaer'a naeda.
IV. Data
Thla aectloa deala with the aubject of data and bow they are obtained, recorded and reduced ao aa to ba uaeable In a report and pet readllp available for referral and lnepectlon.
HONS 023971 9
The aanplaa vlll b labeled with a log number at aaapla login according to tha procadura daacrlbad In tha ISC Section CLP Manual. Vhan delivered to tha roepoaalbla technical pareon. tha aanplaa nay then receive additional labeling aa leaned aeceeeary. Thla additional labeling will be docuaented In a laboratory logbook and/or notebook. Thtae logbooka and notebooke will bn uaed by the analyate to record all pertinent work and reaulta obtained from the aanplaa. The laboratory notebooke will be tilled out In accordance with Honeanto Uniform Notebook Procedurea.
*11 raw data generated tor a given project, which cannot be conveniently placed In tha laboratory notebook (e.g., chronatograna, computer output, etc.), will be filed under aone preecrlbed order (l.a., log ounber) In a central file under tha auperviaon of the Project Leader and/or QA Speciallet.
Moat of the data generated by the Ultratrace Analyela Croup are computer data atored on aagnetlc dleca. In order to archive theee data the epeclflc file oaae and dlac number aaaoclated with tha analyela will be written down In tha laboratory notebook and/or lnatrunent logbook. When the dlac la completely full of data an entire unedited dlac lnage or copy of the fllea on the dlac will be tranaferred to aagnetlc tape. A logbook will be kept for recording the dlac nuuber, naae and prefix aaaocl ated with It, along with the aaaoclated tape and file nunber to which tha dlac waa tranaferred. An exaaple of auch a logbook la given In Figure 3. When the data are tranaferred a verification progran la uaed to check all tranaferred recorda for correctneaa. When tepee are filled (they typically hold aeven to ten dlac laagee) they ehould be atored In a fireproof vault.
All calculatlena of the reaulta of the data will be apeclfled In the aethod weed. Theee calculation! will he entered In the analyata laboratory notebook unleee they are computer generated. In thla caaa, a copy of the computer output will be filed with the raw data. The Project Leader will be reeponelble for checking the correctneaa of the data.
V. Sample Dlapoaal
gaaplee will be dlepoeed of In accordance with the lnatructlona on the Analyela Segueet form. The only exception to thla would reault when the analyela reveala a problem which requlreo aample dlapoaal la a manner other than that originally apeclfled. If the Project Leader notea from the reaulta of tha analyela that a potentially tonic product waa preeent In the aanplaa then the aaaplee will be dlapoaed of In a manner deemed aafe by the Safety Department. The date of aaaple dlapoaal and the manner ahould be noted on the requeat form atored with the raw data completing the chain of euatody of tha aaaple.
HONS 023972
10
(KlUt-trln Nrm B*U
.
CM 0HM4 T*m<
MU TuM
tn t (nu n
/*> (*)
i/lfc
bnft j/'i/c ODWrt
t>i
V-
/ ft) /3 V
OO
iW
t0
/
/'/t3
. )
I
smT
pt^*"/&
0KH
I
w V/r V'Y/b
Go 4Vi,)
6(fO)
G*>Wt)
&*") ovvK$)
IX. IM*)
l*A*
LSK. j1//! /!i
iy? (D owj n 3*11-0
i>t (*) laA] sn' 3*11-0
/ /AM>)U*Q - -
Jto> OMjiXAcI - <WcViK^K.
#*.
BW
//3 ftAi>r*a e* /
/N OMO&Q -
%
J-
I3n (nfttl)Ciun
i*o
caS
/V/ ^<V)
S>1 Sh
SM 3/Ap
Mi yfa
st>
i
s/l/ft
*Jfr/ts l
a/hiIts
6073/y,
)Gt>bl6o,
<St>1Kt) Ot>7/ W
CW<*J
M3(4
GJTSW
7A (
f/i* /At**) /*> (Afoz)
'Sk S> %?/&
G2>nSCT)
P*/3<P)
/<// (AM)
Wf
S>23 Of/
r/S //#<&}
5i> s}y>/it> <SM3 Q/
tit* (w)
Wilts
til (AUn)
sa Usi/ts
M (AM>
J2 iUth
ffl cam)
33
c/j^u
(SO CAM)
-13 Wih3
JLSa (M) JrTJ>Pry>-*-7K
s/1 biS
/Si /AM)(fa3 ftmrt- Cb^fli
oOrt. nMti
(Su 6*o*3 | |
fy'fa
ofJK
I
Ki (***> 'V -*
"
&K V
cif*- o*> o (J) (3 TJX. Ul ^T-Cc) j>Tt<. <
6>1A (7)
I$
riGUM 3. tsaaplo of DISC/Tapo Logbook paga.
HONS 023973
11