EPA-600/4-84-054
June 19S4
EPA METHOD STUDY 29,
METHOD 624—PURGEABLES
by
Radian Corporation
P. 0. Box 9948
Austin, Texas 78766
Contract No. CI-63-03-3102
Project Officer
Raymond Wesselman and Bob Graves
Quality Assurance Branch
Environmental Monitoring and Support Laboratory
Cincinnati, Ohio 45268
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
EPA-600/4-84-054
3. RECIPIENT'S ACCESSION NO.
PM* 20991 5
4. TITLE AND SUBTITLE
EPA METHOD STUDY 29, METHOD 624 —
PURGEABLES
5. REPORT DATE
June 1984
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Radian Corporation
B. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
P.O. Box 9948
Austin, TX 78766
10. PROGRAM ELEMENT NO.
CBL1A
11 CONTRACT/GRANT NO.
68-03-3102
12. SPONSORING AGENCY NAME AND ADORESS
Environmental Monitoring and Support Laboratory
U.S. Environmental Protection Agency
26 W. St. Clair Street
Cincinnati, OH 45268
13 T^FflfPgRgJND PERIOD COVERED
I
14. SPONSORING AGENCY CODE
EPA 600/06
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The work which is described in the report was performed for the purpose of
validating, through an inter!aboratory study, Method 624 for the analysis of the
volatile organic priority pollutants. This method is based on purging and
concentration of the various analytes on an adsorbent followed by thermal
desorption onto a gas chromatographic column. A low resolution mass spectrometer
serves as the measuring device.
Participating laboratories were selected based upon technical evaluation of
proposals and upon the analyses results of prestudy samples. The laboratories were
supplied with ampuls containing various concentrations of the pollutant compounds.
These solutions were aliquoted into four different water types which were
subsequently analyzed according to the appropriate methods. In addition to the
sample concentrates, each laboratory was supplied with an industrial effluent which
was know to contain various pollutants and which was used to estimated false
positive and false negative data.
The data obtained from the interlaboratory study were analyzed employing a
series of computer programs known as the Interlaboratory Method Validation Study
(IMVS) system which was designed to implement ASTM procedure D2777.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENOEDTERMS
c. COSATi Field/Group
MS. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
246
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
CPA F*»m 2220-1 (R«v. 4-77) prrviou* edition is obsolete
-------
DISCLAIMER
The information in this document has been funded wholly or in
part by the United States Environmental Protection Agency under
contract 68-03-3102 to Radian Corporation. Radian prepared this
report using EPA's procedures for data analysis and reporting of
data. The conclusions and recommendations follow EPA review
comments. It has been subject to the agency's peer and adminis-
trative review, and it has been approved for publication as an
EPA document. Mention of trade names or commercial products does
not constitute endorsement or recommendation for use.
ii
-------
FOREWORD
Environmental measurements are required to determine the quality
of ambient waters and the character of waste effluents. The En-
vironmental Monitoring and Support Laboratory (EMSL)-Cincinnati
conducts research to:
• Develop and evaluate techniques to measure the
presence and concentration of physical, chemical,
radiological pollutants in water, wastewater,
bottom sediments, and solid waste.
• Investigate methods for the concentration, re-
covery, and identification of viruses, bacteria,
and other microorganisms in water.
• Conduct studies to determine the responses of
aquatic organisms to water quality.
• Conduct an Agency-wide quality assurance program
to assure standardization and quality control of
systems for monitoring water and wastewater.
This publication, Interlaboratory Method Study for EPA Method
624 reports the results of EPA's interlaboratory method study
for the volatile organic compounds.
Federal agencies, states, municipalities, universities, private
laboratories, and industry should find this interlaboratory study
useful in monitoring and controlling pollution in the environment.
Robert L. Booth, Acting Director
-------
ABSTRACT
The work which is described in the report was performed for the
purpose of validating, through an interlaboratory study, proposed
Method 624 for the analysis of the volatile organic priority pol-
lutants. This method is based on purging and concentration of
the various analytes on an adsorbent followed by thermal desorp-
tion onto a gas chromatographic column. A low resolution mass
spectrometer serves as the measuring device.
Participating laboratories were selected based upon technical
evaluation of proposals and upon the analytical results of pre-
study samples. The laboratories were supplied with ampules con-
taining various concentrations of the pollutant compounds. These
solutions were aliquoted into four different water types which
were subsequently analyzed according to the appropriate methods.
In addition to the sample concentrates, each laboratory was sup-
plied with an industrial effluent which was known to contain
various pollutants. The purpose of this sample was to ascertain
the propensity of the method to produce false positives and
false negatives.
The data obtained from the inter laboratory study were analyzed
employing a series of computer programs known as the Interlabora-
tory Method Validation Study (LMVS) system which was designed to
implement ASTM procedure D2777. The LMVS analyses included tests
for the rejection of outliers (both laboratory and individual),
estimation of mean recovery (accuracy), estimation of single-
analyst and overall precision, and tests for the effects of water
type on accuracy and precision.
iv
-------
This report was submitted in partial fulfillment of contract
number 68-03-3102 by Radian Corporation under the sponsorship
of the U.S. Environmental Protection Agency. The report covers
a period from January, 1982 to June, 1983.
v
-------
CONTENTS
foreword iii
Abstract iv
F inures vi i
Tab :es vi i i
1. Introduction 1
2. Conclusions 3
3. Recommendations 14
4. Description of Study 15
Test Design 16
Selection of Participating Laboratories 18
Preparation of Youden Concentrates 18
Verity, Homogeneity and Stability of
Prepared Ampules 20
Proof of Feasibility of the Study Plan 20
5. Statistical Treatment of Data 24
Rejection of Outliers...' 25
Statistical Summaries 27
Regression Analysis of Basic Statistics 58
Comparison of .Accuracy and Precision
Across Water Types 60
6. Results ana Discussion 94
Accuracy 94
Precision 99
Effects of Water Types 101
Comparison of Published Method Perforxance
Data to Inter laboratory Study Data 103
Revised Equations 106
Responses to Cuesticnr.aire 106
Method 624 Ill
7. Evaluation of Surrogate Compounds 119
References 124
Appendices
A. Study on False Positives and False Negatives 126
B. Results on GC/KS Feasibility Study 129
C. Raw Data 132
D. EPA Method 624 - Pureeables 223
-------
FIGURES
Number Page
1 Spike Recoveries Vs. Surrogate Recoveries {%)
VOA Fraction - Chlorobenzene 122'
vii
-------
TABLES
Number Page
1-1 through Regression Equations for Accuracy and
1-7 Precision 6
2 Accuracy and Precision Estimates (Com-
puted From the Regression Equations) for
a Prepared Concentration of 100 pg/L 13
3 Fifteen Laboratories Selected for Parti-
cipation in the Method 624 Interlaboratory
Study 19
4 Concentration of Analyzed Volatile Organic
Solutions 21
5 Spiking Concentration of Surrogate Compounds.. 22
6 Performance Sample for Method 624 22
7-1 through Statistical Summary for Each Compound
7-28 Analyses by Water Type 30
8-1 through Effect of Water Type on Each Compound
8-28 Analysis 66
9 Accuracy and Precision Estimates for Pre-
pared Concentrations of 10 and 100 yg/L 95
10 Summary of the Tests for Differences Across
Water Types 102
11 Comparison of Accuracy and Precision of
Inter-laboratory Study Data (for a Prepared
Concentration of 100 ug/L) and Published
Method Performance Data 104
12 Revised Regression Equations for Accuracy
and Precision 107
13 Revised Accuracy and Precision Estimates
for 100 ppb Concentration Levels 110
viii
-------
TABLES (Continued)
Number Page
14 Summary of Instrument and Calibration Para-
meters 112
15 Summary of QA/QC Procedures 114
16 Correlation Coefficients of Surrogate Recov-
eries and Spike Recoveries 120
ix
-------
SECTION 1
INTRODUCTION
The various analytical laboratories of the U.S. Environmental Pro-
tection Agency (EPA) gather water quality data to provide informa-
tion on water resources, to assist research activities, and to
evaluate pollution abatement activities. The success of these
pollution control activities depends upon the reliability of the
data provided by the laboratories, particularly when legal action
is involved.
The Environmental Monitoring and Support Laboratory-Cincinnati
(EMSL-Ci), of the EPA develops analytical methods and conducts
quality assurance programs for the water laboratories. The qual-
ity assurance program of EMSL is designed to maximize the relia-
bility and legal defensibility of all water quality information
collected by EPA laboratories. The responsibility for these ac-
tivities of EMSL is assigned to the Quality Assurance Branch (QAB).
One of these activities is to conduct interlaboratory tests of the
methods. This study reports the results of the validation effort
on Method 624 for the volatile organic compounds.
The interlaboratory study of EPA Method 624 consisted of three
distinct phases. Phase I involved the preparation and ampuling
of concentrates of the compounds. The prepared concentrations
were then verified using GC methods.
The second phase involved the selection of participating labora-
tories. Solicitations were made for both paid participants and
1
-------
volunteer participants. Selection of laboratories was based on
experience, facilities, quality control procedures, and cost
estimates received from laboratories. Final selection of fif-
teen laboratories was made after the successful analysis of a
performance sample. No laboratories chose to participate in
the study as volunteers.
The third phase involved the conduct of the study. The prepared
ampules were distributed to each laboratory. Each laboratory
supplied the required four water types into which the ampules
were spiked. in addition, a single water sample was supplied
by Radian to evaluate the method's tendencies for false-positives
and false-negatives. After analysis, results were reported on
standard data sheets. Data were keypunched and validated by
Radian. The final step in the study was to conduct an analysis
of all data obtained using US EPa's IMVS computer programs.
2
-------
SECTION 2
CONCLUSIONS
Method 624 is acceptable for the analysis of purgeable priority
pollutants. The accuracy of the method is judged very good while
overall precision and single-analyst precision are considered ac-
ceptable. For most compounds, matrix does not significantly ef-
fect the analysis. Method 624 was characterized in terms of
accuracy, overall precision, single-analyst precision, and the
effect of water type on accuracy and precision through statisti-
cal analyses of 9,880 reported values. Estimates of accuracy
and precision were made and expressed as regression equations,
shown in Table 1 for each compound. The equations were based
on the 8,446 data values remaining after eliminating 1,434 values
(.approximately 15%) designated as outliers by the IMVS programs.
The development and interpretation of these regression equations
are discussed in Section 5. To facilitate the interpretation of
these equations, Table 2 was prepared. In Table 2, accuracy
(percent recovery), overall precision (percent standard devia-
tion) , and single-analyst precision (percent standard deviation)
were computed (using the regression equations) at a concentration
of 100 yg/L.
Accuracy is obtained by comparing the mean recovery to the pre-
pared values of the concentrations and computing the percent re-
covery. Overall, recoveries for the volatile organic compounds
are very good for all of the water matrices with an average re-
covery of 1007o. The mean recovery statistics (at 100 wg/L) for
the volatile organic compounds range from 68% for bromomethane
in the surface water matrix to 123% for cis-1,3-dichloronronene
3
-------
in the distilled water. One-half of the mean recoveries are be-
tween 94/0 and 105/o, with one-fourth of the mean recoveries above
and below these values. Recoveries for bromomethane are consis-
tently low (ranging from 68% to 75%,) for all water matrices.
Mean recoveries for cis-1,3-dichloropropene and 1,2-dichloropro-
pane are high with recoveries ranging from 116% to 123%, while
the recovery of trans 1f3-dichloropropene is uniformly low,
averaging 83%. It is known that the isomers of 1,3-dichloropro-
pene are relatively unstable and may decompose to 1,3-dichloro-
propane.
The overall standard deviation of the analytical results is an
indication of the precision associated with the measurement gen-
erated by a group of laboratories. The percent relative stan-
dard deviation (RSD) at 100 ug/L for the volatile organic com-
pounds range from 13% for trichloroethene, 1,1-dichloroethane,
and 1,2-dichloropropane in the various water matrices to 60%
for chloromethane in the industrial effluent with a median value
of 24%. Precision for chloromethane is relatively poor for all
water matrices with percent relative standard deviations rang-
ing from 457<> to 60%. One-half of the RSDs are between 20% and
29%. In 95% of the cases the RSDs are less than 44%.
The percent relative standard deviation for a single analyst
(RSD-SA) indicates the precision associated within a single
laboratory. The RSD-SA for samples at 100 yg/L ranges from
11% for carbon tetrachloride (distilled water matrix) and 1,2-
dichloropropane (tap water matrix) to 58% for chloromethane in
the industrial effluent with a median RSD-SA of 19%,. Single-
analyst precision for chloromethane is relatively poor with
RSD-SAs ranging from 37% to 58%. One-half of the RSD-SAs at
100 yg/L are between 15% and 23%,. In 9570 of the cases, the
RSD-SAs" are less than 36%.
4
-------
Three compounds used in this study, bromoraethane, chloromethane
and chloroethane, are gases in pure form. Although there are
no clear trends for accuracy in the gaseous species as opposed
to less volatile compounds, it is possible that the low recovery
observed for bromomethane and the poor precision for all three
compounds may be due to inherent difficulties in handling gaseous
and extremely volatile compounds during the various preparation
and analytical procedures required in the method. Bromomethane
is also known to be unstable, which could also account for low
recoveries.
The effect of water type was different for the various volatile
organic compounds. For most compounds the water matrix does
not have a great effect on either the accuracy or precision.
Over all, recoveries for the volatile organic compounds averaged
1007:, in distilled water, 10173 in tap water and surface water,
and 97% in the industrial effluent matrix. Precision (RSD and
RSD-SA) for the volatile organic compounds ranged from a median
RSD of 217c and a median RSD-SA of 167a for the distilled water
to a median RSD of 257* and a median RSD-SA of 237o for the indus-
trial effluent matrix.
A trend toward higher recoveries Cahove 1007o) for the lowest con-
centration Youden pairs was observed for 10 compounds. One expla-
nation could be sample contamination from the presence of these
compounds in the laboratory. Methylene chloride displayed the
most pronounced example with recoveries averaging 14270) 7670 and
8370 for the low, medium and high pairs respectively. Low-level
contamination may be responsible for the 14270 recovery of the low
pair. Blank concentrations were also higher for methylene chlo-
ride than for many of the other compounds, indicating a greater
likelihood of low-level sample contamination. This explanation
is less clear for other compounds. For example, the trend is more
pronounced for the chlorobenzenes than for benzene or chloroform,
yet the latter compounds would be expected to be more ubiquitous
in a laboratory environment.
5
-------
TABLE 1-1
ENVIRONMENTAL HON I TONING AND SUTPOM LAHORATuM
orrjct 01 research and development
ENVIRONMENTAL PROTECTION AGENCY
•* FPA r E 'HOD t?4 VAI IDATION STUOT - PURbEAPlFS ••
Mf-RESSICN EQUATIONS FOR ACCURACY AND PKfCTSIOfc
UATFR TTPf HINMNE IftOMOftJfHLORO^E THANF BRO"OfOR«* DROMOHfTHANf
APrilCAniC CONC. »
DISTILLED WATER
SINGLE-ANALYST PRECISION
SP
= 0.26X -
1.74
s«
= C.15* ~ 0.59
SP
= 0.14 X « 0.19
SR = f>.?7x
- 0.50
0VF9All PR f CIS1OM
s =
0.25* -
1.3?
s
= 0.20 x ~ 1.13
S =
u . 201 ~ 1.18
S = 0.25% «
0.44
ACCURACY
X =
0.9J( «
2.CC
X
= 1.03C - 1.5P
I =
1.01C - 0.89
X = C.72C -
0 .79
TAP UA T F P
SINGLE-ANALYST PRECISION
SR
= nt2z* -
C.24
SR
* f. 17* « 0.94
SR
=• 0.31* • 1.36
SR * 0.29x
t
o
overall iricision
s -
o.??* -
0.75
S
= C.29X « 3.76
S =
0.33X « 1.03
S - 0> 54k «
0.57
ACCURACY
* *
0.95C «
1.40
X
= 1.03C ~ 1.35
X =
1.13C - 1.07
X " C . 6 9 C -
1.14
SURFACE WATER
single-analyst rptClSION
SP
= C.15* -
P.60
SR
= T.18* ~ 0.43
SR
= 0.13m « 0.06
SR = 0 . 2 4 X
- 0.15
OVE P A| L PRECISION
S
C .2'* -
1.0?
s
= C .22% « o.eo
S -
0. 2^ X < 0.93
S = C.25X «
0.6 7
ACCURACY
I =
0.94c ~
1 .SP
X
= 1.0CC - 1 .T2
I =
0.97C - 0.67
X « 0 * 69C -
0.51
INDUSTRIAL t (FLUENT
siwgif-analyst precision
SR
= 0. 14X -
C.91
SR
= 0.23* - 0.15
SR
= 0.28X - C.O2
SR « C.37X
- 0.21
OVERALL PNEC1SION
S s
0.22* -
9.86
S
=¦ C.22X ~ 1.01
S =
0.33X •» 0.49
S = 0.41X -
0.0?
ACCURACY
X =
Q . S 9 C ~
1.60
X
« 0.94c - 0.93
X =
0.95C - 1.65
X * 0.76C -
0.P0
* "FAN RFCOVFRY
C = TRUE VALUE FOR THE. CONCENTRATION
^Revised regression equations and estimates of accuracy and precision are given in-Tables 12 and 13.
-------
TABLK 1-2
IKVl RONf'f NTAl r ON I I 0 RING *N0 SUPPORT LAHORATORY
o r r ice of r£sfarcm and dfvfiopmfnt
i NV I HONME NT Al PHOItfMOU AGENCY
•• rr* kfthoo *24 valioatjon study - purgeaules *•
R»fRESSICN E Ou*1 I ON S FOR ACCURACY AND PRECISION
UATFR T YpE CAfil'ON lfTRAC»'lOPI0f * CNlOROflfNHNt C H L 0 ROE T H ANf * CHIOROFOR*
APPLlCAPIf COMf. RANG! <15.5 " 600.0) (7.3 " 438.0) C 4.5 - 5CP.CI
0 I ST ILL E 0 VAIER
SINGLE-AWALTSI PRECISION $R • C.11* ~ C.35 SR = C.16* - P.C* SR * 0.25* « 2.02 SR = 0.16* ~ 0.22
OVERALL PRFCIS10N S - J.14* « g.17 5 = C.26X - 1.92 S = 0.27X # 1.95 S = 0.1** ~ 0.16
ACCURACY * = 1.01C - 0.84 i = G.S8C ~ 2.28 * = 1.W8C ~ 1.50 * * 0.9IC ~ C.33
TAP WATER
SINblt-MJALTST PRFCJSION SR = 0.?'* - P.fi5 SR = C.19X ~ 0.69 SR = O.'IX - (J . 7 1 SR ¦ C.?3x 4 0.42
OvfRAu PRECISION 5 » 0.24* - 0.S7 S = C. 22 * - 0.3C S * C.J5* « C.C4 S = 0-51* « 5.58
ACCURACY X 1.07C - 1.66 X « 1.C2C ~ 2.14 II - 1.10C « 0.13 * = 0.R7C ~ 5.7e
SUMf AC F WA IfP
S1NGU-anal TS T PRECISION SR = P.16* ~ C.90 SP - 0.19* - C.81 S» = 0.22* « 1.63 SR = 0.22* - 0.30
OVFR All PRFCJSION S = C.19X « C.9 ^ S = 0.29* - 2.6? S =- J.2P* « 1.47 S = 0.23X - O.OP
ACCURACY * = 1.0U - 0.22 * = 1.01C ~ 2.91 X = 1.J9C * 1.83 * 0.91C ~ 0.6!
industrial effluent
SINGL6-ANAI 1ST PRECISION SR - 0.20* - 0.29 SR = 0.23* ~ 0.13 SR = 0.32* ~ 0.25 SR » C.H* « 0.3J
OVERALL PRECISION S = 0.2C* ~ C.54 S = 0 .36X - 2*20 S =¦ 3 . 3 P X - 0.21 S C.18* ~ 0.65
ACCURACY X s 0.95C - C.62 X = C.92C ~ 2.36 X = 1.12C « 0.44 X = 0.94C « 0.37
* m f A N RFCOVCRV
C = TRIJF VALUF FOR IHI C ONC F N f P A T I ON
^Revised regression equations and estimates of accuracy and precision are qiven in Tables 12 and 13
-------
TABLE 1-3
ENVIRONMENTAL K0NI10RING AND SUPPORT LAflORATORY
OMKf OF RfSFARCH AND DFVflOPHENI
ENVIRONMENTAL P RO T F C 1 ION AGEMCT
*• EPA rflHOD 624 VALIDATION STUDY - PlIRGEAHltS **
BiroESSICN { Oil* I 1 ON S fOR ACCURACY ANO PRECISION
WATER TYPE CMl0R0«fTHAN£* CI $- 1«3-DICMLOROPROPENt 01BROnOC H LOROIL THANE I T M Y I BENZENE
ArPL ICApLt CONC. RANG* 17.0 - 469.C) <«.C - 557.0) (8.1 - 360.0) 115.0 - 6*0.0)
DISTILLEO WATER
SJNGIF-ANALVST PRECISION SR = ?.41X « 1.75 SR = 0.19* ~ 0.44 SB = 0.17* - 0.18 $R = 0.141 « 1.00
OVERALL PNEC1SI0N S = 0.4?X ~ 1.21 S = 0.24* « 0.07 5 * U.17* ~ 0.49 S = 0.26* - 1.7?
ACCURACY x - 0.94f ~ ?.37 * = 1.24C - 0.55 * = 1.01c - 0.03 * = 0.98C ~ 2.48
TAP VATFR
SINGLt-Af.AtYSI PRECISION S» s 0.43* « H.P9 SR = 0.21* ~ 0.38 SR = 0.23* - 0.24 SR » 0.22* ~ 0.90
OVERALL PRECISION S =¦ C.45* - 0.21 S = 0.27* ~ 0.55 S = 0.26* ~ 0.88 S = 0.24* - 0.77
ACCURACY * = 0.9CC « 0.20 * = 1.21C - 0.47 X * 1.07C - 0.44 * = 0.99C * 2.97
SURFACE WATEO
SINGLE-ANALYSt PRECISION
OVERALL PRfC ISfOfV
ACCURACY
JNOUSIR|AL EfFLUENT
SINGLE-ANALYST PRECISION
OVERALL PRFCISION
ACCURACY
SR = 0.57* - 0.46
S - C.<5* ~ 0.55
I = 1.1?C - 0.56
SR = 0.26* - C.09
S * 0.32* - 0.33
* = 1.16C ~ 0.1ft
SR - 0.20* - 0.39
S = 0.21* - 0.18
I = 1.01C • 0.10
SR = C.15* ~ 0.38
S - C.22* - 1.25
* > 1.01C < 3.88
SR * 0.59* - 1.33
S = C.61K - 1.10
X ^ 1 .C2C - 0.3P
SR * 0.15* ~ 0.33
$ = 0.25* « 0.01
* * 1.20C - 0.44
SR - 0.18* - 0.38
S - 0.26* - C.87
* = 1.07C - 0.70
SR • C.24* ~ 0.03
S = 0.29* - 1.27
* = 1.01C ~ 3.73
* - PEAN RECOVERY
C ^ 1 RUC VALUE EOR I HE CONCENTRATION
*Revised regression equations and estimates of accuracy and precision are given in Tables 12 and 13.
-------
TABLE 1-4
(NVtPOh^E'JlAl MONITORING *ND SurrORT LABORATORY
0 r F I c E or RESEARCH AND D F V E L 0 PT N T
i NVJ RONKENTAL PROJECTION AGENCY
«• f PA fFTHOO 624 VA( ) P A T J ON STUDY - PUfiGEAhlFS ••
MfRJSSICN IOU* T 1 ON S I0R ACCURACY AND PRECISION
WAT(R TYPE
Ml T M Y L E NE
CMLORIDt*
TE TRACHLOROE T M E N E
TOLUFME
TRANS-1,2-DICML0R0FTHFfcF*
A P PL 1 CAP! f CONC. RANGE
f 7.
2 - mo
.0)
(9
.0 - 400.0)
C 1 3
. 5 - 600.0)
(4.
5 - 300.D
DISTILLED WATER
SINGLE-ANALYST PRECISION
SR
= ?.19x
~ c.7 e
SR
» 0.13* - 0.18
SR
» CM5* - 0.71
SR
=• 0.T6X ~ 0.03
OVERALL PRECISION
S =
0.3CX
4 .09
S
• C.16X - 0.45
S =
0.22X - 1.71
S =
0.19X ~ 0.13
ACCURACY
X =
O.f TC
2 .31
1
* 1.06C ~ 0.60
X =
0.98C ~ 2.0!
x -
0.99C ~ 0.3C
TAP VA TE ®
SINGLE-ANALYST PRECISION
SR
= C.26X
~ 5.78
SR
= 0.23* ~ 0.04
SR
= 0.18X ~ 0.71
SR
= 0•17 x ~ 0.20
OVERALL PRECISION
S =
C. 36*
5 .37
S
= 0.27* - 0.64
S s
0.24* - 0.66
S 2
0.17X ~ 0.52
ACCURACY
X =
0.73C
5.97
X
= C. 9BC « 0.71
X -
0.98C * ?.7b
X =
1.05C - 0.17
SURFACE W A T fc ft
SlNf.l F-ANAI YST PRFCISION
SR
- P. 1ft*
~ 9.45
SR
= 0.18X - 0.2c
SR
= 0.15X - 0.03
SR
= 0.16 X ~ 0.10
OVERALL PRECISION
S *
0 .15 *
7.91
S
= C.25X - 1 .16
S =
0.23X - 1.67
S -
0.16X ~ 0.37
ACCURACY
* =
c.e?c
P .57
1
= 1 .C2C ~ 1.54
X =
1.30C « 2.25
X =
0.98C ~ 0.2*
INDUSTRIAL EfflUCNf
SINGLE-ANALYST PRECISION
SR
= C.'&x
• 3.54
SR
= 0.27* ~ 0.54
SR
= 0. 2 x - 0.93
SR
= 0.21X - 0.09
OVERALL PRECISION
S =
C.44X
1 .94
s
= C.31* - C.I 5
S =
0.26x - 1.07
5 =
0.23x ~ O.C?
ACCURACY
1 *
C.71C
3.15
X
= C.97C ~ 1.62
X =
0.92C ~ 2.63
X =
0.96C « 0.02
X " A N RECOVERY
C s TRUE VALUE fO» T»E CONCENTRATION
*Revised regression equations and estimates of accuracy and precision are given in Tables 12 and 13.
-------
TABLE L-'j
ENV I RONHfcNTAL MONITORING AND SUPPORT LABORATORY
orncE or research and development
INV1RONME MU PROTECTION AGENCY
•• EPA KfTHOO 624 VALIDATION STUDY - PURGEAEiLES ••
P'fPESSICN E 0 U•I J ON S fON ACCURACY AND PRECISION
WATER T TP f
IRAH5-1,!-
DICHLOROPROPENE
!« ICHLOROETHENE
TRlCHLONQfLUORQMETMANE*
1.1
-OICHLOROCTHANE *
APPLICABLE conc. r a N f> c
19.
4 - 416
.0)
15
.4 - 360.0)
C 7.2 - 480.0)
I1C
.8 - 4P0
.0)
DISTILLED WA TEP
SINGLE-ANALYST PRECISION
SR
" f).?0*
- C.5 3
SR
* 0.1JX « 0.36
SR = 0.31X - 1.34
SR
= 0.15*
- C.22
OVERALL PRECISION
s =
0.261
- 0.09
S
= C.I?* ~ 0.59
S » 0.36* - 0.48
S =
0.15* ~
0.5 3
ACCURACY
I
0.80C
~ 0.2?
X
= 1.04C ~ 2.2?
1 = 0.92C ~ 0.83
X =
0.98C «
1.09
TAP WATER
SINGLE-ANALYST PRECISION
SR
- 0. UX
•» 0.94
SR
= C.23X - 0.34
SR = 0.1SX ~ 0.66
SR
=¦ 0.16X
- 0.21
0V{R A LI PRECISION
s =
0.25*
~ 3.23
S
= 0.26* - 0.28
S » 0.31* - 0.15
S =
0.14X *
0.82
ACCURACY
X :
0.83C
- 3.58
X
* 1.03C ~ 1.65
X = 0.98C ~ 0.34
x =
1.01C «
C.11
SURFACE WATER
SINGLE-ANALYST PRECISION
SR
' 0.15*
~ 0.03
SR
= C.14X ~ 1.05
SR = 0.28* - 0.30
SP
= 0.11*
~ 1.07
OVERALL PRECISION
0.24*
* 0.1R
S
= 0.19X • 0.94
S * 0.31* « 0.0?
s =
0.12* «
1.06
AC CURACY
X -
G.89C
~ 0.69
X
= 1.03C ~ 2.91
* = 0.8 5C ~ 0.70
X =
C.99C ~
1.1!
INOUSTRIAL effluent
S1NG t F-AN A L Y S T PRECISION
SR
= 0.1 ft X
- 0.37
SR
= 0.22* ~ 0.75
SR = 0.24X - 1.36
SR
= 0.23*
- 0.27
OVERALL precjsion\
S =
0 • 2 2 x
- 0.48
S
• 0.33* - 0.03
S - 0.28* - 0.56
s =
0.24X 4
0.84
ACCURACY
X =
O.B2C
- O.Ufi
X
= 0.99C ~ 1.76
X = 1.00C ~ 0.25
X -
1.04C ~
l). 39
I = MEAN RECOVERY
C * T RUt VALUt FOR IH E CONCENTRATION
*Revised regression equations and estimates of accuracy and precision are given in Tables 12 and 13.
-------
TABLE 1-6
ENVIRONMENTAL MONITORING AND SUPPORT LA ('ORATORY
or f ICC 01 RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PPO'ECUON AGENCY
•• EPA K F T HOD 6 24 VALI0A1JON STUDY - PURf.MUlES ••
R'FftESSICN EQUATIONS FOR ACCURACY AND PRECISION
MATER TYPE 1,1-DlCHLOQOCTHfNE* 1,1,1-TftICMLOROFTMANE 1,1.2-TRICHLCROETMANf 1,1,2t2-TfTPACHlOPOFTKANE
AFPLICARle CONC. RA^GE (7.? - 48?.C> - < 9.0 - 400.0) MO.8 - 480.0) (15.0 - 6flC.0>
D I STILLED WA TE P
SINGLE-ANALYST PRECISION SR - t.22* * C.5R SR * P.12X - 0.15 SR = O.U* ~ O.C? SR =• 0.16* « 0.69
OVERALL PRECISION S = G.37« « 0.24 S • C.21* - 0.59 S = D.1B* ~ G.OC S = 0.20* ~ 0.41
ACCURACY A = 1.01C ~ 1.43 * * 1.36C 4 0.73 * = J.95C ~ 1.71 * = G.93C « 1.7f
TAP VATfc*
SINGLE-ANALYST PRECISION
OVERALL PRECISION
AC CURACY
SUHFACf WATER
SINGLE-ANALYST PRECISION
OVC RAL L PWfCISION
ACCURACY
SR - Mtl ~ 1.7 3
S " C.2!x ~ 3.6?
I « 0.9
-------
TABLE 1-7
CMVIHON'HNIAL WON | T 0 R1NG AND SUPPORT LAE*ORAIO»T
oifice or research and development
E NVIRONtUNlAL protection agfncy
• I PA PifTHOD 624 VALIDATION STUDY - PURf.EAOLES
B*fBISSlCN (0 UA 1|ON S lOR ACCURACY AND PRECISION
UATER TYPE
1»2-DlCHLOROBfN7CNt/1v4-P 1,2-DlCMLOROETMANE
<16.3 - 799.0) C9.9 - 440.0)
1.2-DJCHLOROPftOPANE
(13.5 - 600.0)
SR = 0.14* - 0.85
S = 0.17* - 0.41
* = 1.18C * ?.DO
1 • J-OICHLOHOBf NIIui
( 7 • 2 - 4P0.0)
SB = O.U* - 0.4ft
S = 0.18* - 0.82
* = 1.06C ~ 1.68
APPLICABLE CONC. RANG!
DISTILLED WATER
SINGLE-ANALYST PRECISION
OVERALL PRECISION
ACCURACY
SR = 0.221 - 1.45
S = 0.30* - 1.20
X = 0.V4C « 4 .47
SR = C.17* - P.32
S * 0.21* - 0.38
* - 1.02C ~ 0.45
TAP WATER
SINGLE-ANALtST PRECISION
OVERALL PPFCIS10N
ACCURACY
SURFACE WAIF*
SINGLE-ANALYST PRECISION
OVFRAll PRECISION
ACIURAC Y
INDUSIRPl CMLUCHT
SINGLE-ANALYST PRECISION
OVERALL PRECISION
ACCURACY
SR = 0.36* - 2.57
S - 0.38* - 1 .56
* = 0.9?C ~ 4.65
SR = C.25* ~ 0.95
S = 0.10* ~ 1.48
* = 0.97C • 6.9?
SB = 0.25* ~ 2.55
S « 0.29* • 4.!?
* = 0.95C ~ 5.14
S« = 0.18* - 0.21
S - 0.17* ~ O.U
* = 1.06C - 0.4S
SR « 0.10* ~ 0.95
S * 0.13* ~ 0.53
* = 1.16C ~ 1.70
SR =• 0.15* ~ 1.01
S = 0.18* ~ 1.69
* =¦ 1.01C ~ 0.97
SR = 0.13* - 0.5?
S = 0.17* - 0.33
* - 1.18C ~ Z.89
SR ~ 0.14* « 0.96
S = 0.18* ~ 1.44
* T 1.01C - 0.28
SR « 0.13* ~ 0.77
S = 0.18* « 0.53
* = 1.2?C - 0.25
SR = 0.22* ~ 3.41
S « 0.24i « 2.34
* = 1.02C • 3.80
SR • 0.15* « 1.44
S = C.16* ~ 1.72
* = 1.11C ~ 1.9P
SR = 0.15* ~ 2.CI
S C.17* ~ 1.83
* = 1.03C ~ 1.79
* * MEAN MECOVtRV
C = FRUF VALUF FOR THE CONCENTRATION
anmcPT
pp)nti
-------
TABLE 2. ACCURACY AND PRECISION ESTIMATES (COMPUTED FROM THE REGRESSION
EQUATIONS) L'OK A PREPARED CONCENTRATION OF 100 Pfi/L
(> 1 ^ I
I l i. t.U
V:A tR
TAP
WA1LH
blJHKALL
VA1 tR
I NO .
ef-Fi
DEN T
7.I.M)
S/.R
%RSD
RSI)
( UMl-OUHl)
7»K I. (
7M -,l>
• SA
7-RhC %R
SI)
- -j A
UK t L
x(< So
i> A
'AUtC
7«R-jO
- SA
RhN/fcNE
ir:
2 4
24
96
2 1
20
J >
) 4
y i
2 1
I J
HROMOO1 ( Ml OHUML1MANfc
10 1
2 1
6
1 04
24
fi
99
23
i a
9 3
2 3
2 3
UROMOf ORM
1 l)i)
2 1
• 4
1 2
34
32
9f)
27
\a
9 3
34
2a
GROMOMCTHANC
/ l
.'»>
2 b
b8
35
2b
68
2b
24
7 b
4 1
3 /
CARBON TETRAU-li OH1DC
l 1)0
1 4
1
1 Ob
2 3
22
101
20
1 7
94
2 1
/O
CHI ORODEN2ENE
11)0
2 4
b
104
2 2
20
104
2b
10
94
3 1
~ 3
CHI ()ROh I HANE
i i r,
J 9
25
I 10
35
30
\ 1
29
2 3
\ 1 2
3»3
12
Cill OROhORM
9 3
10
6
93
37
23
92
23
22
94
1 9
1 4
CHLOKOWr ThANI-
4 9
43
90
45
43
1 1
4S
3/
10 2
m
SM
C I 5 1,3 DI CHI OHOPROf'tNh
1 23
2 4
10
1 2 1
2 7
2 1
i r>
3 2
26
1 20
25
i r.
DI BROMOCHl OROMCTl lANh
1 0 1
1 /
7
107
27
23
101
2 1
2 0
106
25
1 H
ETHVL OENZENC
i no
.'•1
5
1 0 2
23
23
105
2 1
5
1 05
2rt
24
ME fHYLENE CmLON1OE
03
35
20
/9
43
33
09
34
27
M
4 /
IS
Tfc1RACHLOROfc THENE
107
1 c»
3
99
2 b
23
04
24
10
09
3 1
2 H
101ULNL
1 00
20
4
I 0 1
23
y
02
2 1
15
95
25
2 1
1 RANS • 1 . 2- 01CHlOROE IHfcNfc
93
1 9
I)
1 Ob
1 7
/
98
1 6
6
96
2 j
2 1
1 RANS- 1 . 3- 01 CHL OKOPROPENL
BO
2 b
19
02
2fj
4
90
24
5
H 2
2 1
1 6
I R I CHi OR0E T Hi rlf-
1 06
i 3
J
1 or»
2b
23
Ob
2 0
b
10 1
3 3
2 3
TR I CHI OR OF I IJOROMM HANE
9 J
35
JO
9B
3 1
19
OB
3 1
20
1 00
27
2 3
1.1 DIOlLOROFTHANt
99
l b
lb '
10 1
lb
b
00
13
2
1 04
2 5
2 3
I . 1 OICHLCKOCIliCNC
10/
3 /
23
9 b
24
10
90
22
h
HO
2 j
2 3
1.1.1 IRICHLO^OClHANC
1 0 /
2 \
2
I 10
23
20
1 0 1
2 7
23
1 00
2 j
1 7
1 . 1 . 2 ~ 1 R I CHLOROt I HANC
9 7
) H
4
1 04
16
1 3
106
20
G
10 1
^ 2
1 H
1.1.2. 2~TETHACHLOROETHANE
9h
2 0
1
93
24
1 6
100
22
5
09
3 1
3H
1.2-/1,4-DICHI OKMBfcNZENE
90
29
2 1
103
3t>
33
1 04
3 1
2 6
100
3 J
?H
1 . 2-1)1 ( HI ()R()»- iHANt-
i 0 2
2 1
I
1Uf>
1 7
1 B
1 0 2
20
6
10 1
1 9
1 5
1 . 2-Dir.MLOROPHDPANH
i 20
1 7
3
1 10
13
\ \
1 2 1
\ /
3
1 2 2
13
1 4
1 . 3 DICHLORODCN2ENE
1 OB
1 7
4
1 OG
26
25
1 1 J
1 H
b
10b
19
1 7
-------
SECTION 3
RECOMMENDATIONS
Gaseous compounds, bromoraethane, chloromethene and chloroethane
should be handled with care. Recoveries and precision may be
negatively.affected due to inherent difficulties in handling
these species and other highly volatile compounds unless extra
caution is used at the various stages of sample and standard
handling and preparation.
If possible, any hot metallic (active) sites in both the gas
chromatograph and the detector should be eliminated. These
sites could cause breakdown of some compounds. Bromoform,
bromomethane and the dichloropropenes are known to be unstable.
Standards should be prepared regularly and stored in a freezer
to avoid decomposition of these species.
Special care must be taken in handling samples and blanks to
avoid contamination from the laboratory atmosphere. This is
especially true for methylene chloride. It is recommended that
at least daily checks be made for contamination by the use of
appropriate blanks.
Carry-over of the analytes from the analysis of high concentra-
tion samples to the next analysis was noted. It is recommenced
that the purge device be filled with distilled water and purged
for 10 minutes after the analysis of samples containing high
concentrations of purgeable compounds.
14
-------
SECTION 4
DESCRIPTION OF STUDY
The design of the interlaboratory study of Method 624 was based
on the technique described by W. J. Youden [1]. According to
this technique, samples are analyzed in pairs where the concen-
tration of each analyte in the sample pairs is slightly different.
The analyst is directed to perform a single analysis and report
one value for each sample.
The samples were prepared as concentrates in sealed ampules and
shipped to the participating laboratories. Each laboratory was
responsible for supplying laboratory pure water, finished drink-
ing water, a surface water, and an industrial effluent water for
use in the study (two laboratories, numbers 10 and 16 used water
treatment plant effluents which may have had primarily municipal
origins). The analyst was required to add an aliquot of each
concentrate to a volume of water from each of the four water
types and subsequently to analyze the spiked water samples.
Sample pairs for each method were prepared at three concentration
levels; low, medium, and high, all of which were within the linear
range of the mass spectrometer.
In addition to the sample ampules, an Industrial effluent water
selected by Radian was furnished to each participating laboratory
for analysis. This sample was- known to contain a number of the
priority pollutants and was judged to be somewhat difficult to
analyze. The purpose of the Industrial effluent sample was to
determine the propensity of the method to produce false positives
and false negatives.
15
-------
After all analyses were completed, the results were subjected to
statistical analysis using EPA's IMVS system to determine the
precision and accuracy of Method 624.
TEST DESIGN
The following is a summary of the test design used based on
Youden's nonreplicate technique for samples.
1. Three Youden pairs of samples were analyzed for
each analyte with the deviation from the mean
of each pair being at least 570 but not more than
20%. The three pairs were spread over a usable
and realistic range such that the lowest pair
was somewhat above the minimum detection limit
and the upper pair was within the linear range
of the method.
2. The spiking samples were supplied as liquid con-
centrates in organic solvents sealed in glass
ampules. Sufficient sample was provided to al-
low withdrawal of the appropriate amount of solu-
tion to spike one water sample from each ampule.
3. Twenty-four volatile organic ampules were pro-
vided to each of the 15 laboratories.
4. The concentrates were spiked into laboratory pure
water, drinking water, a surface water, and an
effluent waste water by the participants prior
to analysis. In addition, an industrial effluent
sample was supplied to each laboratory by Radian.
This sample was analyzed without addition of
analyte concentrates.
16
-------
5. Each of the 15 participating laboratories was fur-
nished with the following materials:
• Four Youden pair ampules of each of three
concentration levels for the volatile
organics. (A total of 24 spiking sample
ampules.)
• Sufficient surrogate standard solution to
analyze all samples and blanks.
• A 1 liter sample of an industrial effluent
to be analyzed without addition of spiking
sample.
• Copies of method 624.
• A questionnaire covering difficulties
encountered with the method and sugges-
tions for imorovements.
• Data report forms to be completed and
returned to Radian.
• A set of instructions detailing the method
for spiking the samples and the order in
which samples were to be run.
17
-------
SELECTION OF PARTICIPATING LABORATORIES
Laboratories were invited to submit bids to participate in the
study through announcements placed in Commerce 3usiness Daily,
Analytical Chemistry, and Environmental Science and Technology.
Approximately 80 responses were received. Of these respondents,
34 cost bids were obtained from which 15 laboratories were se-
lected. Selection was based on the experience, qualifications,
facilities, quality control plans, and cost estimates received
from the laboratories. Final selection was also dependent on
the laboratories successfully analyzing the performance evalua-
tion samples prepared by Radian.
The laboratories selected for participation are given in Table 3.
The laboratories numbers used in the report do not reflect this
order.
PREPARATION OF YOUDEN PAIR CONCENTRATES
The Youden pair solutions for the volatile organics were pre-
pared by accurately weighing the pure standard compounds 'into
volumetric flasks and dissolving in acetone. The pure materials
were obtained from EPA's Repository.for Toxic and Hazardous
Materials which was maintained by Radian.
Several stock solutions were prepared for each class of compounds.
Each compound was weighed only once. A portion of each stock
solution was then diluted by addition of fresh solvent. The
diluted and undiluted stock solutions were aliquoted and further
diluted to give various concentrations of the individual analytes
in each Youden pair.
The surrogate standards and prestudy test sample solutions were
prepared by dissolving weighed standards into volumetric flasks
and diluting to volume with acetone.
18
-------
TABLE 3. FIFTEEN LABORATORIES SELECTED FOR PARTICIPATION
IN THE METHOD 624 INTERLABORATORY STUDY
Laboratory
Acurex Corporation
California Analytical Laboratories, Inc.
Envirodyne
Environmental Research Group, Inc.
Environmental Science and Engineering, Inc.
Foremost-McKesson
GCA Corporation
Mead CompuChem
Pedco
Rockwell International
Rocky Mountain Analytical
Spectrix
Stewart Labs
The University of Utah Research Institute
West Coast Technical Service, Inc.
19
-------
When diluted with water according to instructions, the calculated
concentrations of the various analytes in the diluted samples in
jjg/L are given in Tables 4 through 6. These values are based on
the weighed amounts of the individual analytes.
Solutions which were prepared from gaseous compounds were obtained
by bubbling the pure gas from cylinders into tared volumetric
flasks partially filled with methanol. The gas was conducted into
the flask through Teflon tubing connected to a Pasteur pipet. Af-
ter additions of the appropriate amount of gas, the flask was re-
weighed and the added weight of standard compound obtained by dif-
ference .
The diluted spiking solutions were subsequently filled and sealed
in glass ampules under nitrogen.
VERITY, HOMOGENEITY, AND STABILITY OF PREPARED AMPULES
For the verity study and homogeneity study, Radian analyzed
three ampules in duplicate for each of the six concentrations.
These ampules were collected early, middle and late during the
filling and sealing operation. For the stability study, only
one concentration of the middle Youden Pair was examined by
Radian at both 45 and 90 days. Examination of the data indi-
cated that further analyses were necessary. At this time, the
Quality Assurance Branch, EMSL-Cincinnati, analyzed the samples.
In general, according to EMSL-Cincinnati, the studies indicated
that the true values were correct and that the ampules were
homogeneous and stable. Exceptions did occur. For details see
the section entitled Revised Equations.
PROOF OF FEASIBILITY OF THE STUDY PLAN
To prove the feasibility of the mixture of analytes in the am-
pules, Radian analyzed the Youden pairs by spiking them into
20
-------
TABLE 4. CONCENTRATION OF ANALYZED VOLATILE ORGANIC SOLUTIONS
Youden
Pair
High
(Pair 1)
Medium
(Pair 2)
Low
(Pair 3)
Compound
1
z
1
2
1
2
Bromodichloromethane
432
480
120
114
8.0
9.2
3romoform
400
360
95
100
9.0
10
Broraonethane
546
607
152
144
10.1
9.1
C'nloroethane
447
488
122
116
8.1
7.3
2-Chloroethyl Vinyl
Ether"
480
432
114
120
10.8
12
Chioromethane
422
469
117
111
7.8
7.0
Dibromochloromethane
360
324
86
90
8.1
9.0
1,1-Dichloroethene
432
480
120
lu
8.0
7.2
1,1-Dichloroethane
480
432
114
120
10.8
12
1,2-Dichloroethane
440
396
104
110
9.9
11
1,2-Dichloropropane
600
540
142
150
13.5
15
cis-l,3-Dichloropropene
357
321
85
89
8.0
8.9
trans-1,3-Dichloropropene
416
374
99
104
9.4
10.4
Ethyl Benzene
680
612
162
170
15
17
Methylene Chloride
432
480
120
114
8.0
7.2
1,1,2,2-Tetrachloroethane
680
612
162
170
15
17
Tetrachloroethene
400
360
95
100
9.0
10
1,1,1-Trichloroethane
400
360
95
100
9.0
10
1,1,2-Trichloroethane
480
432
114
120
10.8
12
Trichloroet'nene
324
360
90
86
6.0
5.4
1,2-Dichlorobenzene"»
378
420
105
100
7.0
6.3
1,3-D ic'nlorobenzene
432
480
120
114
8.0
7.2
1,4-0 ichloro benzene**
400
360
95
100
9.0
10
Trichlorofluororaethane
432
480
120
114
8.0
7.2
Benzene
480
432
114
120
10.8
12
Carbon Tetrachloride
400
360
95
100
9.0
10
Chlorobenzene
600
540
142
150
13.5
15
Chloroform
270
300
75
71
5.0
4.5
Trans-1,2-Dichloroethene
270
300
75
71
5.0
4. 5
Toluene
600
540
142
150
13.5
15
^Decomposed in the solution mixture
AASpiking concentrations were summed - compounds co-eluted from the GC column.
21
-------
TABLE 5. SPIKING CONCENTRATION OF SURROGATE COMPOUNDS
Compound Prepared Concentration - ug/m&
Method 624
l,2-dic'nlorobenzene-d4 150
1,4-dichlorobutane-da 151
2-Bromo-l-chloropropane-d6 150
Bromochloronethane-d 2 151
Fluorobenzene 150
4-Broraofluorobenzene ' 152
TABLE 6. PERFORMANCE SAMPLE FOR METHOD 624
Compound Concentration, Jg/L
1.1.1-Trichlcroethane 23.7
1.1-Dichloroethane 27.2
1.1.2-Trichloroethane 37.2
2-Chloroethyl vinyl ether 34.4
1.2-Dichlorobenzene 15.0
Ethyl benzene 18.3
Chlorodibromoraethane 7.0
Carbontetrachloride 5.2
Acetone* 25.3
Chloroethane 28.3
*Nonpriority pollutant interference
22
-------
laboratory pure water and performing the analyses according to
the instructions provided to the participants. The results of
Radian's analyses are presented and discussed in Appendix B.
23
-------
SECTION 5
STATISTICAL TREATMENT OF DATA
Data obtained from the interlaboratory method validation study
were subjected to statistical analyses employing US EPA's IMVS
system [2] of computer programs. This system of programs was
designed to implement ASTM procedure D2777, "Standard Practice
for Determination of Precision and Bias of Methods of Committee
D-19 on Water" [3], The analyses conducted using the IMVS
programs included tests for the rejection of outliers (whole
laboratories for a water-type and individual data points), es-
timation of mean recovery (accuracy), estimation of single-
analyst and overall precision, and tests for the effects of
water test on accuracy and precision.
Prior to employing the IMVS system, the interlaboratory method
study data was reduced to a standard form and validated. Tables
C-l through C-84 in Appendix C present the standardized data from
the 15 participating laboratories. All values shown in the tables
have been corrected for the blank values presented in Tables C-85
through C-88. Corrected values less than zero and values reported
as "not detected" or "detected, but the concentration could not
be quantitated" are shown as zero. Asterisked values were re-
jected as outliers using the various IMVS software tests presented
in the next section.
Prior to formal analysis by the IMVS software, data were screened
for incorrectly transcribed data values through the use of de-
scriptive statistics, graphical aids and visual scanning of the
data base.
24
-------
REJECTION OF OUTLIERS
An ouclying observation, or "outlier," is a data point that ap-
pears to deviate markedly from other members of the group of
values with which it is associated. Outlying data points are
often encountered during interlaboratory test programs; if they
are not removed, they can result in a distortion of the accuracy
and precision statistics which characterize the analytical method.
These outlying points should not be removed indiscriminantly, how-
ever, because they may represent an extreme manifestation of the
random variability inherent in the method.
ASTM procedure E178-80, "Standard Practice for Dealing with Out-
lying Observations" [4] and ASTM procedure D2777-77 [31 present
explicit statistical rules and methods for identification of out-
liers. The IMVS software [21 was used to screen the concentration
data for outliers.
Data from outlying laboratories for a particular type were re-
jected employing Youden's laboratory ranking test procedure [3, 5]
at the 5% level of significance. Data remaining after the labo-
ratory ranking procedure were subjected to individual outlier
tests. After all zero, missing, "detected, but could not be
quantitated" and "nondetect" data were rejected as outliers, the
remaining data were examined using the two-sided outlier rejection
T-test constructed by Thompson [6]. All data rejected as outliers
for this study are identified by an asterisk in the tables of data
(Tables C-l to C-84, Appendix C). Of the 9,880 reported concen-
trations, 1,434 were deleted as outliers (approximately 157.) •
Youden's Laboratory Ranking Procedure
Using the data for each water type, Youden's laboratory ranking
test [3, 5] was performed at the 57o level of signif icance. The
25
-------
Youden laboratory ranking procedure requires a complete set of
data from each laboratory within each water type, so that, missing
data had to be replaced. The natural logarithms of the recovery
data were regressed against the natural logarithms of the spiked
ampule concentrations to find the line of best fit. The predicted
log-recovery measurements were computed from the least-squares re-
gression equation, and the missing values were estimated by taking
the exponential of the predicted value. (For complete details of
this procedure, see Reference 2.)
With a complete set of data, the laboratory ranking test was used
to identify laboratories (for a particular water type) that were
so consistently high or low that their results are unrepresentative
of the method1s capabilities.
Data from outlying laboratories were rejected at the 5% level of
significance. When a laboratory was rejected, all the lab's data
for that water type were flagged as outliers for further analyses.
After ranking was complete, all estimated "missing values'1 were
deleted from any further analyses.
Test for Individual Outliers
The data remaining after rejection of all zero, missing, "detected,
but could not be quantitated" and "nondetect" data were subjected
to an individual outlier test based on calculation of the T-value
[3, 6].
In these calculations the mean recovery, X, is givenvby
(1)
i=l
26
-------
and the standard deviations, s, is given by
1=1
!_ V (X.-X)2 (2)
where X. - individual analyses
i J
n = number of retained analyses values in the
ampule set
The outliers may be rejected if the value of T\ defined by
X -X
Ti - -f-
exceeds the critical value of the Thompson's T (two-sided at 570
significance level). In the equation, Xg represents the value
farthest away from the mean X of this set of retained data. If
the extreme value is rejected as an outlier, the test is repeated
until the value being tested passes the test.
STATISTICAL SUMMARIES
After the outlier rejection tests were performed, the following
summary statistics were calculated employing the remaining data
for each ampule (single analyte, single concentration, single
water matrix):
• Number of retained data points, n
• Mean recovery of retained data, X
• Accuracy as a percent of relative error, % R.E.
• Overall absolute standard deviation, S
• Percent relative overall standard deviation,
% RSD
27
-------
• Absolute single-analyst standard deviation,
• Percent relative standard deviation for a single
analyst, 70 RSD-SA
All of these statistics, except the single-analyst absolute and
relative standard deviations, were calculated using the retained
data for each ampule. The basic statistical formulas used for
these calculations are given below, where Xi( X2, . . • » Xn ^e~
note the values for the n retained data points for a given ampule
Mean Recovery (X):
*-5 £ xt (1)
1=1
Accuracy as % Relative Error:
Overall Standard Deviation:
•-vfei £
S =-Jzrrr ^ - X) z (2)
i=l
ana
Percent Relative Overall Standard Deviation:
S
70 RSD = z x 100 (5)
X
The overall standard deviation, S, indicates the precision asso
ciated with measurements generated by a group of laboratories.
This represents the broad variation in the data collected in a
28
-------
collaborative study. A measure of how well an individual labora-
tory can expect to perform in his own laboratory is another im-
portant measure of precision. This "single-analyst'1 precision,
denoted by S , is measured by
sr -/tstttIT (DrB)' (6)
i= 1
where m = number of retained Youden-paired observations
th
D. = difference between observations in the iu pair
1 ^
D = average of values
The Youden-pair design employed in this study permits the calcu-
lation of this single-analyst precision without making duplicate
measurements on the same sample. This helps to avoid the well-
intentioned manipulation of data that can occur when laboratories
make duplicate analyses.
The percent relative standard deviation for the single-analyst
precision is calculated by
S
% RSD-SA = ^ x 100 (7)
X*
where X* is the average of the two mean recoveries corresponding
to the two ampules defining the particular Youden pair. These
summary statistics are presented in Tables 7-1 through 7-28 for
each of the 28 Method 624 compounds in the four water matrices.
29
-------
IN Jin J i I W 1 HI SI10K 1 - 7
3)«Jtjf)S - i
di!»« «i - Z
a 41»n QJll 11SIQ - I
ON 1 Jll «3lVA
79' U
76
"02
93*Z1
2 Z" 2 2
2 4 A 3 (J tin iSllvHV
rzt
3*
18
Z*£Z
l**>3
(ms) *Ai3 ois n<)'• 79
i* 94
l*9«
7*m
£*7ll 1*98
Z'Zii 6*901
IS) A J ADtaniD*
5HJC
3* i07
5 • 29£
0 * 06 i
£ * ? 1 7 b*307
l*Z7l o*z£7
(X) 1M 3 A3}4 M Mv 3U
0*2»7
o'oat
0*2t7
o*jfir
0 * 2 k 7 C*Jtf7
0 * 2 i 7 0 * j 3 7
1/Ofl O) 3NOJ 3H01
21
(I
71
n
11 a
a u
SlNlOd vivQ JO (J39^nh
1 a3o ois aiDnts
SS*9?
2? *61
7Z*7l
6 Z * 6 I
I J*VI Oi* 12
ZJ*n 31 • 2 k*
t • A10 1 IV M iAU
8 7*1
it *2-
zi*i
l£*£
fcl'J !»*£
ZJ*J «i*7
(bOrtSJ 1 ?t> X J 1 3 VfclU 3 ¥
9*121
t'lll
7*921
rn i
2*021 6 ® z 11
1*021 0 * 611
(X) A83A033B fcvlk
0*021
3*711
0*021
e*»u
0*021 (j * 7 11
0 * C 21 0*711
1/9H (3) 3N03 3llttl
21
£1
71
u
il IV
21 £1
SINtOJ VIVO JO aj0wnn
r
£
*
£
7 I
7 i
Mitfd Niono* wniQ3u
77*9
6£
*01
2 7 * Z I
Oi'U
X * A 3 0 11U iSllvNv
3'P
I*
1
1*2
*•1
(HS) 4 A 1 fl aiS J 1 'J N I S
15"2l
21*91
6£*Sl
37* U
7 Z * 71 96*91
ll*V| Z £ * 11
X ' A 3 0 Ois 11H 11V tl 3 AO
9' I
Z * 1
0*2
i * I
6*1 0*2
2*2 9*1
(S) A 3 0 QL% 11V d1AO
OZ* 7
£l*C
Oi*v
62*01
£«*S 95*3
>i*2l 6 7 * Z
(ftOdtfi 13«XM)*an)D¥
9*21
3 * JI
I * £ 1
6*11
Z * 2 I Z'll
S * £ I 9*11
( K > IbJAOJatJ
0*21
V'ul
0*21
3*01
0*21 2*:i
0*21 3*01
i/9n oi ) no j jnji
11
1 k
7 I
a
11 2l
21 11
SIMOd V 1 V 3 I 0 H3d«.nri
2
I
2
i
2 1
I I
dltfd NJ0I104 AO 1
7 £ 1)1)1 2 aii»« l Jilv
Idlt dilVA Ab SJSllrNJ IVJ/NJd H 0 J AaVWrfrtS UMlSlUli
»• $3~H»3'_)efM - iOOlS NOtlVOIIVA 72* vJOMllU tdl ••
U3ll3JlO*d 1 VI N J/JNOd I AN j
JA 3d ONV H)t)v3S)d iO Dlno
Aaoifaosvi ifiojjns onv dnI^0i tno4 itf is jwNoatAN)
I-L 3'I9VX
-------
TABLE 7-2
ENVIRONMENTAL MONITORING AND SUPPORT LAPORATORY
office or research anb development
ENVIRONMENTAL PROTECTION AGENCY
•• EPA METHOD 6£4 VALIDATION STUDY - PlIRGEAGLES ••
STATISTICAL SfKAPT FOR pROMOOICHLORO^f THANE ANALYSES GY WATER TYPE
WATER 1 WATER 2 WATER 3 WATER 4
LOW VOUDFN PAIR
1 2
1
2
1
2
1
2
NUMBER OF DATA POINTS
13 15
12
14
15
15
13
14
TRUE CONC UG/L
*.0 9*2
e.o
9.2
8.0
9.2
e.o
9.2
WEAN RE C OVf R Y (X)
7.2 7.3
9.6
11.C
P.I
6.6
7.3
6.9
"CCURACVdRlL ERROR)
-10.48 - ?0 .8 7
20.CD
19.57
1. 5C
-2P.19
-8.69
-25.00
OVERALL sto dev (s >
2.8 2.3
6.4
5.0
2. ¦
2.1
2.1
3.1
OVERALL REL SID 0 fc V, X
39.22 11.72
66.67
45 .72
34.78
32.40
26.39
44.43
SINGH STD DEV, CSR)
1.7
2
. 7
1 . 7
1 .5
ANALYST PEL DEV, X
2 3.17
26.
25
23.44
2C.86
1EDIU* YCUDEN PAIR
3 4
i
4
3
4
3
4
NUMBER OF DATA POINTS
13 1 *
13
14
15
15
1 3
13
TRUE CONC f C1 UG/L
120.0 111.0
12C.0
114.C
120.C
114.0
120.C
114.0
*
14C.5 100.7
132.2
94.6
131.1
103.3
116.0
99.2
ACCURAC1**REL t P R OR >
17. Ct -11 .67
1C.14
-17. C3
9.25
-9.36
-3.35
-12.94
OVERALL STD DEV (S)
12. 4 23.9
29.5
22.4
27.0
25.6
24.1
28.3
OVERALL REL STO DEV, X
8.P2 23.78
2 2 .28
23 .64
20.60
24.81
20.80
28.48
SINGLE STD DEV, (SR)
17.4
26
.8
25.4
26.9
analyst pel DEV, X
U .39
23.
61
21.64
25.02
HIGH YOUCEN PAIR
5 6
5
6
5
6
5
6
NUMBER OF DATA POINTS
15 15
14
14
15
1*
13
14
TRUE CONC (C) UG/L
<32.C 480.0
4 3 2 .0
460.0
4 3 2.0
480.0
4 32 .0
480.0
"E A N RECOVERY (X)
462.0 472.3
4 7?.?
515.5
419.5
490.6
399 .6
482.3
ACCURACY <*»fI FRPOR 1
6.95 -1.60
10.P3
11.57
-2.90
2.20
-7.49
0.48
OVERALL STD DEV (S>
125.9 99.4
It?.3
11 3.4
111.9
92.4
7D.4
125.4
OVFRAII RF1 STD DFV, X
2 7.25 21.04
22.40
21.18
26.67
1 ? . 8 2
17.61
25.99
SINGLE STD DEV, CSR)
?4 . 8
64
.6
65.7
92.4
ANALYST REl DEV, X
U.f 0
12 .
7 P
14.44
20.96
WATER LEGEND
1 - DISTHLCD WATER
2 - TAP WATER
3 - SUR FACF WA Tf R
4 - INDUSTRIAL EFFLUENT
-------
TABLE 7-3
c N v J P CNH E «j 1 A L MONITORING AND SUPPORT LAPC&ATQRY
OFFICE OF RESEARCH AND DEVEIOP»ENT
ENVIRONMENTAL PROTECTION AGFNCY
• * E P# r.fTHOO 624 VALIDATION STUDY - PURGE.ABLES *•
STATISTICAL SUMMA R T FOR BRO M 0 F OR ANALYSIS BY WATER IVPi
WATER 1 WATER 2 W AT E " 3 WATER 4
LOW VOUOEN PAIR
1
2
1
2
1 2
1
2
FR Or OATA POINTS
12
13
12
13
14 14
13
15
TRUE CONC
2.4
3.5
2.9
6.7
3.0 3.3
2.2
3.8
OVERALL PPL S T t> DfV, X
28.77
37.42
37.79
54.52
3<.V 37.28
31.58
47.67
SINGLE ST© D E V « (SR)
1
.4
£.4
1 .6
2.0
ANAL VST RFI DFV, X
15.
f ?
44.C9
18.37
2 6.44
1L DIUM YCUDEN PAIR
X
4
3
4
3 <
3
4
NtJMRFR OF DATA POINTS
1 3
12
15
14
15 15
15
14
TRUE C ON C (L) UG/L
55.C
ico.o
95.0
100.0
95.0 100.0
95.0
ICO.O
MEAN RECOVERY
-------
TABLE 7-4
ENVIRONMENTAL rONIIORtHG AND SUPPORT LAHORAIORY
OffltE or RESEARCH AN 0 OCVEL0PMN1
ENVIRONMENTAL PROTECTION AGENCY
•• EPA METHOD 624 VALIDATION STUDY - PURf-E ABLLS ••
STATISTICAL SU*«»RY f 0 R OR0rO«ElHANf ANALYSES 0* W A T I R TYPE
WA11R 1 WATER ? W A T k ft 3 VAILft 4
LOh YOUDEN PAIR
1
2
1 2
1
2
1
2
NurOEfi Of DATA POINTS
1?
11
11 11
12
13
12
11
IRl'f CONC (C) UG/L
1C.1
9.1
1C.1 9.1
10.1
9.1
10.1
9.1
«fAN RECOVERY < K »
6.?
6.0
5.5 5.5
6.3
5.8
5.9
6.9
ACCllRACVdREi ERROR)
-36.C4
-34.?7
-45.99 -39.66
- ! 7 . 4 6
-35 .93
-41.hJ
-24.03
OVtHALL SIP DEV (S>
1.9
2.4
?. 7 2.3
1.9
2.5
2.0
3.1
OVERALL PEL STD DEV, *
30.6?
4C.?6
4?. 97 4 1 .C4
29.49
42.63
34.60
44.29
SINGLE STD 0 6V,
1.1
1.2 •
1.3
2
. 1
analyst PEL DEV, *
1®.5K
2 1 • 1 4
2C.9?
3 3.
20
"fMUl YOUDEN PAIR
3
4
3 4
3
4
3
4
NlJ*P f R Of DATA POINTS
13
13
11 12
1 3
1?
11
14
TRUE C Oh C
117.7
73.4
1CC.2 73.7
101.5
94.3
9* .9
126.0
ACCURACVUR^L EMROR)
-22.54
- 4 9 • C 6
-24.C9 -48.83
-33. ?C
-34.54
-3 4.92
-12 .52
OVERALL STD OEV
30.9
15. 5
31.2 17.7
32.7
21.6
28.3
9H.8
OVERALL R EI STD DfV, X
26.25
21.18
3 1 . 1 5 24 .04
32.18
22.94
2 8.60
78.42
SINGLE SID DEV, CSfi )
26.5
26.5
25.5
53
.B
ANALYST R E L DtV, X
27.73
30.47
26.02
47.
84
H)GH YOUDEN PAIR
5
6
5
6
5
6
5
6
NU"9ER Of OATA POINTS
13
13
12
12
11
13
14
11
TRUE CONf (C) UG/L
546 . C
607.0
546 .P
6 ? 7 . C
546.0
607.0
546 .0
6C 7.0
If AN RECOVERY < X)
41C.1
498 .6
404 .9
494 .8
354 . 1
463.0
424 .6
444 .6
ACCURACY UPEL ERROR)
-24.89
-17.86
-25 .84
-18.49
-35.U
-23.72
-22.23
-26 .75
OVERAIL STO DEV
e7.5
162.3
UP.8
224 .5
64.5
14U.6
112.9
126.5
OVERALL PCI STD 0£V, X
21.33
32.55
*6.75
4 5.38
18.22
3?.36
26.58
<8.t4
SINGLE S10 DEV, ISR)
1U.6
125.1
! 5 .9
114
.9
ANALYST PEL DEV. X
25.22
27.80
21.0!
26.
45
w* Tf 0 L EGE ND
1 - DISTILLED WATER
2 - TAP WATER
3 - SURFACE WATER
4 - INDUSTRIAL EMLUtNT
-------
TABLE 7-r)
ENVIRGNMINIAL K0NI10N1NG AND SUPPORT LABORATORY
orrtcc cr research and Drvfior-TNi
ENVIRONMENTAL PROTECTION AGENCY
• * IP A HFTHOD 624 VALIDATION STII6T - PIJRGEA(HES **
STATISTICAL SUMMARY FOR CARRON TETRACHLORIDE ANALYSES BY WATER TYPE
WATER 1 WATER 2 WATIR 3 WATER 4
LOW TOUDtN PAIR
1
•>
4
1
2
1
2
1
t
NUMBER or DATA POINTS
1 2
10
11
10
14
14
14
14
TRUE CONC UG/L
9.1
10.0
9 . "3
10.0
9. C
10.0
9.0
1C.C
AS RECOVERY IX)
8.0
9.6
'.2
8.9
R.6
10.2
7.8
9.1
• C CURACY CtREL tRPOR )
-1C.B3
-4.1Q
-f .69
-10.60
-4.80
1.93
-13.81
-8.57
OVERALL STD oev (s)
1 .B
C . 7
1.4
t.7
2.9
2.3
2.1
2.3
OVERALL REI STD DEV» Z
2 2 . 3 ?
6.99
17.5*
8.0C
5 4.39
22.IP
2 7.56
25 .42
S I Nf,[ F STD D E V | t SR )
1
.3
1
.0
2.5
1 .4
analyst pel D fc V » *
14.
95
12.
21
26.52
16.69
1ED1UH YOUOEN PAIR
3
4
3
4
3
4
3
4
NU«HE* OF DATA POI'US
1 1
11
11
12
u
14
1 3
14
TRUE CONC IC) UG/L
9s .r
1°0.0
9 5.0
1C0.0
95.0
100.0
V5 .0
100.0
HE AN RECOVrCY IX)
10 7.6
71.3
114.8
72.0
1C».2
81.9
91 .6
78.4
ACCURACYIXREl ERROR)
13.?R
-20.74
2C.85
-27.98
13.93
-10.13
-3.61
-21 .55
0V f RA 11 STD DEV (S)
7.6
15.0
28.3
25.5
20.n
1 7.8
16.1
19.2
overall pel sid dlv, X
7 .C5
21.12
24 .62
35 .35
18.44
21 .79
17.53
24.48
SINGLE SID DEVf (S H)
9
.0
24
.9
17.3
17.5
ANALYST KEL dev» *
IC.
C 9
2 6.
66
18.24
20.59
HIGH YOU D L N PAIR
5
6
S
6
5
6
5
6
nukrfr or data poinis
10
1 2
12
12
13
14
1 3
12
true CONC
49
.0
77
.6
60.4
7 3.9
aNALYST REI DEV. X
17.
U"
17.
71
15.M
19. !6
WATF B IE f»E NO
1 - DISTILLED WATER
2 - TAP UATE R
J - SURFACE WATER
4 - INDUSTRIAL (FfLUENT
-------
TABLE 7-6
EfcVlPOM*FNTAl H0NI1CR1NC, AND SUPPORT LAnORAlORV
Of r IC £ or RESEARCH AND DEVFLOPrENl
ENVIRONMENTAL PROTECTION ACE NC Y
f PA FflMOD 624 VALIDATION STUD* - PURGEARLES ••
STATISTICAL SUMlABf fOR CHLOROHfNZE^f ANALYSES OY WATfcR TYPE
WATER 1 WATER 2 WATf ® 3 WATER 4
LOW YOUDEN PAIR
1
?
1
2
1
2
1
2
Nlllfl F R or DATA POINTS
u
14
12
12
U
1?
15
15
TRUE CCNC IC) I'G/L
13.5
15.0
13.5
15.0
13.5
15.0
13.5
15.0
MEAN RECOVERY (!)
15.5
16.7
15.8
17.4
16.5
1B.C
14.7
16.2
ACCURACVftREL ERROR)
14 .81
11.62
16.79
16.22
22.12
20.14
8.94
8 .09
OVERALL S7D D E V (S)
2.C
2.6
2.4
4.6
3.0
1.7
3.7
2.8
OVERALL BEL $td CEV, X
12.97
15.69
15.48
26.33
17.96
9.69
25.42
17.53
SINGLE STD DEV. (SR)
2
.6
*
.e
2
.5
5
.6
analyst rfi dfv, t
15.
97
22.
63
14.
56
23.
61
1E D101 YOUDEN PAIR
3
4
i
4
3
4
3
4
NUt»Bf R or OA t A PO IN I S
H
1?
12
13
14
13
15
15
TRUE CONC (C) UG/L
142.C
150.0
U2.0
150.C
142.0
150.0
142.0
150.0
MEAN RECOVERY (X)
152.7
160.2
143.0
1 A 2 . 4
165.6
162.8
136.3
153.8
«ClURACYE V IS)
3^.8
? 3.5
42.5
22.9
JT .9
29.6
41.0
48.9
OVEPALL OIL SID DEV• )
22.ec
20.94
29.71
U.08
19.27
18.17
30.06
31.81
SINGlf SIC 01V , ( SR )
15
.1
30
.8
22
.6
35
.2
ANALYST RCL DEV. X
9.
67
20.
17
13.
77
24,
31
HIGH TOUDfN FAJR
5
6
5
6
5
6
5
6
NUMBER 01 DATA POINTS
14
1
*
12
1!
14
14
15
15
IRUE CONC (C) Ub/L
60C.0
540
.0
60C.0
540
.0
600.0
540
.0
600.C
540.0
"IEAN rfcovery <*>
5 50 .2
487
.'J
52C.3
6 3 C
. 7
50".1
55 1
.2
520.7
4 7 8.8
AlCURAC1 CtREL 1R H OR )
-8.30
-9.
81
-13.29
16.
* 0
-15.32
2.
C?
-13.2?
-11.33
OVERALL STD CEV
-------
TABLE 7-7
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
Of rice Of RESEARCH AND DEVELOPMENT
ENVJ»ON*UN1Al PROTECTION AGENCY
• • tPA RFTHOO 62' VALIDATION STUDY - PUBGEAUL£S ••
STATISTICAL SUMMARY FOR C Hi 0 R 0 E 1H A N t ANALYSIS f?l W A T £ R TYPE
fa A 1 E R 1 WAUH 2 WA1ER 3 WATER 4
LCU YOUCfN P A ] R
T
2
1
2
1
2
1
2
NUMniR Of DATA POINTS
14
14
13
13
14
13
1 3
15
TRUE CCNC FV, t
49.97
4 1 ,PT
29.4 7
39.25
*6.67
49.46
25.02
4 P .33
SINGLE STO DEV, CSR)
4.2
2.0
3
.9
3
. 1
ANAl YST Rft DEV, X
42.<8
22.91
37.
P 4
34 .
96
"FOIUM YOlJCfN PAIR
3
4
X
4
3
4
3
4
NUMBER Of OATA POINTS
14
1*
14
15
13
14
1 5
13
TRUE CON C
53.7
2C.9
43.9
36.8
29.6
34.6
69.1
27.5
OVFRALL CU STD DEV, Z
36.6h
22.45
30.33
3 7 .00
21.75
r\j
•o
43.10
3C.55
SINGLE SID DEV,
16. P6
17.25
13.61
16.97
6.55
21.5C
1 7,87
24.62
OVERALl STD DEV «S>
12 8.3
152.P
197.4
191.4
151.C
189.3
175.6
251.8
OVERALL PEL SID DEV* X
24.56
26 .70
38 .66
33.52
! 1 .71
31.92
33.32
41.41
* 1 NGlE STD DEV, < SR >
M .4
155.5
134
. 1
1 79
.P
ANAL YST PfI D £ V , 2
14.PP
28.?4
25.
CP
31 .
68
UAT|P LECCNO
1 - OlSTltiro W A T £ R
2 - TAP mATTP
J - SURFACE WATER
4 - lNDUSfRIAL ffrLUCK'V
-------
TABLE 7-8
ENVlRC*.rC'JTAL rCM?0RlN6 AND SUPPORT L A p OR A T<>R T
OFFICE OF RESEARCH AND D F VE LOP*F NI
ENVIRONMENTAL PROTfCflPN AGENCY
EPA "E THOt) 624 VALIDATION S T 1)0 ¥ - PUDGE ARLf S *•
statistical suhmapv fOfi CHLORrronr* analysfs at water type
W A T C B 1 WATER ? WATER 3 WATER 4
1OW VOUDFN PAIR
1
2
1
2
1
2
1
2
NU«OER OF DATA POINTS
u
1?
f
11
13
11
11
11
TRUE CONC DEV
-------
TABLE 7-9
(K'tflROfcNF N1AL H0»JM0B1NG AND SUTP0RT LAPORATORY
Office Of RfSt««fM A D DtVFLOpKTNT
ENVIRONMENTAL PROTECTION AGf NC V
•• EPA «tlHOO 624 VALIDATION STUDY - PURGEAULES ••
STATISTICAL SU1"ARY FOR CHI 0ROMCTHANI ANALYSIS HY WATER TYPE
WATER 1 WATER 2 WATER 3 WATfcR 4
LOW YOUDEN P A|P
1 2
1
2
1
2
1
2
NUMR F R Of DATA POINIS
11 11
e
1 1
11
11
1i)
11
TRUE CONC CC) UG/L
7.® 7.0
7.8
7.0
7.e
7.3
7.8
7.0
M£ AN RECOVERY (i)
7,4 1 C. 9
6.3
7.2
7.4
8.0
• .6
5.9
ACCURACYCXPEL ERROR)
-5.59 56.2!
•18
.75
2.99
-4.7* I7
.8 3
1 J.64
-15.13
overall sid rev UG/L
117.0
m.o
117.0
111.0
117.0
111. C
117.0
111.0
CO
MEAN R(COVF R Y (!)
130. 8
ec.3
14C .9
82.1
161.6
87.8
126.7
73 .1
Oo
AC(U«ACY (IREL ERROR)
1 1.80
-27.6!
20.4 3
-26.01
38.08
-2C.93
9.2 8
-34.13
ovfrali std rev
-------
TABLE 7-10
INVjftrMHCNIH K0NI10H1NF AND SUPPORT LAPORATORY
OFFICE Of RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
•• | T A nflHOD 624 VALIDATION STUDY - PURGEABLES ••
STATISTICAL SURMRV FOR { 1 S-1 , !-DI CHLO»OP»OP» Kt AHALYSfS B* WATER TYPE
WATEP 1 WATER c WATER 3 WATER 4
LOW YOUD{N PA|R
1
2
1
2
1
2
1
2
NUMBER OF DATA POINTS
10
10
11
11
11
12
12
12
TRUE C ON C (C> L'G/l
8.H
e.9
0.3
8.9
e.o
8.9
8.0
8.9
•"IAN RECOVERY 1*)
9.6
10.1
f .5
11.1
9.6
10.1
9.2
10.0
ACCURACYIXREL ERROR)
19.50
13. P3
6.14
24.41
20 . 34
13.81
15.21
12.87
OVERALL STD 01V
2.1
2.9
2.6
4.1
1.7
4.2
2.1
2.9
OVERALL oEL STD DEV. X
21. 48
2?.12
3C.17
36.84
17.25
41.05
22.66
29.08
SINGLE SID DEV, CSR)
2.3
2
.5
2
.5
1
.8
analyst REL DEV. X
23.ec
25.
54
<5.
29
18.
41
ME D1 UN YOUDEN PAIR
3
4
3
4
3
4
3
4
NU*3ER OF DATA POINTS
10
9
11
12
12
12
12
12
TRUE C ON C
18.9
23.6
27.7
25.0
3P.0
19.5
22.3
22.7
OVERALL PEL STD DEV. X
16.64
2C.33
24.39
21.96
!4 .46
16.65
20.64
19.51
SINGLE SID DFVv (SRI
15.6
14
.8
26
.0
14
.4
ANALYST REL D(V( X
13.50
12.
99
22.
84
12.
84
HIGH YOUDEN PAIR
5
6
5
6
5
6
5
t
NUMBER OF OATA POINTS
10
9
11
12
12
11
12
11
TRUE C ON C (C> UG/L
357.0
321.0
? 5 7 . 0
321.0
35 7 .0
321.0
357.0
32 1.0
^tAN RECOVERY IX)
440.5
342.0
38 7.2
365.8
362 .5
336.0
4 52.3
32 3 .8
ACCURACYUREl ERROR)
23. J*
6.55
8 .45
13.96
1 .55
4.68
21.10
0.89
OV f R A LI STD DEV (S)
163.9
t 7.8
151.7
80.0
1 70.3
91.1
1 39.2
90. 3
OVERALL REL STD DEV* X
37.22
19. f 3
39.18
21.87
4 6.91
27.13
32.20
27.89
SINGLE STD OEV,
-------
TABLE 7-11
lNVIRONMNI At HONMORING AND SUPPORT IAPORATORY
Office 01 RtSCARCH A WO DIVlLOPKENI
ENVIRONMENTAL PROTECTION AGENCY
»* fPA KfTMOD *24 VAl 1 DA T1 ON STUDY - PURGEAOLES ••
STATISTICAL SUr^ARV FOR D]OROr«OCHLOROr(lHANE ANALYSES BT WATER 1YPE
WATER 1 WATER 2 WATER 3 WATER <>
LOW youden pair
1
t
1
2
1
2
1
2
NUMBER Of DATA POINTS
14
13
15
13
13
15
1 1
13
TRUE C ON f CO UG/L
* .1
9.0
8.1
9.C
8.1
9 . C
P.I
9.0
AN RECOVER* <*)
8.0
9.?
7.8
9.8
8.8
8.7
7.7
9.3
ACCURACVOREL ERROR)
- 0 . s 8
? . 39
-3.21
9.23
8.07
-3 .67
-5.50
2.99
OVERALL STO DEV CS>
1.8
2.1
3.3
2.9
1.2
2.2
1.0
1.7
OVERALL RfcL SID DEV, X
2 2.01
22 .95
41.91
29.77
13.26
25.41
12 . 7*
18 .82
SINGLE STD DEV*
* 6 >• . 1
3*1.6
412.0
3P8.1
37?.2
326.8
*96.5
349.4
A C CURAC Y CX&EL ERROR)
2.24
2.35
14.43
19.78
5.05
r.86
10.15
7.85
OVFRAIL STO OEV CS)
74.1
44.9
V».7
14 2.2
101.0
5 8.0
76.8
99.6
OVERALL RFI STD DFV, X
?c. n
13.54
7 < .74
36.65
26.71
17.74
19.37
28.51
SJ'vGLt STD DtV, (SR)
45.2
83
.C
65
. 1
51
.9
ANALYST BEL DEV. X
12.91
20.
75
18.
47
13.
9?
WATER IFGE ND
1 * OISTIILfD WATFR
2 - TAP W A T fR
3 - SURFACE JAIF H
4 - INDUSTRIAL EFFLUENT
-------
TABLE 7-12
F N V1R ON* fc NI A L MONITORING AND SUPPORT I AHORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
•• EPA PfTHOO 624 VALIDATION STuOT - PURCEAPLES ••
STATISTICAL SUf-ARV FOR E IMYL PfNMNE AN AL Y 5 E S PY WATER TYPE
WATER 1 WATER 2 WATER 3 WATfcR 4
LOW YOU 0 r N PAIR
1
2
1
2
1
2
1 2
NUHRFR OF DATA POINTS
U
U
11
12
14
14
1 5 12
TRUE C ONC CO UC / L
15.C
17.0
15.P
1 ?.C
15.C
17.0
15.0 17.C
HEAN RfCOVERY (*)
16.7
19.6
17.6
PC.2
19. 0
? 1 .n
19.8 19.5
ACCURACYCXPFI FRROR)
11 .62
15.^9
17.39
18.82
26.76
23.47
12.2! U.fiO
OVERALL STD tfV
3
. 5
5
.1
3
.4
4 . 7
A N AI tST RFL DEV. X
19.
19
27.
CP
17.
22
2 5.99
MFOIUM VClirEN PAIR
3
4
3
4
3
4
3 4
NUMBER OF DATA POINTS
15
14
12
11
14
14
13 13
TRUE CONC UG/L
162.0
170.0
162.0
170.C
162.0
170.0
162.C 170.0
AN R fCOVF RY (X >
167.7
164.8
166.1
174.5
18< .8
175.8
166.1 191.0
ACCURAC V(XPFL ERROR )
3.49
-3.C6
2.54
2.66
14 .68
3.40
2.50 12.35
OVERALL STD DEV (S)
37.C
*4.2
36,9
1 2 ~ C
52.9
26.7
27.5 59.7
OVf RAlL RFL STD DfcV, X
22.C6
20.76
22.21
6.87
17.72
15.20
16.57 31.27
SINGLE SIC DEV, < S R)
20
.3
27
.7
24
• 9
4 Ci. 9
ANALYST R£L DfcV, X
1?.
24
16.
25
13.
76
22.91
HIGH YOUDFN PAIR
5
6
5
t
5
6
5 6
NU"OCR OF DATA POINTS
15
15
12
12
14
14
13 13
TRUE C ON C CO tlf./L
68C.n
612.0
t PC.3
612.C
68C.0
612.0
6 80.0 612.0
1EAN RECOVERY (!)
6^1.3
615.4
591.6
673. 7
631. 5
615.0
659.4 604.6
ACCURACY(XRtL FRROR)
-5.69
T.<6
-13.00
10.P9
-7.13
1.49
-3.03 -1.18
OVFRALL SIO DIV
181.0
1>C.2
2 2 4,0
171.5
1 8 £ . 9
15C.0
260.2 164.6
OVTRALL REL SID DEV* X
28.2?
29.28
!?.£*
25.46
29.92
24.39
39.47 27.22
SINGLE STD DEV, (SR)
97
.2
173
.5
1 C 4
.3
155.5
ANALYST REL DEV, X
15.
4 7
27.
<2
16.
73
24.60
WA T E ° LCCENO
1 - D1SMILED W A I fc R
2 - TAP WATFR
3 - SURFACE WATER
4 - INDUSTRIAL F FFlUtNT
-------
TABLE 7-.1.3
ENVIRONMENTAL W0NI10RING AND SUPPORT LA POR A T 0 R Y
OMlCE Of "[SE'flCH AND DEVELOPMENT
(MVlBONhEM*L PROTECTION AGENCY
•• ETA MTHOD ft?4 VALIDATION STUDY - PURGEAGLES *~
STATISTICAL SUKWARY FOR ^ETHYLENE CHLORIDE ANALYSES UT WATER TYPE
WATER 1 WATER 2 W A T f ® 3 WATER 4
LOW YCUDEN P A IP
1
2
1
2
1 2
1 2
NIPPER OF DATA POINTS
1 J
12
1?
12
10 13
8 11
TRUE CONC Ev, csr)
2.3
8
.6
12.C
6.2
ANALYST RFI DFV, X
27.41
75.
9ft
8 *2
69.88
P1ED1UH YOUDEN PAIR
3
4
3
4
3 4
3 4
NUMBER OF DATA POINTS
14
1!
13
14
13 IP
13 13
TRUE CONC (O UG/L
12P.0
IH.O
1CC .0
114.0
120.0 114.0
120.0 1U.0
Wf AN RECOVERY IX)
135.8
74.1
UC.1
75.1
1C 7•7 91.3
1D3.1 54.9
ACCURACYfXREL ERROR)
-11 .«,n
-35.01
-It.01
-34.12
-10.2? -19.93
-14.12 -51.83
OVERALL STD DEV (SI
32.1
2 3.1
43.7
27.2
25.2 19.0
32.0 29.9
OVERALL RFI STD DEV. X
30.31
31. ?3
45.37
36.21
23.34 2f.80
71.09 54.50
SINGLF SID DEV, (SR )
?1 .4
30
.9
13.9
27.6
ANAL YST REL DEV, X
23.76
35.
11
14. CO
34.93
HIGH YOU D F N PAIR
5
6
5
6
5 6
5 6
NU*B F ft OF DATA POINTS
14
13
1 3
1 5
1? 11
1 3 12
TRUE CONC CC) UG/L
432.0
480.C
4!?.?
4 P 0 . 0
432.0 480.0
432.0 48C.0
-CAN RECOVERY (It)
390.6
4n9.2
323.2
390.4
399.4 J 9 ? « C
743.7 357.9
ACCURAClCXRFL ERROR)
-9.59
-14.76
-25.19
-IP .6ft
-7.56 -1P.13
-20.44 -25.44
OVERALL STD DEV (S)
159.R
117.9
1CC.Q
174.0
166.4 9C.T
165.? 185.2
OV f R A L L REL SID DEV, T
4 0. 91
28.80
3C.93
44.57
41.66 22.9C
4P.07 51.75
SINGLE STD DEV, ISR)
59.5
91
.3
114.4
1C7.8
ANALYST PEl DFV, X
U.?9
25.
6C
2P ."9
3?. 74
UAHR LEGEND
1 - DIST1LLEO WATER
2 - TAP w A T f ft
5 - SURFACE WATER
4 - INDUSTRIAL EIFLUENT
-------
TABLE 7-14
E*V1 fiON'HN1AL MONITORING AND SUPPORT IA90RAT0RT
office or research ano dfvflop^ent
E NVI RONffc NT AL POOlldlON AGfNfV
•* EPA r.fTMOO 624 VALIDATION S TUO T - PURGE ABL E S • •
STATISTICAL Str-HBf FOR 1FTNACHI 0ROETMENF ANALYSES Rf UA I fR TYPE
WATER 1 y A T f 9 2 WATER 3 WATER 4
LOW TOUDEN PAIR
1
2
1
2
1
2
1
2
NU^OER Of DATA POINTS
11
11
12
12
13
14
14
13
TRUE CONf
1
.2
2
.4
1
.9
3
.2
ANALTST *EL t»EV, X
11.
C 4
23.
66
16.
71
32.
28
1EDIUP TOUDEN FAIR
3
4
3
4
3
4
3
4
NUMBER OF DATA POINTS
12
11
12
13
13
14
14
1?
TRUE C ON ( (C) CI C / L
9S.L'
1°0.0
9^.0
IOC.(J
95 .C
1"0.0
95.0
1C0.0
•UAN PECOVERT
-------
TABLE 7-15
ENVIRONMENTAL ffONlTORINb AND SUPPORT LAPCRATORT
Off ICE or RESEARCH AND DEVELOPMENT
E N V 1R ONH E N T A L PROTECTION AGENCY
•• EPA PtTHOO 624 VALIDATION STUOY - PURC.FABIES ••
STATISTICAL SUMMARY FOR TOLUENE ANALYSES 0 Y WATER TYPE
WATER 1 WATER 2 WATER 3 WATER t
LOW YOUDF N P«1B
1 2
1
2
1
2
1 2
NUMBER OF 0AT4 POINTS
1? 1?
T 3
14
1 4
1 3
12 11
TRUF CONC
3 1.1
5C.4
2 * .4
16.1
27.5
20.1
38.4
41.5
OVFRALI REL STD DEV. X
20.33
19.30
20.63
11.74
17.23
13.15
27.29
28.10
SINGLE STD DEV.
516.7
52U3
552.7
571.7
536.9
55 1.2
516.1
494.5
ACCURACYUREL ERROR)
-1J .89
-3.44
-7.88
5.PP
-10.51
2.07
-1 J.9P
-P.42
HVfRALL SID DEV (Si
159.4
71.7
178.1
155.2
175.3
149.0
159.4
73.3
OVERALL REL STO DEV. X
3C.C6
11 .78
12.12
27.15
32.65
27.04
30. 70
14.8J
SINGLE STD DEV,
na
.1
118
.4
103
.3
U O. 2
ANALYST REL DEV, X
21 .
24
21.
06
IP.
99
19.A3
WATFR LEGEND
1 - DlSTIiLTO WATER
2 - TAP WATER
3 - SURFACE W A T r R
4 - INDUSTRIAL EFFLUENT
-------
TABLE 7-16
ENVIRONMENTAL «ON|TORING AND SUPPORT LABORATORY
Off Kt Of RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
•• fcPA F E 1 HO D 624 VALIDATION STUDY - PURGE'() ICS ••
STATISTICAL SUGARY FOR T R A N S -1 , 2 - 0 I C HI OR 0 E 1 N E N E ANALYSES HY WATER IYPE
WATER 1 WATER 2 HATER 3 WATER 4
low YOUDFN PAIR
1
2
1
2
1
2
1
2
NUIOCR Of DATA POINTS
14
IS
12
13
1 5
14
12
13
TRUE C ON C
12.P
12.0
U.4
15.2
14.5
11.4
12.0
18.7
OVERALL REL STD DEW, X
16.U1
21.71
19.25
24 .Pf»
1R.3?
19.13
15.07
33.80
SINGLE STD DEV, ISR)
12,1
17
.2
10. 3
11 .4
ANALYST PEL DEV, 1
1 7 . ? fl
23.
55
14.98
16.85
HIGH YOUDEN PAIR
5
6
5
6
5
6
5
6
NUMBER Of DATA POINTS
15
15
12
13
14
1?
12
13
TRUE CONC CO UG/L
270.0
300.0
2 70 .3
300.0
270.0
30C. 0
270.0
300*0
«EAN RfCOVfRY (X)
?P4. ?
311.4
282.3
340.5
25 3 .3
323.0
271 .7
300.9
ACCURACYUREL ERROR)
5.29
I .61
4.55
13.49
-6.20
7.66
0.63
0.31
OVFRALL STD DEV
-------
TAKI.E 7-17
ENVIRONMENTAL NOMIOfiINC AND SUPPORT LAPORATORY
office or research and development
environmental pPOTffrroN *crnci
•• EPA RF1H0D ft?* VAI I 0 A TI ON STUD* - PUR Gt A P L E S ••
STATISTIC*! SIJMPARY FOR 1 R A N S -1 , 3 - D I C H L OR 0 P « OP £ NE ANALYSIS BY WATER TYPE
WATER 1 WATER 2 WATER 3 WATFR 4
LOW VOUDEN PHP
1
2
1
?
1 2
1 2
NU^BFR OF DATA POINTS
1 1
1?
12
12
11 11
12 12
TRUE C ON C liC i L
9.1
10.4
9.4
1 C . 4
9.4 1C.4
9.4 10.4
Hf AN RECOVERY (X)
7 . 7
H.4
7.?
e.u
9.5 9.2
7.6 8.4
ACCURACKtREL ERROR)
•17.60
-19. C7
-22.5?
-23.16
1.06 -11.45
-19.50 -18.83
OVERALL S7D DFV f S >
1 . 9
2.2
2.0
2.3
2.5 2.3
1.1 1.5
Ovf RALl * k I S T D 0 E V , X
24.49
25.83
28 .06
28.32
26.63 25.28
14.33 17.22
SINGLE SID DEV. (SR)
1.2
2.0
1.5
1.0
analyst PEL t)EVt X
14.25
25.92
1 5.97
12.84
PEDlun TOUDEN PAIR
3
4
3
4
3 4
3 4
NUMBER OF DATA POINTS
11
1C
11
13
11 11
12 12
TRUE CON C CO UG/L
99.0
1C4.0
99. 0
104.0
99.0 104.0
99.0 104.0
"EAN RECOVER* CD
08.7
98.6
77.9
95.9
97.1 10C.6
84.6 88.6
AC CUPACt fXREL FRROR )
-1C.42
-14 .84
-21.27
-7.no
-1.97 -3.79
-14.30 -14.80
OVERALL SIP 0[V
11.5
17.9
16.7
25.4
25.5 25.7
17.9 16.8
OVERALL PEL STD DC V» Z
12.98
?0.?1
21.41
26.54
26.23 25.«3
21,11 18.92
SINGLE STD D E V •
a?. 2
1 C 5 .1
8? .2
78.4
7 A.4 70.7
78.5 61.2
overall rel std dcv, x
27 .43
40.81
25.12
27.38
22.79 22.73
23.77 21.C6
single STD DEV. CSR)
8 5.8
49.7
63.2
49.2
ANAL YS T REL OtV, X
29.44
15.60
19.55
15.86
WATER legend
-------
TABI.F. 7-18
ENVIRONMENTAL *ON|TCRING * NO SUPPORT L A COR A T 0 R Y
office or research and develof*eni
tNVIRONTENTAL PROftCllCN AGFNCY
•« tPA TE1HOO 624 VALIDATION STUDY * PIJRGEA«LES «•
S1A11STICA1 SUBPART FOR TRICHLOROETMEUE ANALYSES BY WATER lYPfc
WATER 1 WATER 2 WATER 3 WATER 4
LOW YOUOFN PAIR
1
?
1
2
1
2
1
2
NU'OER Or D A 1 A POINTS
11
11
1!
13
13
13
12
12
TRUF C ON C
2t.!
77.3
It .0
118.3
73.8
54.8
9? .4
13e.4
OVERALL R EI STO DEV, X
7.48
22.96
24.46
29.92
23.81
ifc.r»3
*1.93
39.34
SINGlE STD DFV,
-------
TABLE 7-19
CNV I RCN1ENf*1 MONITORING AMD SUPPORT LABORATORY
Of f t C t or RESEARCH ANO DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
• • EPA KETMPD 624 VALIDATION STUDY - PIJRGEAULES •»
STATISTICAL SUBPART FOR TR I C HLOR 0 F LUOR 0* E 11IA U f ANALYSES BY WATER TYPE
WATER 1 WATER 2 WATER 3 WATER 4
LOW YOUOFN PAIR
1
2
1
2
1 2
1
2
NUHDER OF DATA POINTS
10
11
1C
10
11 11
11
11
TRUE (ONE (() U(Wl
e.e
7.2
P.3
7.2
8.0 7.2
8.0
7.2
«EAN RECOVERY (K)
*~5
7.3
7.«
7.7
7.9 6.4
8.0
7.6
ACCURACY(ZPEL F R R 0 R )
6.1?
1 .m
-2.75
7 .64
-1.02 -1C.73
0.57
5 .8 7
OVFRAU STD DtV IS)
2.1
2.4
2.2
2.4
2.7 1.9
1.6
1.6
overall »el std dev, x
24 .54
33.41
27.78
30.71
*3.49 29.64
20.37
20.41
SINGLE STD flfv, (SR)
1.1
2.1
1.8
0.5
ANALYST REL DEV, X
14. C1
26.70
24.58
6. 78
MEDIUM YOUDEN PAIR
4
4
3 4
3
4
NU'RfR OF DATA POINTS
11
1C
1C
11
11 11
11
11
TRUE CON C CO UG/L
120.C
114.C
12C.0
114.0
120.0 1U.C
120.0
114.0
MEAN RECOVERY fV, X
36. ir
34.91
2 9 • 3 A
32.44
44.35 22.07
23.69
30.31
SINGLE STD DEV* (SR)
14C.7
79.4
127.4
127.2
ANALYST REl DEV, X
! 2 . * 5
16.PI
3 2 . P 2
26.89
WATER LEGEND
1 - DISTILLED WATER
2 - TAP WATFR
5 - SURFACE WATER
4 - INDUSTRIAL EFFLUENT
-------
inmiijj lviuisnoNt - 7
bin* nvjans - t
ajirn d«i - 2
d jivp onilisio - i
QN3-J31 tlltn
Qi *£2
26
•01
27*71
0 7 * £ 1
t 'AJO 13M 1SA1VNV
84M I
7*
6 7
9*69
6*75
(US) *A3Q
s* us
9*SS7
S*677
i* 19*
£*jOS
0*777
£•724
( X ) A «3AOD 38 NV 3h
0*2£>
0*087
0"2£7
0*087
0*2*7
0-097
0*2*7
0*387
l/9fl O) 3 NO) 3(ldl
SI
71
21
£ I
21
21
71
£ I
siNiod viva jo dSQ-jn*
9
%
9
S
9
S
9
t
dlVd NJOnOA H'JlH
97'22
07
*21
9t * Z 1
9i*9l
X * A JQ 1 3d ISA 1VNV
1*9*
7*
7 1
2*64
£ 'I V
(dS> * A 3 0 QlS 3 ION IS
S£*2£
68*£ I
ZZ*7l
2 S * 91
99'S I
S£*7l
00*71
Li' I I
1 * A 3 0 Q1S lid 11V d i AO
3'ȣ
7*22
6 * 5 t
i*G2
7'Sl
S*U
2 * £ I
8*02
(S) A30 CIS 11va3AO
/t'Ol-
U'b
S S * 01 -
S9'6
22*21-
22*2
2 7 * I £ -
7 £ " 2
(HOddi 13dX)A3Vdn]]«
9*^01
I * 52 I
f *Z0l
0*521
2*06
2*221
2*76
i*m
(X) 19JAODJd Hflu
0*021
0*711
0*021
0*711
0*321
C*H1
0*021
0' 7 I I
I/on ( )) )NOJ 9)1 M1
SI
u
il
U
11
U
21
71
siNiod viva jo djy^nh
7
s
7
c
7
£
7
£
divd NjanoA uniai»
68"02
i9
"61
96'il
*6*21
t •a3a 13a iSAivNt
9* 2
7*
2
9*i
9*1
(Si) *A30 ais HONfS
01*82
lO * £ £
16*91
8£*72
I Z*£2
89" 8 I
£9*91
69*02
I 4a3a ais 13a iivu3ao
2*C
8*£
2*2
6*2
6*2
0*2
£ * 2
S * 2
(S) A3Q <11S HV^iAO
£3*6
08*5
£2*8
Z**6
0 7" £
7}'0
V £ " 7
h\• ii
(dOddi lidZ)AJVdrt)3v
2*U
7*U
0 * £ I
8*U
7'2l
6*31
5*21
0*21
(K) Ad3*3)3d N V Ik
0*21
8*01
0*21
8*31
0*21
3*31
0*21
8*31
1/9(1 (3) 3NOJ 3nai
Si
si
kl
£ I
21
11
£ I
71
SINlOd ViVO JO d3Q40N
2
1
2
1
2
I
2
I
a(v<« Nionoi noi
* imvn i blivn ; aJiYfl i d3ivn
3dAl dllVA A A S3SA1VNV 3HVH130MOTH }10-I•I dOJ A8VUJU1S lVlllSUtflS
• • S3inv3
-------
TABLE 7-21
(NvlRCMFNTAl MONITORING AND SUPPORT LAPORATORY
QffHi 01 RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGFNCY
•• fPA Pi THOO 624 VALIDATION STUDY - PU«$t*HLES **
STATISTICAL SUMMARY FOR 1 , 1 - 0 I C H L 0 RO E T Mf N E ANALYSES BT UAKR TYPE
WATFR 1 WATER 2 WATFP 3 WATER A
LOU YOUOEN PAJR
1
2
1
2
1
?
1
2
NUMBER OF DAfA POINTS
n
14
1C
12
13
14
11
13
TRUE C ON C (C) UG/l
8.?
7.2
8.0
7.2
B.C
7.2
8.0
7.2
"•FAN RECOVERY < A)
9.4
8*9
P »9
9.4
9.?
8.1
7.6
8.3
AC CURACY<*R£L FRROR >
17.02
2? .51
11 .n
31.25
15.10
11.95
-5.57
15.22
OVf R ML STD DEV < S >
3.7
3.7
1.1
4.6
2.2
2.9
1.4
2.7
OVERALL PEL SID OEV, X
59. 16
41 .*4
12.77
4 8 , 4 G
23.36
35.94
19.01
32.63
SINGIF SID DEV, (SR)
2
.6
3
.2
2
.2
1
.5
ANAlYST REL DEV, X
2f>.
1C
35.
02
2 5 .
16
18.
94
"EDIU" YCUDEN PAIR
3
4
3
4
3
4
3
4
NUMBER OF DATA POINTS
15
14
12
13
13
14
12
12
TRUF COUC < C > UG/l
120.0
114.0
12C.0
11 4.0
12C.0
114.0
120.0
114.0
*ian recovery (i)
12C.1
75.3
119.9
79.1
111.8
85.3
105.4
65.5
ACCURACY(XRf 1 FRROR )
o.ot
-33.97
-0.2H
-30.65
-A. 79
-25.13
-12.13
-42.51
OVERALL 5 T D DEV 1$)
41.7
13.4
28.6
H.I
17,3
12,2
U. 8
2C.5
OVERAI| REL SID DFV, 1
34.74
17,85
2 3 . 8R
20.^8
15.43
14.^0
u.04
31.22
$ I NO LI STD DEV,
27
.9
22
.6
13
.7
19
.C
ANALYST REL OEV» X
28.
55
22.
75
13.
8e
22.
22
MICH YCUDEN PAIR
5
6
5
6
5
6
5
6
NUMBER OF DATA POINTS
15
15
12
12
13
1!
13
12
TRUE C ON C
-------
TABLE 7-22
ENVIRONMENT AL «ON|TOPI*G ANO SUPPORT LAOORATOPY
OMICE 0 F RESEARCH ANO D f Vf L 0 P*E N T
ENVIRONMENTAL PROTECTION AGENCY
•• EPA HETMOD 6?4 VALIDATION STUOY - PURf.EARIES "
STAY ISTICAl SUGARY FOB 1 f 1 9 1 -Tft JCNL0ROETMANE ANALYSIS BY WATfP TYPE
U A1 (P 1 WATER 2 WA1(R 3 WATER 4
LOW YOUDtN PA1P
1
2
1
2
1
2
1
2
NUT FR 0 F DATA POINTS
15
u
1 3
1 3
1 3
14
1 1
11
TP»t CONC UC/L
9.0
10.0
9.0
1C.C
9.0
1C.0
9.0
10.0
TfAN RECOVERY (*>
1C.C
11.7
S.3
10.9
9.1
1C. 7
9.8
10.7
>. CURACY(tPEL ERROP)
11.6?
17.36
2.91
8.62
1.37
6.64
9.29
7.18
OVERALL STD DEV CS>
1.8
1.9
1.9
2.2
1.?
2.9
2.0
1.8
0 V r R A L L PEL SU OEVi X
.08
1< .14
2C.73
20.32
13.06
£6.99
20.6!
16.44
SINGLE STD 0 E V « UG/L
95.0
100.0
95.0
10C.0
95 .C
100.c
95 .0
100,0
AN RECOVERY (X>
110.5
87.9
1 U.I
90.7
104.7
95.8
95.0
90.2
ACCUPACYfXREL CPROP>
16. 34
-12.1?
20.09
-9.28
10.23
-4.19
-0.00
-9.78
OVERALL STD DEV
1C
.5
19
.4
19
.8
16
.9
ANALYST PEL CEV, X
1C.
59
18.
99
19.
74
18.
26
HIGH YOUDEN PAIR
5
6
5
6
5
6
5
6
NUf0 E R OF OATA POINTS
u
14
U
14
15
15
11
12
»RUE CONC < C > UG/L
A c c. c
360.C
4 00. C
360.C
400.0
360.0
40C.0
360.0
MEAN RECOVERY (X)
<5d.7
386.9
465.1
411,1
375 .0
374 .8
397.6
390.9
ACCUVACYtXHtL E P POP >
n.m
7.48
16.27
14.18
-6 . 26
4.10
-0.61
8.57
OVFRALL S10 DEV C S >
1C6.1
81.1
1C(f .0
94.0
136.6
85.0
92.6
93.9
OVERALL PEL SID DEV, X
2 3.??
20.95
22.6?
22.87
36.44
« ? . 6 7
? 5.29
24 .02
SINGLE SID DEV, (SR)
51
.7
n p
.9
93
.5
64
.2
ANALYST ftCL PEV, X
1 2.
2 5
20.
29
24.
93
U.
3 C
WATER KGFNd
1 - DISTJILEO WATER
2 - 1AP WATfP
3 - SUPFACt WATER
4 - INDUSTRIAL EMIUCN1
-------
TABLE 7-23
ENVIRONMENTAL MONITORING A N 0 SUPPORT LAPORATOPY
Office Of RESfARCM AND DEVELOPMENT
»NVIKCN"fcMAL PROTECTION AGFNCY
•• tP A KUHOO 624 VALIDATION STUDY - TURGIAHliS ••
SfAl ISTTCAI SUGARY F OR 1 . 1 . 2 - T 9 J C M L 0 R 0F T H AN f ANALYSES RT WATER TYPf
WATER 1 WATER 2 WATER J WATER 4
LOW YCUDCN PAlli
1
2
1 2
1
2
1
2
NU*PfR OF DATA POINTS
1 3
12 12
1 1
12
12
13
TRUE C ON C (C> Uf./L
ic.p
12.0
K.«5 12.0
K.F
12.0
10.®
12.0
MAN RECOVERY <*>
12.r
12.9
12.D 14.9
13.0
1 ' . 5
11.2
13.7
ACCUPACYfXPEL f R R OR >
11 .04
7.P8
11.4? 24.?6
20.12
12.92
4.U9
14 .1C
OVERALL STD DFV (S)
1.9
2 . 7
1.5 4.7
1 . 7
2.5
1 . 3
2.4
OVERALL PEL STD DtV, X
16.2?
2C .62
12.6? 51.57
12.94
17.01
11.47
17.84
SINGLE STO DEV,
1
.9
3.0
1
.8
2
.3
ANALYST PEL DEV, X
14.
P 5
22.17
13.
90
18.
33
IfOIUH YOUCEN PAIR
3
4
3 4
3
4
3
4
NUMpfR OF DATA POINTS
12
1'
12 1!
1J
13
13
13
TRUE C ON C tC> UG/l
114.0
1 ? 0. r
1 14.T 120.C
114.0
120.0
114 .0
120.0
i E A N RECOVERY Ik)
124.5
121.8
12C.2 13C.9
133.n
137.5
115.5
134,9
Ln
ACCURACY(XPEL ERROR >
9.2C
1 .46
5.42 9.eg
16.66
14.58
1.3C
12.38
NJ
OVFRAIL SIT DEV (S)
9.1
U.3
22.3 12.9
27.r
17.f
12 .n
28.6
0 V f R A LI PEL STD DEV, X
7 .20
11.4fr
It.55 9.5J
20.3?
12.97
10.36
21.18
SINGLC SID DEV, CSR)
11
.2
ie.8
18
.2
21
.5
analyst PEL DEV, X
9.
ce
14.96
13.
42
1 7.
1 7
H I GH YOUDE N PAIR
5
6
5
6
5
6
5
6
NU'RFR Of DATA POINTS
14
1 3
12
13
13
1 ?
1 3
1 3
TNUE C0*4C (C) UG/L
4XC.0
432.0
48C.C
4 32 .C
4fcC.O
4 ? 2 . C
430. G
4 3 2 . C
IE AN RE COVE R Y (* >
43».0
36C.9
447.7
447.7
444 . }
417.6
461.9
4 01.0
AlCURACYlXREL F R R0P )
-8.75
-U .47
-6.72
3.64
-7.4?
-!. 3 2
-3.77
-7.17
OVERALL STD DEV (S)
115.4
*7.8
6C.fc
83.4
1 GO. 5
138.7
103.1
130.0
OVERALL PEL STD DFV, X
26.^5
24 . M
1 5.48
18.62
22.61
26.04
22. 31
32 .62
SINGLE SID DEV,
76.5
44.9
76
.4
7 V
.V
• NAL1ST Rt L DEV, X
19.16
1
:.?4
17.
73
18.
52
U A T I 9 LEGI.UD
\ - OISTJUFD WATFR
2 - TAP WATER
5 - SURFACE WATER
4 - ! HOIJS IR I AI F f I LtlF N T
-------
TABLE 7-24
f NV I ROM NT AL rONUORING AND SUPPORT LAPORATO
Office Of RESEARCH AND OTVflOP^EhT
iMVlHOlJKENlAL PROTECTION AGENCY
•• IF* K F T HOP fft. VAI10A1I0N STUDY - PURGFARIFS ••
STATISTICAL Su^APf FOP 1 ,1f2 ,2-TETP A C H L OR 0 F 1 M A N F ANALYSE? UY WATER TYPf
WATffil V M £ K 2 WATER! UT[? t
LOW YOU 0 F ^ P«IP
1
?
1
2
1 2
1
2
'JUMRFR OF 6 A T A POINIS
1 3
i?
1 !
12
1 ? 12
1 3
n
TRUE CONC CC) UG/l
is.:
1 ?.c
15.0
17.0
15.0 17.0
15.0
17.0
*EAN RECOVER Y ( * )
ia . i
1 <¦.?
15.*
15.7
17.1 16.8
1A . 7
1 4.ft
ACCURAfYltBtl ERROR)
8.*2
-1 .42
1 .95
-7.5C
15.2* -1.42
11.3!
-12.73
OVERALL S I 0 OCV
-------
TABLE 7-25
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE 01 RESEARCH AMD DEVELOPMENT
F N V IRONH t N T A L PROTEE1ION AGFNCY
•• tPA 'EThOD 624 VALIDATION STUD* - PUR&EAbLfcS •«
STATISTICAL SUMMARY TOR I,?-0ICHL0ROBEN7ENE/1,*-DICHL0 A N A | T S F 5 Rt UATfR TYPE
WATER 1 WATER 2 WATER 3 WATER 4
LOW VOUDFU PAI»
1
?
1
2
1
?
1
2
NU'^n E R OF DATA POINTS
10
11
9
9
10
10
11
11
TPUF C ON f (C) UG/l
16.0
16.3
16.0
16. 3
16.0
16.3
16.0
16.5
ML AN RECOVERY <*>
If.9
21. 5
2C.8
20.1
2?.5
?2.6
21.3
19.6
ACCU'ACVUPEL ERROR)
IP ~ CO
25.71
30.C7
23.52
40.56
38.90
33.35
19.99
0VFPA1L STD DFV
3.8
5.4
7.1
5.4
11.5
4.9
10.2
10.0
OVERALL RLL STD DEV, X
19.90
26.28
34.13
26.69
50.31
21.53
47.88
51.04
SINGLE STD D E V • UG/L
778.0
7*0.0
778.0
780.0
778.0
780.0
778 .0
78C.0
it A N RECOVERY (*)
781.8
718.6
721.1
8 ?5. 3
783.1
670.2
713 . 3
732 .7
ACCURAC T CXREl F R R OR>
0.49
- 7 . ft 7
-7.3?
5.81
0.65
-14.07
-8.3?
-6.07
OVIRAII SID DEV
-------
TARIFF. 7-26
ENVIRONMENTAL MONITORING AUD SUPPORT LABORATORY
OFflCt Of RESEARCH AND DEVELOPMENT
fNVl&ONf«FNTAL PROTECTION AGFNCV
•« EPA K|IHOe 624 VALIDATION S^UDY - PUKGCARLES «•
STATISTICAL SUM1APT *0« ? ~^"OICHLOPOE TMAWf ANALYSES *> Y WATER TYPE
WATER 1 WATER 2 WATER 3 WAft" 4
10U tOUDFN MA|®
1
2
1
2
1
2
1
2
VU**eFR Of DATA POINTS
11
14
12
12
14
1!
1 4
13
TRUE CONC UG/L
9.9
11.0
9.9
11.0
9,9
11.0
9.9
11.0
HAN Rf.COVfHT (JC)
1 ?. 9
M . 5
9. *
M. 5
11.4
11.5
9.2
11.5
AC CURACY URFl ERROR )
10.10
2 . P 6
-Z.t 7
4.P5
15.OP
4.90
-7.14
4.65
overall SID OEV (S)
1 .*
2.6
2.1
1.6
4.7
2.7
3.5
2.9
OVERALL Rfl SID DEV, X
11.63
23 .02
21.89
14.13
41 .1 *
23.48
37.59
25.26
SINGLE SID DEV,
IV.4
27.5
2 3.7
22.2
21.2
19,5
15.5
27.4
0 V f R A L L PEL STD D F V , *
16. 5P
2P . 3 5
19.PI
22.31
17.47
1P.16
15.99
27.75
SINGLE STD DEV. tSR)
2
2
. 7
26.1
1 7
.2
17.4
ANALYST RFL DEV, I
21
•
1 9
23.77
15.
09
16.61
HIGH YOUDFN PAJR
5
6
5
6
5
6
5
6
NU19 E R Of DATA POINIS
15
1 5
13
14
13
14
13
13
TRUE CONf CC) UG/L
44C.0
396.0
44C.0
396.0
440.0
396.0
440.0
396.0
rtAN RECOVERY (*)
46F.9
407.6
467.0
439.3
412.4
4C0. 1
440.1
419,1
AC CUPACrUREl ERROR)
6.5?
2.92
ft.U
1C.?5
-6.26
1. C 3
0.03
5 .82
OV {»'LL MD OEV IS)
1 C T . ?
6 4.1
4P.9
78.1
67.1
flP.2
67.2
R2 .6
OVERALL R £ I STD OEV, X
22.1?
15.73
1C.43
17.?0
16.2a
22.P4
15.26
19.70
SI'JGLf STD DFV, ISR)
<
.0
59.1
6?
. 5
53.0
ANALYST R t L DIV, *
13
.
<9
13.C5
15 .
39
12.33
WA7EP I fft NO
Y - DISTILLED WATER
2 - TAP wATfR
3 - SURfACl WATER
4 - 1NOHSTRIAL FffLUENT
-------
TABLE 7-2 7
i NV I HON"! I * T*L MONITORING UND SUPPORT LABORATORY
office or research and DEVFior*ENi
FNVI®ONKENTAL PROTECTION AGFNCY
•• {PA MFIHOO 624 VALIDATION STUDY - FIJRGfAhlES *•
STATISTIC*! SUK«ARY ION 1 , 2-D1CHLOROPR0PAMF ANAIYSFS BY WATER 1 Y F F
WAT£fi 1 WATER 2 WATER 3 WATER 4
LOW YOUOFN PAIR
1
2
1
2
1
2
1
2
NUMBER 01 OATA POINTS
1 ?
12
1?
13
13
1?
12
12
TRUE CONC 11 0 1 U-i YOUDtN PAIR
3
4
J
4
3
4
3
4
MUlOEft OF DATA POINTS
12
11
13
13
1 3
1 3
1 1
14
TRUf CCNC UG/L
u;.r
15C.0
142.0
150.0
142.0
15 0.0
H2.0
150.0
1E A N RECOVERY <*)
Z 0 3.5
181.7
18 4.1
186.3
189.1
202.6
176.0
218.5
ACCURACY(IR'L ERROR>
4 3.34
21.15
29.65
24.19
33.16
35.°6
? S.92
45.65
OVERALL STD 01V
30.6
19.6
4c.:
u.e
29.7
27.4
16.9
57.4
overall rel std oev, x
15.14
1C.8C
21.73
10.09
15.6°
13.53
9.62
26.28
SINGLE STO DFV,
-------
TABLE 7-28
ENVIRONMENTAL MONITORING *ND SUPPORT LAPORATORY
OFFICE OF RESEARCH AN 0 DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
•• EPA METHOD 62* VALIDATION STUDT - PURGEAOIES ••
STATISTICAL SUMMARY FOR 1t3-OJCHLORORENZENE ANALTSES HT WATER ITPE
WATER 1 WATER 2 WATER 3 WATER 4
LOW TOUDFN PA|N
1
2
1
Z
1
2
1
2
NU^OER OF DATA POINTS
8
9
9
10
9
11
1 1
11
TRUE CONC (C) Ur»/L
P.0
7.2
8.0
7.2
8.0
7.2
8.0
7.2
1C.0
9. 5
10.2
12. t
10.3
10.2
11.4
8.1
ACCURACYUREl FRROR)
24.53
32.41
27.36
74.44
28.89
4 1.41
42.05
12.25
OVE R «l 1 S Tt> DF V < S >
0.4
1.6
2 . B
8.3
4.1
2.7
4.9
2.6
overall rel std DEV, t
3.52
16.36
27.57
66.17
39.72
26.26
43.11
32.59
SINGLE $ T f> B'V, CSR)
0
.9
5
.9
3.0
3
.5
analyst rfl dfv, X
9.
CA
51.
f 7
29.52
. i
O I
»•*> i
4C
1EPIU"* YOUDCN PAIR
3
4
3
4
3
4
3
4
*IIKBFR OF DATA POINTS
9
9
1G
10
11
11
10
9
TRUE CONC UC/L
120.0
114.0
120.0
114.C
12C ,n
114.0
120.0
114.0
•*E AN RECOVERY ( * )
12f .1
124.0
127.3
121.8
145.5
127.6
124.2
123.3
ACCURACY 11F E L ERROR)
6.7?
8.76
6.07
6.80
21.27
11.89
3.50
8.16
overall std dev <$>
13.1
28.6
3C.6
36.3
17.2
19.8
13.8
17.1
OVFRAll REl $10 DEV, T
10.26
23.C5
2 4 .04
29.79
11.84
15.49
11.11
13.90
single sto rtv, <$*>
17
. 5
38
.9
17.8
13
.3
ANALYST PEL DEV, I
13.
88
31.
22
13.01
10.
73
HIGH YOUDEN PAIR
5
6
5
6
5
6
5
6
NUMBER OF DATA POINTS
10
10
9
1C
11
IP
10
11
TRUE CONC UG/L
4 32 . P
4*0.0
4!2.3
480.0
4 3 2 .0
480.0
432.0
480.0
MAN RECOVERY (X)
451.1
526.C
36 2 .3
560.2
462.0
491.9
4C4 .8
517.8
ACCUQACYIlREL ERROR)
4.4?
9.59
-11.50
16.72
11.59
2.49
-6.29
7.P7
OVERALL STD DEV (S)
109.2
78.5
69.9
132.4
139.6
51.6
59.6
141.0
overall pel stc dcv, z
24.21
14 .93
ie.29
23.63
28.97
10.48
14.72
27.22
S | NGIF S T D DF V , 1 SR >
66
.5
81
. 7
91.2
ICO
.3
ANALYST REl DEV, X
13.
62
17.
33
18.73
21.
75
WATER LEGEND
1 - DfSHLlfD HATER
2 - TAP WATER
3 - SURF A C E WATF R
4 - IN0UST9IAL CFFlUENT
-------
REGRESSION ANALYSIS OF BASIC STATISTICS
Systematic relationships can exist between the mean recovery sta-
tistics and the prepared concentration levels across ampuls„ and
between the precision statistics and the mean recovery statistics.
Given a plot of precision values versus concentration levels, a
smooth curve drawn through the points can show that the precision
is found to: (1) be constant and not vary with level; (2) vary
directly with level in a linear manner; or (3) vary with level in
a curvilinear fashion.
In order to derive statements for method accuracy and precision,
the basic statistics were regressed assuming linear relationships,
fitting the data to a line using weighted least-squares. The
weights were chosen to be inversely related to the prepared con-
centration in the case of accuracy and inversely related to the
mean recovery in the case of precision. The inverse weightings
were employed to minimize skewing created by the high Youden-pair
data. The results of the regression analyses are discussed below.
Statements of Method Accuracy
The accuracy of Method 624 for each compound is characterized by
comparing the mean recovery of the analyte, X, to the prepared
concentration level of the compound, C, in the ampule. The IMVS
program conducts these calculations via matrix algebra, where
weighted least-squares linear regression of X versus C is con-
ducted with weights chosen to be inversely related to the square
of the true concentration levels (see Page 108 of Reference 2
for details). This method is equivalent to that suggested by
Britton [7] where the linear regression for X versus C is achieved
by using the customary least-squares algorithm to fit:
(3)
58
-------
which can then be converted to the desired relationships by mul-
tiplying through by C, giving:
These equations were presented in Table 1 in Section 2 of the
report.
If the intercept (b) associated with the fitted line is negligible
(i.e., essentially zero), then the slope (a) provides a unique
value which represents the percent recovery over all of the con-
centration levels.
Statements of Method Precision
The precision of Method 624 for each compound is characterized by
comparing the overall and single-analyst standard deviations to
the mean recovery, X. The IMVS program conducts these calcula-
tions via matrix algebra, where a weighted least-squares linear
regression of S and Sr versus X is conducted with weights chosen
to be inversely proportional to the square of the mean recovery
(see Page 108 of Reference 2, for details). This method is equiva-
lent to that suggested by Britton [7] where the linear regressions
for S and S^. versus C are achieved by using the customary least-
squares procedure to fit the equations
In this study, however, the regression was conducted versus X as
follows:
X = aC + b
(9)
(10)
(11)
59
-------
which is then converted by multiplying through by X to yield the
linear relationships
S = aX + b (12)
and
Sr = cX + d (13)
These equations were also presented earlier in Table 1 (Section
2).
If the intercepts, b and d, are negligible, then the slopes, a
and c, are estimates of the overall and RSD-SA deviations respect-
ively. These in turn, are measures of the method precision.
COMPARISON OF ACCURACY AND PRECISION ACROSS WATER TYPES
It is possible that the accuracy and precision values of Method
624 depend upon the type of water being analyzed. The summary
statistics X, S, and Sr are calculated separately for each con-
centration level within each water type. They can be compared
across water types in order to obtain information about the ef-
fects of water type on accuracy and precision. However, the use
of these summary statistics in this manner has several disadvan-
tages. First, it is cumbersome because there are 24 mean recov-
ery statistics (X) (6 ampules x 4 waters), 24 precision statistics
(S), and 12 precision statistics ($r) calculated for each compound.
Comparison of these statistics across concentration levels and
across water types becomes unwieldy. Second, the statistical
properties of this type of comparison procedure are difficult to
determine. Finally, due to variation associated with X, S, and
60
-------
Sr, comparisons based on these statistics can lead'to inconsis-
tent conclusions about the effect of water type. For example,
distilled water may produce a significantly lower value than
drinking water for the precision statistic S at a high concen-
tration, but a significantly higher value for S at a low concen-
tration.
An alternative approach, described in detail in Reference 2, has
been developed to test for the effects of water type. This al-
ternative approach is based on the concept of summarizing the
average effect of water type across concentration levels rather
than studying the local effects at each concentration levels If
significant differences are established by this alternative tech-
nique, then the summary statistics can be used for further local
analysis.
Thus, in order to check for the effect of water type on the ana-
lytical results, first a global F-test of the accuracy and pre-
cision is calculated. If the global F-test shows no water type
effects, no further calculations are required. If the F-test
shows significance of water type, calculations are performed to
determine if the individual differences are statistically signi-
ficant by calculating a confidence interval for the difference
between water type. A statistical significance is established
if at least one of the confidence intervals for the differences
does not include zero.
The global F-test for the effect of water type is calculated using
the following statistical model. If denotes the measurement
reported by laboratory i, for water type j, and ampul k, then
xijk - 6j • ckv3 • li • Eijk
61
-------
where i = 1,2, . . . , 15
j - 1.2
k = 1,2, . . . ,6
Model components 0^ and are fixed parameters that determine
the effect of water type j on the behavior of the observed mea-
surements (X. .i ). The parameter CT is the prepared concentration
2.1 iC rC
level associated with ampule k. The model component is a ran-
dom factor which accounts for the systematic error associated
with laboratory i. The model component Is the random factor
that accounts for the within-laboratory error.
The model is designed to approximate the global behavior of the
data. The multiplicative structure was chosen because of two
important properties. First, it allows for a possible curvilinear
relationship between the data and the true concentration
level (C^) through the use of the exponent Yj °n C^. This makes
the model more flexible in the data and the concentration level
C^. in this model. This property is important because it is typi-
cal of interlaboratory data collected under conditions where the
true concentration levels vary widely.
Accuracy is related directly to the mean recovery or expected
value of the measurements (X..
ij
data modeled by Equation 14 is
value of the measurements . The expected value for the
E • 3j • ck'3 • e
Precision is related to the variability in the measurements (X^^)
The variance of the data modeled by Equation 14 is
Var(X.Jk) > ^ • Cjjjv.rai ¦ cijk> , (16)
62
-------
which is an increasing function of C^. (See Reference 2 for a
complete discussion of this model.)
The accuracy and precision of Method 624 depend upon water type
through Equations 15 and 16 and the parameters 8^ and y^ . If the
and y^ vary with j (i.e., vary across water type), then the
accuracy and precision of the method also vary across water type.
To determine if these parameters do vary across water type and to
compare their values, they must be estimated from the laboratory
data using regression techniques. Equation 14 represents the basic
model. However, taking natural logarithms of both sides of Equa-
tion 14, the following straight line regression model is obtained.
in X. = in 3. + y. in CL + in L. + in £... (17)
ijk j j k l ijk v y
The parameter in g. is the intercept, and v. is the sloDe of the
J J *
regression line associated with water type j. It is assumed that
in L. is normally distributed with mean 0 and variance a, *, that
1. Li
in £..n is normally distributed with mean 0 and variance a 2, and
ijk J e
that the in L. and in terms are independent.
l ijk r
Based on Equation 17, the comparison of water types reduces to the
comparison of straight lines. Distilled water is viewed as a con-
trol, and each of the remaining lines is compared directly to the
line for distilled water.
Using the data on the log-log scale and regression techniques, the
parameter in 3^ (and hence Bj) and y^ can be estimated. These es-
timates are then used to formally test the null (no water type ef-
fect) versus alternative (water type effect) hypotheses
• Hq: in Sj - in 6^ = 0 and y^ - y^ = 0 for j = 2 (18)
63
-------
versus
H^: In £j - In 3^ ^ 0 and/or y - y^ i- 0 for some j = 2 (19)
The null hypothesis (Hq) is tested against the alternative hy-
pothesis (Ha) using an F-statistic. The probability of obtaining
the value of an F-statistic as large as the value which was ac-
tually observed, Prob(F > F OBS), is calculated under the assump-
tion that Hq is true. HQ is rejected in favor of if Prob(F > F
OBS) is less than 0.05, showing a possible effect due to water
type.
If Hq is not rejected, then there is no evidence in the data that
the 3. vary with j or that the y. vary with j. Therefore, there
J J
is no evidence of an effect due to water type on the accuracy or
precision of the method. If Hq is rejected, then some linear
combination of the differences (in 3. - in 6) and (y. -y,) is
J J
statistically different from zero. However, this does not guar-
antee there will be a statistically significant direct effect
attributable to any specific water type since the overall F test
can be overly sensitive to minor systematic effects common to
several water types. The effect due to a specific water type is
judged to be statistically significant only if one of the dif-
ferences (£n £ - in 3^) and/or (y - y^) , is statistically dif-
ferent from zero. This is determined by checking the simultaneous
95% confidence intervals which are constructed for each of these
differences. Each true difference can be stated to lie within
its respective confidence interval with 957c confidence. If zero
is contained within the confindence interval, then there is no
evidence that the corresponding difference is significantly dif-
ferent from zero and no further calculations are required.
64
-------
If at least one of the confidence intervals for the differences
(in 3. - In £_) or (y . - v ) fails to include zero, then the
j 1 j 1
statistical significance of the effect due to water type has
been established. Even if a statistically significant effect
due to water type were to be established, that would not neces-
sarily mean that the effect would be of practical importance.
Practical importance is related to the size and interpretation
of the differences. The computer generated data for the point
estimates, analysis of variance, and confidence intervals are
shown in Tables 8-1 through 8-28 for each compound.
The comparison of accuracy and precision across water types just
discussed is based on the assumption that Equation 14 approxi-
mately models the data. It is clear that in practical monitoring
programs of this type such models cannot model the data completely
in every case. This analysis therefore is viewed as a screening
procedure which identified those cases where differences in water
types are likely to be present. A more detailed local analysis
can then be pursued using the basic summary statistics for pre-
cision and accuracy.
65
-------
TABLE 8-1
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OM1CE or RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
•• CPA MET HOC 624 VALUATION STUOY - PURGE A 8L E S •«
EIFECT Of k»HI TYPE ON UEN7INC ANALYSIS
POINT ESTIMATES ••
DISTILLED y A1 E N SL OPE : 6 AMM A C I ) > .927^6
WATER INTERCEPUwAUR-DISTILLED) SLOPE(WATER-D)STILLED)
2 -.0764. .0217
3 -.0257 .0045
4 -.0903 .0107
SOURCE
•• ANALYSIS Of VARIANCE '*
01 SUM OF SQUARES MEAN SQUARE
o>
cr>
REb
-------
TABLE 8-2
tNVIRONHtNlAl MONITORING AND SUPPORT LAPORATOBl
OMICE Of RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
• • EPA Hi 1 HOD 624 VALI 0 A 11 ON STUDY - PURGLABLES *•
flHCI CI WAUfi 11PE ON BROMODlCHLOROMElHANE ANALYSIS
•• POINT ESTIMATES ••
DISTILLED WATER SI OPE : G AAA A C 1 ) «= 1.07709
WATER lNIEHCEPHWATER-OlSTILLED) SLOPE(WATER-DISTILLED*
2 .379* -.0607
3 .1339 -.0281
4 .0850 -*0263
SOURCE
ANALYSIS Of VARIANCE ••
Df SUM Of SQUARES MEAN SQUARE
-•J
R(G 1 1006.25185 1006.25185
REGIUATFR/DISTULED) 6 1.41103 .23517
ERROR 314 38.81922 .12363
PAOB
1.90 .C800
10TAL
321 1046.46210
»• TABLE Of 95X CONflDENCl INTERVALS EOR THE DlfHRCNCES BETWEEN INTERCEPTS ANO THE DlffEKENCES BETWEEN SLOPES ••
WATER
INTERCEPT(WATER-DISTILLED)
estimate INTERVAL
SLOPE(WATER-DISTI&LED)
ESTIMATE INTERVAL
.3794
.1339
.0950
-.0311 ,
-.2625 .
-.3225 .
•7899) -.0607 ( -.1461 • .C26fi>
•5303) -.0261 ( -.1130 , .C56B)
.4924) -.0283 I -.1156 . .0590)
NOTE: II ZERO IS CONTAINED WITHIN A GIVEN C0NI1DENCE INTERVAL INEN THERE IS NO STATISTICAL SIGN1I1CANCE BETWEEN
DISTILLED WATER AND THE CORRESPONDING WASTE WATER fOR THE ASSOCIATED PARAM£T£R(IN1ERCEPT/SLOPE>.
iHfc SlOPE ANO INTERCEPT ESTIMATES E ROM THIS ANALYSIS ARE NOT THE SAME AS IhOSE OBTAINED f ROM THE PRECISION
AND ACCURACY REGRESSIONS PEMOBMED EARLIER.
-------
TABLE 8-3
tNVlHGfctfNIAt MONITORING AND SUPPORT LAbORATORV
OMICl Of RtStARCH AN 0 DEVELOPMENT
L h VI RONM L N I A L PROTECTION AGENCY
•• EPA HE 1 HOD 624 VALIDATION STUOV - PURGEABLtS ••
IM{(1 Of WATfR T VP E ON fiROMOTORM ANALYSIS
•• POINT ESTIMATES ••
DISTILLED W A11 R SLOPE :GA*NA<1> * 1.06375
WA1ER INTERCEPT (UATER'OlSTlLLfD) Si OPE CwATCR-DISTILLED)
2 .00 SO .0135
5 -.0023 -.0107
4 -.2433 .0279
SOURCE
• • ANALVSIS OF VARIANCE ••
or sum or squares mean square
00
REG(OIStUlfb) 1 85*.28306 B5B.2*306
REG
ESTIMATE INTERVAL
•0030 < -.5456 , .5515) .0135 ( -.1C64 , .1334)
-.002 3 ( -.5380 , .5333) -.0107 I -.12B5 , .U72)
-•2403 I - .7640 , .2874) .0279 < -.0699 , .1456)
NOTE: If HRO IS CONTAINED yiTHIN A LIVEN CONMOENCE INTERVAL THEN THtRE IS NO STATISTICAL SlGNlEICANCt BETWEEN
0 I SI 111 E D WATER ANO THE CORRESPONDING WASTE WATER fOR 1HE ASSOCIATED PARAMETERSINTCRCEPTJSLOPE).
THE SLOPE AND INTERCEPT ESTIMATES IRON THIS ANALVSIS ARE NOT THE SAME AS THOSE OBTAINED EROM THE PRECISION
AND ACCURACY REGRESSIONS PtfrORMEP EARLIER.
-------
TABLE 8-4
(NVJfiON'UNlAl nONlTOUNG AND SUPPOfcT LABORATORY
Office or RESEARCH AND DEVELOPMENT
tNV I RON*(NlAi PRO I £ C1)ON AGENCY
•• EPA KETMOD 624 VALIDATION STUDl - PURGEAbLES ••
EFFECT Of WATFR TtPE ON 6RCN0MTHAhE ANALYSIS
•• POINT ESTIMATES
DISTILLED MATER SLOPE:G ANR A II) = 1.0499*
WATER INTERCEPT (WATER-D1ST 111 16) SLOPE
2 -.2355 *0300
3 .owe -.cm*
4 .0616 -.0001
•• ANALYSIS Of VARIANCE ••
SOURCE
DF
SUM 01 SQUARES MEAN SQUARE
PkOB
On
REGfOlSTllLEO) 1 906.54495 906.54495
REG4WA1ER/DISMILED) 6 .61162 .135)0
ERROR 270 31.24459 .11572
1.17 .3230
TOTAL
277
940.6L136
•« TABIC Of 951 COhfloENCE INTERVALS FOR THE DIFFERENCES BETWEEN INTERCEPTS AND THE DIFFERENCES BETWEEN SLOPES ••
WATE R
2
3
4
INTERCEPT(MATER-D1STliLED)
estimate interval
-.2355
.04 70
.1616
-.6731
-.3764
-.3711
.2021)
.4724 >
.49*2)
SLOPE(wATER-blSTIltED)
E ST I MA 11 1N1ERVAL
.0300 I -.0592 , .1192)
-.0154 I 1C27 , .0/20)
-.0061 < -.0962 . .0801)
NOTE: IF JE RO IS CONTAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE BETWEEN
OlSllllEO WATER AND THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PAftANETERCINTE*CEP1/SL0P|).
THE SLOPE AND INTERCEPT ESTIMATES F RON THIS ANALYSIS ARE NOT THE SAME AS THOSE OBTAINED fROM IHfc PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLiS 8-5
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
Office OF RESEARCH AND DEVELOPMENT
ENVIMONMENIAL PROTECTION AGENCY
•• CPA METHOD 624 VALIDATION STUDY - PURGLAOLES ••
EffECT Of WATER TYPE ON CARBON TETRACHLORIDE ANALYSIS
•• POINT ESTIMATES ••
DISTILLED WATER SLOPE :GA*AA(1) « 1.0346?
WATER INTERCEPT(WATEft-DtSTlLL(O) SLOPCEWATER-DISTILLED)
2 -.C826 .0204
3 .0688 -.UU«
4 -.04C8 -.00U4
SOURCE
•• ANALYSIS Of VARIANCE •*
0F SUM Of SQUARES MEAN SQUARE
PROS
-J
o
REGfDISTIlLEO) T 734.19919 7)4.19919
REG t .28468 .0474$
ERROR 275 18.60434 .0676$
•70 .6488
total
282
733 .Cb822
TABLE Of 951 CONflDENCE INTERVALS FOR THE DlffERENCES BETWEEN INTERCEPTS ANO IHE DlffERENCES BETWEEN SLOPES *•
WATER
2
3
4
INTERCEPT
ESTIMATE INTERVAL
-.C826
• 0888
-•0408
I -.44C4
C -.2487
C -.3790
SLOPE (WATER-O I STULED)
ESTIMATE INTERVAL
2752) .0204 ( -.0579 , .0987)
42621 -.0139 I -.C9C3 , .05*6)
.2975) -.0004 ( -.0733 , .0746)
NOTE: If f E RO IS CONTAINED WITHIN A GIVEN CONflDENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE BETWEEN
DISTILLED WATER AND THE CORRESPONDING WASTE WATFR EOR THE ASSOCIATED PARAMETERC I NTERCEPT/SLOPE I .
THE SLOPE AND INTERCEPT ESTIMATES fROP" THIS ANALYSIS ARE NOT IHE SAME AS THOSE OBTAINED IRON THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 8-6
t N V 1 H CNM fc NI»t MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
t N V1 fi ONME N f A L PROTECTION AGENCY
EPA METHOD 624 VAL1 DA 11 ON STUDY - PUHGEABLfcS ••
EFFECT OF WATER TYPE OK C HL OR OB E N IE NE ANALTS I S
•• POINT ESTIMATES ••
DISTUUD WATER S LOPE ; GAMMA 11) = .91776
WATFR IhTER(EPMUATER-DISTlLlED) SI OP I C y A 1 i R-D 1 S T IL L 1 0 )
2 -.1135 .0207
3 .1136 -.0231
4 -.CAR) -.0086
SOURCE
•• ANALYSIS Of VARIANCE ••
or sun or souarfs mean square
REC 1 661.80 227 661.80227
RlG 6 .66305 .11051
ERROR 305 18.3967* .0603?
1.03
PROB
092$
TOTAL
312
680.66210
TABLE OF 951 CONFIDENCE INTERVALS FOR THE D I H t Rt NCt S BETWEEN INTfcRCtPIS AND THE DIFFERENCES BETWEEN SLOPES
MATE R
INTERCEPTIVA1ER-D1ST ILLSD)
ESTIMATE INTERVAL.
SLOPE
4
-.0481
(
-.3653 ,
.2691)
-.0086
1
-.0734 ,
.0562)
NOTE: IF 7 E 8 0 IS CONTAINED W ) 1H IN A GIVEN CONFIDENCE INTERVAL THEN THCftF IS NO STATISTICAL SIGNIFICANCE BETWEEN
CISULLED MATER ANO THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PAfiAMETERCJNtERCEPT/SLOPE).
THE SLOPE AND INTERCEPT ESTIMATES FROM THIS ANALYSIS ARE N01 THE SA*E AS THOSE OBTAINEO FROM THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 8-7
tNVl*GN"lNlAt MONITORING AND SUPPORT LACORATORY
office or research iNC development
tNVlRONMENTAL PROTECTION AGENCY
•• (PA HElHOt) 624 VAI I0AT1ON STUDY - PURGEAHLES ••
(IH(1 Of UAlEd TYPE ON CHI 0 ROE T HA Nf ANALYSIS
•• POINT ESTIMATES •»
DISTILLED wMifl S L OPE: 0 AM* A I 1 > = .96084
NATCR |NT£RCCPUwaTER-DISTILLED) SlOPE AR AM E 1ER < I N1 t R C E ¥ I / SL OPE ) .
THE SLOPE AND 1N1ERCCPT ESTIMATES (ROM THIS ANALYSIS ARE NOT THE SAME AS THOSE OUTA1NED ISO* THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 8-8
ENVIRCNMCNTAL MONITORING AND SUPPORT LABORATORY
Officr OF RESEARCH AND DEVELOPMENT
I N VI R ONM E M IA L. PROTECTION AGENCY
• • (PA HF1 HOD <24 VAI1DAT10N STUOY - PUR 6E ABL E S ••
EflECT 01 WATER I YPE Oh C HL 0 H Of ORM ANALYSIS
•• POINT ESTIMATES ••
DISTILLED WATER Si OP E : C ANN k C 1 J = .911507
VATEft INTERCEPTCUATrR-DJSTIllED) SLOPE CwATER-DI ST lLLED)
2 .4 990 -.1192
3 .0588 -.0223
4 -.0637 .0089
•• ANALYSIS Of VARIANCE
SOURCE
Df
SUM Oi SQUARES HI AN SQUARE
PROB
LO
REtfDISTULED) 1 750.33668 750.33668
REGfWATER/DlSTILLED) 6 ?.08399 .34733
ERROR 274 3$•64235 .13091
2.66 .0161
TOIAl
281
788.26302
•• TABLE Of 95* CONFIDENCE INTERVALS FOR THE DIFFERENCES fcClwCCN INTERCEPTS ANO THE DIFFERENCES BETWEEN SLOPES •
WATER
INTERCEPT!WATER-DISTILLED)
tSllMAU INTERVAL
SLOPE(WATER-DISTILLED)
ESTIMATE IN 1 E RVAL
.(.990 I «C915
.0586 I -.3243
-.0637 ( -.4577
.9065) -.1192 C -.2145 , -.C239)
•4418) -.0223 C -.1126 , .C680)
.3100 .0089 ( -.0843 , .1022)
NOTE: IF 1CR0 IS CONTAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN ThFRE !S NO STATISTICAL SIGNIFICANCE BETWEEN
DISTILLED WATER AND THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PARAMETER!INTERCEPT/SLOPE)•
THE 5>L0Pt AND IhlfcRCEPT ESTIMATES f ROM 1HIS ANALYSIS ARE NOT THE SAME AS THOSt OBTAINED f ROM THE PRECISION
AND ACCURACY REGRESSIONS PERfORMED EARLIER.
-------
TABLE 8-9
ENV I fiONMtNTAl MONITORING AND SUPPORT lAHORATORV
o f r i c i or research ano development
ENVIRONMENTAL PROTECTION AGFNCY
•• (PA METHOD 624 VALIDATION STUOY - PURGEAULlS ••
unci Of WATER TYPE ON CHLOROMCTHANE ANALYSIS
•• POINT ESTIMATES ••
DlSTlLLEO WATER SLOPE :GAMMA<1) = .93207
WATE » INUKCfcPU WATER-0 1 STILLED) SLOPE(WAIEH-01 STILLED)
2 -.2344 .0279
3 -.3617 .1107
4 -.4168 .065 3
SOURCE
•• ANALYSIS Of VARIANCE ••
or sun or squares mean square
-P-
REG(OISTIILEO) 1 747.61220 747.61220
RE6CWATEH/01STILLED) 6 3.83932 .63989
ERROR 256 119.96H92 .46863
1.37
PROB
2289
TOTAL
263
871.42043
•• TABLE or 9SX CONflOENCt INTERVALS FOR THE DIFFERENCES BETWEEN INTERCEPTS AND THE DIFFERENCES BETWEEN SLOPES **
INTERCEPT(WATER-01STILLED)
WATER ESTIMATE INTERVAL
2 -.2344 ( -1.1101 9 .6414)
3 -.381? C -1.2259 , .4624)
4 -.4168 < -1.2727 , .4391)
SLOPE
-------
TABLE 8-10
fNVIRCNMEN1AL MONITORING AND SUPPORT LABORATORY
orri(( or research ano de velopnehi
ENVIRONMENTAL PROTECTION A6ENCY
• • EPA METHOD 624 WAi10 A TI ON STUDY - PURGEAbLES ••
tirco or water type on cIs-1»3-dichloroproplne analysis
•• POINT ESTIMATES •*
DISTILLED bATER SLOPE:6ANNA<11 • 1.00554
WATER INTERCEPTtWATER-OISTlLLED) SLOPE(wAT£R-DIST1LLEO>
2 -.0231 -•QC3 5
3 .1400 -.J 525
4 .0145 -.0052
SOURCE
•• ANALYSIS Or VARIANCE ••
Of SUN or SQUARES mean souarc
^4
u>
RE6(D1ST1LIED> 1 602.74124 602.74124
REGfWATER/DISTJLLEO 6 .52676 .06(13
ERROR 247 27.70625 .11217
PfiOb
.79 .sei9
TOTAL
254
630.97626
•• TA0LE Or 95X CONtlDENCC INTERVALS rOR THE DIMERENCtS UETWEEN INTERCEPTS AND TM( DIMCRCNCES bETwEtN SLOPES ••
WA TER
lNIERCEPTCWATER-DISULLED)
ESTIMATE INTERVAL
-.0231 < -.4003 . .4341)
.1400 C -.3133 , .59321
.0145 < -.4357 , .4646)
St OPE(UATER-DISTILLED)
ESTIMATE INTERVAL
* .0035 1 -.1071 . .icon
-.0525 ( -. 1555 . . C 5 0 4 )
-.0052 C -.1075 , .0971)
NOTl: If ZERO IS CONTAINED MllHJN A blVEN CONE1DENCE INTERVAL THEN THERE IS NO STATISTICAL S16NJI1CANCI BETUtEN
DISTlllfD WATER AND THE CORRESPONDING WASTE WATER I OR THE ASSOCIATED PARAMETER!INTERCEPT/SLOPE) .
THE SLOPE AND INTERCEPT ESTIMATES MOM THIS ANALYSIS ARE NOT THE SAME AS THOSE OttTAIhEO t ROM THE PRECISION
ANO ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 8-11
fcNVlRON*ENTAL KONIIOR1N& AND SUPPOM LAfeGAAIOHY
Office Of RESEARCH AND OEVELOP'ENT
ENVIRONMENTAL PROTECTION AGENCY
•• EPA METHOD 624 V A11 0 A 1 | Oft &1UOV - PUR 6E A&L E S ••
IffCCf Of WATER TYPE ON 0 IH fiOHOC ML 0fi OHETHANE ANALYSIS
•• POINT ESTIMATES ••
OIST1LLED WATER SLOPE:GAMMA<1) « 1.00749
WATER INHRCEPKWAUR-DISIILLED) SLOPE CWATER-DISTILLED)
2 -.1495 ,03S9
3 .0263 -•0056
A -.0350 ,0147
SOURCE
•• ANALYSIS Of VARIANCE ••
Of SUM Of SQUARES MEAN SQUARE
PRO0
RE6(01ST1LLED) 1 764.79784 784.7978*
REG
.0283 I -.2910 , .3477) -.0056 < -.G7fc0 , .06(7)
-.0350 < -.3664 . .2964) .0147 < -.0599 , .0893)
NOTE: If JERO IS CONTAINED WITHIN A 6IVEN CONflOENCE INTERVAL 1HEN THERE IS NO STATISTICAL SlGNlflCANCE BETWEEN
D1STIILFD WATER AND THE CORRESPONDING WASTE WATER fOR THE ASSOCIATED PAftAHITER<1NTfRCIPT/Si OPE).
THE SLOPE AND INTERCEPT ESTIMATES fROM THIS ANALYSIS ARE NOT THE SANE AS THOSE OBTAINED fRQP THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 8-12
LNVlkONMfcNIAL MONITORING AND SUPPORT LAf.QRAtOR*
0 f f 1 (t Of RESEARCH AND DfVELOPMfcNT
fc N V1 M ONML N I A L PROTECTION AGENCY
•• [PA ME THOD 6 24 VALIDATION STUDY - PURGEABLES
EffECT or WATER TYPE ON ETHYL RENffNE ANALYSIS
•• POIN? ESTIMATES
DISTILLED water SLOPE jCAMMAU) = .94978
WATER INTERCEPTIUATER-DISTILLED) SLOPKWATEA-DISHLLED)
2 .0465 -.0141
3 .1472 -.02*0
4 .1053 -.0 242
SIS OF VARIANCE ••
SOURCE D f
KEGCOISTHLCO) 1
REGfWATER/DIST111(D) 6
ERROR 296
SUM OE SQUARES MEAN SQUARE
645.55372
.19892
16.73581
645.5 53 72
.03315
.05654
PROO
.59 .7412
TOTAL
303
662.46845
•• TABLE Of 95X CONFIDENCE INTERVALS fOR THE DIFFERENCES BETWEEN INTERCEPTS ANO THE DIFFERENCES BETWEEN SLOPES •
WATER
2
3
4
INTERCEPT(WATIR-DISTlLLEb)
ESTIMATE INTERVAL
.C465
.14 72
.1053
I -.?S66 ,
^ -.1711 ,
C -.2221 ,
.1818)
.4654)
.4326)
SLOPttwAItR-DISTILLtD)
ESTIMATE INTERVAL
-.0141 ( -.G8C2 , .0520)
-.0
-------
TABLE 8-13
ENVIRONMENTAL MONITORING AND SUPPORT lAHORATORY
OMJCE OF PCSLARCH ANO DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
•• fcPA METHOD 624 VALIDATION STUDY - PURGEAULES ••
crrcci or water type on methylene chloride analysis
•• POINT ESTIMATES ••
DISTILLED WAUM SL OPE :6 AMr A < 1 ) » 1 .01535
WATER lNTERCCPMwATER-OISTlLLEO) SLOPECWAIEK-OIS'lLLlP)
2 .6109 -.1231
3 .7457 -.1381
4 .1730 -.0632
SOURCE
•• ANALYSIS Of VARIANCE ••
OF SUM or SQUARES MEAN SOUARC
PROH
00
REG(DISTILLEO) 1 714.95450 714.95450
REGfUAUR/OISTlLLEO) 6 4.01600 .60267
ERROR 273 89.38194 .32741
2.4 5
. 0 ? 5 2
TOTAL
280
809.15244
»• TABLE Of 95X CONFIDENCE INTERVALS EOR THE DIFFERENCES BETWEEN INTERCEPTS ANO THE 01FIFRENCES BETWEEN SLOPES
WATER
2
3
4
INTERCEPT!WATER-DISTILLED)
ESTIMATE INTERVAL
• 6189
.7457
.1730
-.0584
.0605
-.5451
1.2961>
U43C9)
.8912)
SLOPE (WATER'OISTILLEO)
ESTIMATE INTERVAL
-.1231 I -.2676 ( .0213)
-.1381 I -.2851 . .CCP9)
-.0632 < -.2140 . .0876)
NOTE: IF 2ER0 IS CONTAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE BETWEEN
DISTILLED WATER AND THE CORRESPONDING WASTE WATER (OR 1HE ASSOCIATED PARAMETER!INTERCEPT/SLOPE).
THE SLOPE AND INTERCEPT ESTIMATES (ROM THIS ANALYSIS ARE NOT THE SAME AS THOSE OBTAINED IROH THE PRECISION
ANO ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 8-14
t N V 1 N ONMENI A L HON 110 RING AND SUPPORT LABORATORY
01(1(1 or RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
•• EPA METHOD 624 VALIDATION STUDY - PURGE A01 £ S ••
EffECT OF WATER TYPE ON 1ETRACHL0R0ETHFNE ANALYSIS
• * POINT ESTIMATES ••
DISfllLFO UAIfR SLOPE : GAHHAC1> = .97206
WATER 1NIERCEPI ( W A11 REDISTILLED) SLOPE(WATER-OISlHLfD)
2 -.0720 -»uOU1
S .1168 -.0305
4 -.0222 -.0305
SOURCE
•• ANALYSIS Of VARIANCE •*
Df SUM Of SQUARES MEAN SQUARE
PROtt
vD
RCG 1 651.17994 651.17994
REGfWATER/DISTILLEO) 6 1.26)64 .21061
ERROR 266 14.10820 .04933
4.27 .0C04
TOTAL
293
666.55178
•• TABLE OF 95X CONFIDENCE INTERVALS FOR TNI D I fIE RE NCE S BtlWEEN INTERCEPTS AND I HE DIFFERENCES 0 E T WE EN SLOPES •*
WATER
2
3
I
INTERCEPT!WATER-DISTILLED)
ESTIMATE interval
-.0720
.use
-.0222
-.3681
-.1695
-.1105
.2242)
.4070 >
.2661 >
SLOPL(WAIER-DISTILLEO)
ESTIMATE INTERVAL
-.OJOI ( -.0647 , .06451
-.0303 i -.0934 t .03281
-.0305 < -.0935 , .0326)
NOTE: IF ZERO IS CONTAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE t)E TU EIN
DIS1ILLEO WATER AND IHE CORRESPONDING VASIE W A I ( R FOR IME ASSOCIATED PARAMETERI INTERCEP1/Si OPE>.
THE SLOPE AND INTERCEPT ESTIMATES FROM THIS ANALYSIS ARE NOT THE SAME AS THOSE OBTAINED FROM THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 8-15
CNVlNONHCNTAL KONITORING ANO SUPPORT LABORATORY
OFFICE 01 RESEARCH AND DEVELOPHENI
E N V1 RONME N T A L PROTECTION ACfNCV
•• EP4 Nil MOO 624 VALIDATION STUD* - PURttAbLES ••
EFFECT OF WATER |*PE ON IOLUINE ANALYSIS
•• POINT ESTIMATES ••
OISTILLFD wATfP SIOPE :GAHMAM) - .93734
WATER INTERCEPMWATER-D1ST1LLED) SLOPL(WATER-OISIILLEO)
2 -.Cilt .0066
3 .0049 .0020
4 -.P293 -.0043
ANALVSlS OF VARIANCE ••
SOURCE
OF
SUN or SQUARES MEAN SQUARE
PROD
CO
O
«tf G10ISTUIED) 1 626.04766 626.04766
RfG(WATER/DIST1LLED) 6 .19825 .03)04
ERROR 2 85 11.76791 .04129
.60 .5704
total
292
638.01382
•• TABLE 01 95X CONFIDENCE INTERVALS FOR THE DIFFERENCES BETWEEN INTERCEPTS ANO THE DIFFERENCES BETWEEN SLOPES ••
WATER
1NIERCEPT
-------
TABLE 8-16
E N V IR CNH EN T A t H0NI10RING AN 0 SUPPORT LABORATORY
offict or research and development
f N V I R ONM { N1 A l PROTECTION AGENCY
•• EPA Mil HOD 624 VALIDATION STUOY - PUROtABLCS ••
IMEO 01 WATER TYPE ON TRANS-1 ,2~DICHLOROE THENE ANALYSIS
POINT ESTIMATES ••
DISTILLED W'lER SLOPE :GANMA<1) ¦ .99629
UATER INURCEPT SlOPtfwATER-PISTULCD)
2 -.0891 *0279
J ,0C30 -.0018
4 -.0798 *010$
»• ANALYSIS Of VARIANCE ••
00
SOURCE DF
REGCDISTlLlED) 1
REGIWAVER/DISIILLID) 6
ERROR SOS
SUN Of SQUARES MEAN SQUARE
951.22893
.24B41
16*20177
951.22893
.04H0
•05112
PROfi
78 *5866
101 A L
312
967.67911
•• TABLE Of 9 5 X (ONIIOENCE INTERVALS ION THE DIFFERENCES BE IWtEN INTERCEPTS ANO THE DIFFERENCES BETWEEN SLOPES ••
UATER
INURCEPTCbAHR-DISTlLLED)
ESTIMATE INTERVAL
SLOPE(yA1ER-PlSTILLED>
ESTIMATE INTERVAL
-.0891 C -.3254 , . 14 73 >
.0030 < -.2241 . .2302)
-.0786 ( -.3153 , .1576)
•0279 < -.0282 , .0640)
•0018 < -»G558 • .0523)
.0105 C -.0456 . .0666)
NOtt: II 7E.N0 IS CONIAINLO WITHIN A GIVEN CONFIDENCE INTIRVAL IHEN THERE IS NO SIATtSUCAL SIGNIFICANCE BETWEEN
DISTILLED WATER ANO THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PAftAH£TER<1NTERCEPT/SLOPE)•
THE SLOPE AND INTERCEPT ESTIMATES FROM THIS ANALYSIS ARE NOT THE SAME AS THOSE OBTAINED FROM THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EAHL1EN.
-------
TABLE 8-17
ENVlkOKMENIAL N0NI10HIN6 AND SUPPORT IAOORAIORV
OMICE 01 RESEARCH ANO DEVELOPMENT
E N VI HON*I N I A L PROTECTION AGENCY
•• (PA METHOD 624 VAlJOATlON STUDY - PURGEABLES ••
EMECT OF WATER TYPE ON TRANS-1 ,3-61CML OROPROPE hi ANALYSIS
•• POINT ESTIMATES ••
DISTILLED WATER SLOPE:GAHMA<1 ) = .96667
WA 11 ft INTERCEPT tUAlE R-D1SMLLED) SIOPEIWATER-DISTILLED)
2 -.1816 .0430
. J .0*00 .0011
4 -.06VS .0251
SOURCE
•' ANAL TSI S Of VARIANCE »•
or sum or squares mean square
oo
ro
REGCDISULLEO) 1 634.36306 634.36306
REGCWATfR/DISTILLtD) 6 .39463 .06577
ERROR 260 12.97447 .0499C
PROS
1.32 .2493
T01AL
267
647.73216
•• I ABIE or 951 COkllDENCE INTERVALS fOR THE OIFEERENCES BETWEEN INTERCEPTS ANO THE DIMERENCES BETWEEN SLOPES ••
WATER
1NTERCEPT
ESTIMATE 1NIIRVAL
-.1616
.0600
-.0695
.4/80
.2447
.3666
•1147)
.3648)
.2276)
SLOPE (WATER-DISTILLED)
ESTIMATE INTERVAL
.0430 I -.0215 , • 1C 76)
.0011 I -.C654 , .0675)
.0251 < -.0399 t .09C2)
NOTE
If iERO )S CONTAINEO WIThIN A GIVEN (0NE1DENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE BETWEEN
DISTILLED UATER AND THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PARARETtRC I N1ERCEPI/SLOPf).
THE SLOPE AND INTER CEP1 ESTIMATES fPO" THIS ANALYSIS ARE NOT THE SAME AS THOSE OtlTMNEO FROM THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABI.E 8-18
INWlRONMfNTAl MONITORING AND SUPPORT LABORATORY
Of* 1 C I 01 HtStANCH AND DEVELOPMENT
ENVIROnNEMAL PROTECTION AGENCY
•• EPA METHOD 62* VALIDATION STUDY - PURGEAQLES ••
EFFECT OF WATER TYPE ON TR1CHLOROETHENC ANALYSIS
•• POINT ESTIMATES •*
DISTILLED WATER SLOPE: G AMMA II) - .91194
MATER INTERCEPTlUATLR-DISTILLED) SLOPE
i -.1326 •0219
3 .059? -.0180
4 -.16*5 .0219
SOURCE
•• ANALYSIS OF VARIANCE ••
DF SUM OF SQUARE $ MEAN SQUARE
00
u>
RE£<01ST|LLED) 1 720.51055 720.310S5
RE6.
THE SLOPE AND UTEBCEPT ESTIMATES fftOP THIS ANALYSIS ARE NOT THE SAME AS THOSE OBTAINED FROM THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EAHLIER.
-------
TABLE 8-19
INVIHONfHNtAl MONITORING AND SUPPORT LABORATORY
ornct of research and devflopmini
ENVIRONMENTAL PROTECTION AGENCl
•• EPA METHOD 624 VALIDATION STUD* - PUR G E ABL £ 5 ••
EFFECT 01 MATER 1YPE ON T«ICMLOROFLUOROMETMANt ANALYSIS
•• POINT ESTIMATES ••
DISTILLED WATER SLOPE :GAMMAll) = .96739
WATER INIERCEPTIWAIER-DISTILLED) SLOPE fWAIEft-DISTILLED)
2 -.0626 .0253
3 -.0725 -.1)065
4 -.0578 .0262
SOURCE
ANALYSIS Of VARIANCE ••
Of SUM Of SQUARES MEAN SQUARE
oo
RE6<0IST1LLE0) 1 717.92254 717.92254
fiECIwAIFR/DISTULED) 6 1.33155 .22192
ERROR 241 25.19791 .10456
F PROti
2.12 .0515
TOTAL
248
744.45200
•• TABLE Of 951 CONFIDENCE INTERVALS FOR I ME DIFFERENCES BETWEEN INTERCEPTS AND THE 01FFERFNCES BETWEEN SLOPES *•
WATER
2
3
4
INTERCEPTUAIIR-O I STILLED)
ESTIMATE INTERVAL
-.0626
-.0725
-.0378
< -.4795
I -.4804
( -.4458
.3542)
.3355)
.3701)
SLOPE
-------
TABLE 8-20
INVIRCN*ENTAl RON I 1 OR IN& AND SUPPORT LAUORATOftV
0II1CI Of RESEARCH AMD DEVELOPMtNl
ENVIRONMENTAL PROTECTION AfeEhCf
•• EPA METHOD 624 VALIDATION STUDY - PUR(,EABLES ••
KMfcCI Of WATER TYPE ON 1 , I-1I CHL OR 01 I H ANfc ANALYSIS
•• POINT 6 STlMATfS ••
DISTILLED WATER SLOPE: GAMMA(1 I = .98581
WATER INTERCEP1tWATER-0!ST 111 (0> SLOPECuATfcK-OISTILLEO)
2 -.1156 .025?
3 .03C9 -•D093
A -.08*1 .0189
•• ANALYSIS Of VARIANCE ••
00
Ui
SOURC( Df
rec(distilled> 1
REG
-------
TABLE 8-21
ENU1R0NMENTAI MONITORINb AND SUPPORT LABORATORY
0(11(1 or fit St AS(M AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
•• EPA HE 1 HOD 62* VALIDATION STUDY - PURGEAbLES •*
frrccT or water type on i«i-dichloroethene analysis
•• POINT ESTIMATES ••
DISTILLED WATER SLOPE:6 ANNA( 1) = .97621
WATER INIEKCEPI(WATCK-DISTILLED) SLOPE
-------
TABLE 8-22
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFUCE Of RESEARCH AND Of vr lOPP £ N T
ENVIRONMENTAL PROTECTION AGENCY
•• EPA METHOD 624 VALIDATION STUDY - PURGtAbltS ••
EMECT or WATER TYPE ON 1,1,1-TRICHLOROEThANE ANALYSIS
•• POINT ESTIMATES ••
DISTlLLtO WATE R SLOPE : <> AMM A C t ) • .98366
WATER INURCEPlCWAUR-DlSTlLLED) SIOPE(WATEK-OISTILLEO)
2 -.1610 . C35 1
3 -.0459 -.0055
4 -.088C -.0007
SOURCE
ANALYSIS Of VARIANCE ••
DF SUM or SOUARES HEAN SQUARE
PR06
00
•^J
REGlDISTILLED) 1 714.09659 714.09659
REGfWAIER/DISTlLLED) 6 .62005 .10334
ERROR 297 14.29643 .04814
2.15 .0482
TOTAL
304
729.01507
• TABLE OF 95X CONFIDENCE 1NURVALS FOR THE DlHtRENCES BETWEEN INTERCEPTS AND THE DEFERENCES BETWEEN SLOPES ••
MATER
INTERCEPT! WATER-01SULIED)
ESTIMATE INTERVAL
SLOPE
ESTIMATE INTERVAL
-.1610 < -.4328 . .11G7) .0351 ( -.0246 . .0947)
-.0459 < -.3153 # .22361 -.0055 I -.&643 « .05371
-. C88C C -.3734 . .19741 -.0007 I -.0632 , .0619)
NOTE
ir ZERO IS CONTAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERE IS NO SlAllSTlCAL SIGNIFICANCE BETWEEN
DISTILLED WMfft AND THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED P AR AM E T t R 11N T E R C E PT / SL OPE ) .
THE SLOPE AND INTERCEPT ESTIMATES FROM THIS ANALYSIS ARE N01 THE SAME AS tHOSE OBTAINED F RON 1 HE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 8-23
ENVIRONMENTAL HON 11OR ING AND SUPPORT IABORATOR f
orrict or research ako development
ENVIRONMENTAL PROTECTION AGENCY
•« (PA ME THOD 624 VALIDATION STUDY - PURGEABLES ••
EffECT Of WATER TYPE ON 1,1,2-tRICHLOROE1 HANI ANALYSIS
»• POINT ESTIMATES ••
DISTILLED WATER SLOPE :GAMMA<1) = .9)9*7
WATER INTCRCEPTIwATER-DlSTlLLEO) Si OP E
2 -.0548 .0161
3 .0071 .0052
4 -.1C26 .016)
SOURCE
'• ANALYSIS Of VARIANCE • •
Df SUM Of SQUARES MEAN SQUARE
PROB
00
OO
REGIOISMLLED) 1 651.35177 631.55177
REGlWATER/DlSTILLlO) 6 .17044 .02641
ERROR 283 10.13074 .03580
79
5756
TOTAL
290
641.65295
•• TAOLE Of 95* CONMDENCE INTERVALS (OR THE DlffERENCES BETWEEN INTERCEPTS ANO ThE DlffERENCtS BETWEEN SLOPES ••
WATER
INTERCEPT!WATER-DISTILLED)
ESTIMATE INTERVAL
SLOPE
-------
TABLE 8-24
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
Office OF RESEARCH AND DEVELOPMENT
LNV1RONMENIAL PROTECTION AGE NC V
•• (PA METHOD 6?* VALIDATION STUDY - PURGEABLE S ••
FffECT Of WAUR 1 IP| ON 1,1» 2 , 2 - T ETRACHLOROE THANE ANALYSIS
*• POINT ESTIMATES ••
DISTILLED WATER SLOPE:GAMMAt 1 ) = .969(9
WATER INTERCEPTIUATER-61STILLED) SLOPE(WATER-DISTILL ED)
2 -.0484 . U1U0
3 -.0404 .0152
4 -.1351 .0068
SOURCE
«• ANALYSIS OF VARIANCE ••
Df sun OF SQUARES MEAN SQUARE
PftOB
OO
VO
AfCI0IS1IlLf0) 1 609.72281 689.72281
RE6
-------
TABLE 8-25
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OlFICfc 01 RESEARCH AND DEVELOPMENT
P NV1RONMENTAL PROTECTION AGENCY
•• (PA METHOO 624 VALIDATION STUDY - PUKGEAULES ••
EFFECT 01 yATER TYPE ON 1,2-D]CHLOROBENIfN£/1,4-01CHLO ANALYSIS
•• POINT ESTIMATES ••
DISTILLED WATER SiOPE :6AMMA<1) « .92804
WAIER INTERCEPT ( W A T E R-D1ST1LLED) SLOPE (WATER-DISTILLED)
2 .0039 .(.Oil
3 .08*2 -.024.2
4 -.1855 .0243
SOURCE
• • ANALYSIS Of VARIANCE ••
IF SUN or SQUARES MEAN SQUARE
O
REE(DISTILLED) 1 548.39153 548.39153
REfafWAlER/DlSTlLLED) 6 .39624 .06637
ERROR 228 33.31188 .14610
Pftoe
•45 .6415
TOTAL
235
582.10165
•• TABLE Of 9SX CONFIDENCE INTERVALS rOR IME DIFFERENCES BETWEEN INTERCEPTS AND THE DIFFERENCES BETWEEN SLOPES «•
WATER
2
3
4
INTERCEPT*NATER-DIST1LLCD>
ESTIMATE INTERVAL
.0039
.0852
.1855
-.5953
-.5008
-.7584
.6030)
•6712)
.3673)
SLOPE(WATER-D(STILLED)
ESTIMATE INTERVAL
.0011 < -.1137 , .1160)
-•0242 I -.1371 • .0887)
.0243 4 -•0859 , .1346)
NOTE: It {t H 0 IS CONIAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE BETWEEN
DISTILLED WATER AND THE CORRESPONDING WASTE WATER EOR THE ASSOCIATED PARAMETERI 1NTERCEPT/SLOPE).
THE SI OPE AND INTERCEPT ESTIMATES IROM THIS ANALYSIS ARE NOT INE SAME AS THOSE OBTAINED FROM THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 8-26
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
Office 01 R£SJA*»CM AND C f VFl0PI*£N I
E N V IRONHIN T A L PROTECTION AGF NC Y
• • t PA METHOD 624 VALIDATION STUDY - PURGCAQLtS ••
(MKT Of WATER TYPE ON 1 ,2-0 ICHL080E THANE ANALYSIS
•• POINT ESTIMATES
DISTILLED WATCH SLOPE:GAMMA(1> • .99176
WATER INTERCCPT(WATER-DISTlLLED) SLOPE(WATEfi-DlSTlLLED>
2 -.1183 .0263
3 .0565 -.0143
4 -.2306 .0410
•• ANALYSIS OF VARIANCE ••
SOUR C t Of SUM 01 SQUARES fit AN SQUARE I PROB
(—» Rt6C01S11LLE0> 1 742.07064 742.0706*
REGCMATFR/D1ST ILLfD) 6 .4930* .06217 1.22 .2944
EMROR 300 20.16433 .06721
TO IA L 307 762.72802
•• TABLE or 95X tONFlOENCE INTERVALS I0R THE DIFFERENCES BETWEEN INTERCEPTS AND THE DIFFERENCES BETWEEN SLOPES
UA TE R
INTERCtPT(WATtR-OISTILLEO)
ESTIMATE INTERVAL
SLOPEfVATfcH-DISIILL(D)
ESTIMATE INTERVAL
-.1185
.0565
-.2306
I -.4576
( -.2742
( -.3608
.2209) .0263 C -.045b , .0985)
.3871) -.0143 < -.08 51 , .0566)
.0996) .0410 I -.0301 . .1121)
NOTE: 11 ZERO IS CONTAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERF IS NO STATISTICAL SIGNIFICANCE BETWEEN
DISTILLFD WATER AND THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PARAMETERCINTERCIPT/SLOPt).
THE SLOPE AND INTERCEPT ESTIMATES FROM THIS ANALYSIS ARE NOT THE SAHfc AS THOSE OBTAINED FROM T«E PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLUR.
-------
TABLE 8-2 7
ENV)RONNfNTAl MONITORING AND SUPPORT IAHOR A T OR Y
Office OF RESEARCH ANO DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
• • EPA METHOD £24 VALIDATION STUDY - PURGEABLES ••
UIKT Of WATER Tin ON 1.2-D1(HLOROPROPANE ANALYSIS
*• POINT ESTIMATES ••
DISTILLEO UAIE H SLOPE ;G AMMA< 1 ) * .94595
WATER INURCfPTtWATER-DlSTlLLED) SL OP E < H A T( R-0 1 S T U L ( D >
2 -.1107 .0162
3 .078? -.0135
4 -.2211 .0435
SOURCE
•• ANALYSIS Of VARIANCE •«
DF SUM 0f SQUARES MEAN SOUARf
VO
to
REG(DIST1LLED> 1 630.45804 630.45004
RE6IWAHR/D1STILLE D) 6 .56563 .06427
ERROR 277 9.30513 .033*9
1.91
PROb
,0787
TOTAL
284
640.14880
TABLE Of 95X CONFIDENCE INTERVALS FOR THE DIFFERENCES BETWEEN INTERCEPTS ANO THE DIFFERENCES BETWEEN SLOPES »•
WATER
2
3
4
INTERCEPT(WATER-DISTILLED)
ESTIMATE INTERVAL
-.1107
.0782
-.2211
< -.3687
< -.1782
< -.4808
SLOPE(WATEf)-DlSHllED)
ESTIMATE INTERVAL
.1472) .0182 C -.0343 , .C708)
.3345) -.013* C -.0657 . .0386)
.038!) .0433 < -.0093 . .0962)
NOTE: IF URO IS CON1A1NED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERE IS NO SfAIISMCAL SIGNIFICANCE BETWEEN
DISTULED WATER AND THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PARAMETER!INTERCEPT/SLOPE).
THE SLOPE AND INTERCEPT ESTIMATES FROM THIS ANALYSIS ARE NOT THE SAME AS THOSE OBTAINED FROM THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 8-28
( N V I M ONM fc h 1 A L MONITORING AND SUPPORT LABORATORY
OFFICE or RESEARCH AND DEVELOPMENT
i NV1 HON*t N T A L PROTECTION AGENCY
•• EPA HfTHOO 624 VAL 10A11 ON STUDY - PURGEAbLES ••
EFFECT C# WATER TYPE ON 1 t3-DICHLOROfc)EM7ENE ANALYSIS
•• POINT ESTIMATES ••
DISTILLED WATER SIOPE: 6 AMMA 11) = .94951
MATER INTERCEPT(wATtR-OISTILLEO) StOPE(WA IER-D I ST11LEDI
2 .0717 -.0257
3 .023* -.0019
4 -.1025 .0076
\0
SOURCE
ANALYSIS 01 VARIANCE ••
D F SUN or SQUARES MEAN SQUARE
REG
-------
SECTION 6
RESULTS AND DISCUSSION
The objective of this study was to characterize the performance
of Method 624. Accuracy and precision estimates, expressed as
regression equations, were presented in Table 1 of Section 2 for
each compound. Table 9 was prepared to facilitate the interpre-
tation of these equations. In Table 9, accuracy (percent re-
covery), overall precision (percent standard deviation), and
single-analyst precision (percent standard deviation) were com-
puted using the regression equations in Table 1. Estimates of
accuracy and precision were computed for low and high prepared
concentrations of 10 (or 15) and 100 pg/L, respectively. The
low level concentrations are approximately equal to the lowest
spike level used in the study. Values of the mean recovery, X,
computed as less than zero were set to 1 yg/L to compute the
precision estimates. Accuracy and precision estimates computed
as less than zero were set to zero.
One measure of the performance of the method is that approximately
1570 of the 9,880 data points were rejected as outliers, which is
equivalent to rejecting data from two of the fifteen laboratories.
The discussion which follows is based on the data set after re-
moving these 1,434 values.
ACCURACY
The accuracy of Method 624 is obtained by comparing the mean re-
covery, X, to the prepared values of concentration in ;jg/L. In
the statistical summary Tables 7-1 through 7-28, individual values
94
-------
TABLE 9. ACCURACY AND PRECISION ESTIMATES FOR LOW- AND
HIGH-LEVEL CONCENTRATIONS
COMPOUND
l» I I 1 l LLU V*A 1 EH
Cunt.
I uG/L
VJ< L C
,R5t> -SA
TAP WAT FR
SllRFAl h WAItR
%RSD
%REC #/>RSD SA
y.RSD
,REC '/,R!iD -SA
I NO . EF F i Ut- U I
1,l< M>
%REC %RSD -SA
Mb I NY I ENC CHI OR IDL
1 00
I 01
03
OH
35
?0
20
i 33
/9
t 6
43
/O
33
1 00
B9
/ 3
30
>3
27
1 0 2
74
63
4 /
Ob
35
TLTRACMCOROETl-ENE
I (J
tOO
1 I ?
107
1 2
1 6
1 1
I 3
105
99
2 1
26
23
23
1 1 7
104
15
24
1 6
10
103
09
30
3 I
3 2
2H
TOlUENE
1 5
1 00
1 1 2
100
1 2
2 0
1 1
1 4
1 16
101
20
23
22
19
1 15
102
13
2 1
15
15
1 10
95
19
25
1 G
2 1
1 HANS - 1 . 2-UlChl OROMHtNL
I 0
i on
11) i
so
'.'0
19
1 b
1 *>
1 03
105
22
1 7
19
1 /
10 1
9 b
20
1 b
1 7
16
96
96
24
2 3
vO
IRANS 1.3 01 Oil OROPROPENE.
1 0
100
02
00
25
26
M
19
7 7
02
2fl
25
2 5
1 4
HO
90
2 0
24
15
H 1
0 2
1 o
2 1
1 t
1 H
I U I Cni.OROEThENE
1 0
1 00
I 2 I
I 116
1 7
1 3
1 6
1 3
1 1 9
105
24
26
20
23
132
106
20
20
22
15
I I 1
101
2H
23
1 W 1 Oil OH I )h I 1 lOROMf- I MANb
I U
1 00
1 00
43
1 H
30
10 1
90
30
3 1
25
19
92
06
3 1
3 I
25
20
I 03
I 00
Z i
2 1
1 I
23
1.1 01 Cl luOROC 7 MAfU'
1 0
100
1 09
99
2 0
I G
1 3
1 5
102
10 1
2 2
11)
1 4
1 6
1 1 0
1 00
1 3
2 1
1 2
1 00
1 04
3 2
2 5
'20
2 3
1.1-01CMLOROETHENE
1 0
100
I 1 5
102
.3 9
3 7
2 /
23
1 1 5
96
20
24
3 1
10
1 09
9G
27
22
23
15
100
0 6
25
2 3
1 9
23
1 . 1 . I - IHI CHI OROhIHANf
1 0
I 00
1 1 3
1 0 /
id
2 1
1 I
1 '2
106
1 1 0
2 1
23
15
20
I 04
1 0 1
20
27
20
23
1 07
100
13
23
10
1 7
1.1,2 7 R I OlLOROL THANE.
1 0
100
I 1 2
97
I H
10
1 4
I 4
I 20
104
'2 1
1 6
24
13
1 19
106
1 4
20
14
16
1 10
1 0 1
1 3
22
1 0
1 0
-------
TABLE 9. (Continued)
DIM ILL 1.0 V«A ! c.H
1 A P WATCH
SUHI ACE WA!CR
COMPOUND
t;o:u .
(UO/L)
7-KL(. XHSl)
SA
%klc
%Rb()
SA
%R SO
V.RCC V.RSU SA
o>
6ENZCNE
HRUMOl) ICNl nHOMt- UtANt
BROMOfORM
BRUMOMETHANE
CAKBON I t TRACI I < Ik I [ib
(.HLOKDHt-Nlt-Nt-
Ml OKOC Tt IAnL
lhloroi-onm
;MlOROMt:1MANL
C I S I . 3 U1 I.Ml. < ROf-'KlH'LNL
[J I OkOMOOHLOROVC TMANl:
h IM v I HhN/tNE
1u
HO
in
UO
1 0
ilu
1 :>
00
00
l(j
LI 0
1 0
00
»0
00
10
00
lb
(10
1 1 '.1
9[,
M /
IO I
100
U4
7 »
93
i on
I 1 3
i no
i *•;)
i 10
'Jb
93
1 1 H
9b
I ) 9
1 23
10 1
101
1 1 6
100
1 1
J 4
1.1
1
.»j
~ i
j'j
2b
1 b
] 4
I '>
1
4.1
29
20
IB
bH
49
25
24
1 7
1 6
2 4
1 I
1 b
I h
1 4
1 9
2 b
1 5
1 1
.14
2f>
1 0
1 b
'»(>
411
2.1
I 9
I 5
1 7
20
1 b
1 09
9 6
1 1 h
1 04
1 0 2
I 1 2
50
bH
y 0
I 05
1 1 b
I 04
1 I 1
1 1 0
145
9 3
9 2
9 0
1 1 b
1 ? 1
103
I 07
1 19
102
10
2 I
S 2
24
43
34
44
35
1 4
23
2 0
2?
35
35
70
37
43
45
3 2
27
35
27
20
23
10
20
25
18
44
32
2 1
20
1 4
2 2
23
20
25
30
26
23
44
43
2 4.
2 1
2 I
23
27
23
1 1 3
96
90
99
90
96
64
60
99
10 1
l 20
I 04
1 2 /
1 \ 1
97
92
106
1 1 1
I IB
I 16
102
I 0 I
1 27
105
1 4
2 2
3 1
2 1
3 /
2 /
3 b
2 b
29
20
I'.)
2h
40
29
2 2
23
bO
4 b
29
3 2
19
2 1
15
2 1
10
1 4
23
1 H
1 9
1 0
2 2
24
2b
1 7
1b
1 H
3b
2 3
19
3 3
3 7
2b
2f>
16
20
1 7
lb
lot). Ef f L.ufclU
r.u-.i)
"/JU.C °'LR su • :>A
105 14 5
9 1 2 1 13
Mb 3 4 2 1
93 2 J 23
79 39 2 0
93 3-1 20
Ob 40 34
7 5 4 I 3 7
09 26 17
94 2 1 20
1 uH 2 2 2 4
94 34 2 1
11b 3«j 34
t 1 2 30 3 2
90 2b 1 /
9 4 19 14
90 50 45
102 60 bO
11h 2b 1H
120 2b 10
100 17 14
106 25 10
12 6 2 2 2 4
105 20 24
-------
TABLE 9. (Continued)
CM '•> C 1 I L L l) V.'Ail.R 1AP WATCR SURFACC WATCR 1ND. LTfLULfir
CON(. . %fU
COMPOUND (UCi/L) %RQC yJ 42
100 90 29 21 103 36 33 104 31 2G 100 33 20
1 . 2-OICHLOROfc- IHANt 1U 106 17 14 102 lb lb 111 33 24 98 33 24
10U 102 21 W 106 W 10 102 20 1 (j 101 19 IS
1 . 2-DH.Hl ONOPROPAM 1h 131 lb 10 127 16 lb 13/ 1'.) 10 120 21 1/
«X> UK) 120 17 13 118 13 M 121 1 / 13 12 2 10 14
1.3 I) I LMI UHOHb N/J- Nh 1 (J 123 11 10 140 41 46 130 7V) 26 1.' I 3.' H
10 0 I 00 17 14 106 26 2b 113 IB 16 HIS 1-> 1/
\
-------
of accuracy as percent relative error are listed for each analyte,
in each water matrix, and at each of the six concentration levels
in that water matrix (three Youden pairs). This results in 24
separate values for each compound for accuracy. The weighted
linear regression of mean recovery, X, versus the* prepared con-
centration level, C, provides values representing the percent re-
covery over all of the concentration levels. This reduced the
evaluation of accuracy to one statement for each of the 28 com-
pounds in each of four waters as presented in Tables 1-1 through
1-7.
As seen in Table 9, the mean recovery (at 100 ug/L) ranges from
68% for bromoraethane in the surface water matrix to 123% for
cis-1,3-dichloropropene in the distilled water. Overall,
recoveries at the 100 ug/L level are very good for all of the
water matrices with an average recovery of 100%. The mean
recovery for prepared concentrations at a low level (10 or 15
Ug/L) range from 58% for bromomethane in the tap water matrix
to 166% for methylene chloride and the dichlorobenzene co-
eluters in the surface water matrix with an average value of
109%. The differences observed between percent recoveries at
the low and high levels are directly related to the absolute
magnitude of the intercept tern in the regression equations.
Bromomethane is a gas in pure form. It is possible that the
low recovery observed for bromomethane may be due to inherent
difficulties in handling gaseous and extremely volatile com-
pounds during the various preparation and analytical procedures
reauired in the method. Bromomethane is also known to be un-
stable, which could also account for low recoveries. Some of
the greatest percent recovery differences are seen for methy-
lene chloride and the dichlorobenzene co-eluters.
98
-------
This trend toward higher recoveries (above 100%) for the lowest
concentration Youden pairs was observed for a total of 10 com-
pounds. One explanation could be sample contamination from the
presence of these compounds in the laboratory. Low level con-
tamination of methylene chloride may be responsible for the
higher recovery of the low pair; blank concentrations were also
higher for methylene chloride than for many of the other com-
pounds , indicating a greater likelihood of low-level sample con-
tamination. This explanation is less clear for other compounds.
For example, the trend is more pronounced for the chlorobenzenes
than for benzene or chloroform, yet the latter compounds would
be expected to be more ubiquitous in a laboratory environment.
Recoveries for cis-1,3-dichloropropene and 1,2-aichloropropane
are relatively high (ranging from 116% to 137%) for all water
matrices at both concentration levels. It is known that the
isomers of 1,3-dichloropropene are relatively unstable and may
decompose to 1,3-dichloropropane. It is difficult to explain
the results for these compounds using instability. In theory,
trans-1,3-dichloropropene should have greater stability than
the cis isomer, yet the recovery of the cis isomer is high
while the trans isomer recovery is low. The opposite trend
would be expected if decomposition were playing a significant
role in the analytical results for these compounds.
PRECISION
The overall and single-analyst precisions of Method 624 were
determined as percent relative standard deviations for each
analyte, water type, and concentration level. The statistical
summary Tables 7-1. through 7-28 present 24 individual values of
overall percent relative standard deviation, and 12 individual
values of single-analyst percent relative standard deviation,
for each compound. The weighted linear regression of standard
99
-------
deviation, S, versus mean recovery, X, provides values of percent
relative standard deviation over all of the concentration ranges.
This reduced the evaluation of precision to 112 statements - one
for each of the 28 analytes in each of the four water types.
These precision statements are presented in Tables 1-1 through
1-7 of Section 2.
The overall standard deviation of the analytical results indicate
the dispersion expected among measurements generated from a group
of laboratories. This represents the broad variation (reflecting
the combined effect of systematic and random errors) in the data
collected in the interlaboratory study. As seen in Table 9 the
percent relative standard deviation (RSD) at 100 pg/L range from
13% for trichloroethene, 1,i-dichloroethane and 1,2-dichloropropane
in the various water matrices to 607« for chloromethane in the in-
dustrial effluent with a median value of 2470. Relatively high
precision values for chloromethane, chloroethane and bromethane
may be due to inherent difficulties in handling gases in the
various stages of standard and sample handling. The RSD for low
level prepared concentrations of 10 or 15 ug/L ranged from 11%
for 1,3-aichlorobenzene in the distilled water tu 7o% for methy-
lene chloride for the tap water matrix with a median value of 25%.
As seen for the percent recovery estimates, differences observed
between precision estimates at prepared concentrations of 10 or
15 yg/L and 100 >g/L are directly related to the absolute -magni-
tude of the intercept terra in the regression equations. Some of
the greatest differences between RSD estimates at the low and high
levels are seen for methylene chloride. Precision for chloro-
methane is relatively poor at both concentration levels for all
water matrices with RSDs ranging from 437o to 607o.
The percent standard deviation for a single analyst (RSD-SA) in-
dicates the precision associated within a single laboratory. As
100
-------
seen in Table 9, RSD-SAs at a prepared concentration of 100 pg/L
range from 11% for carbon tetrachloride (distilled water matrix)
and 1,2-dichloropropane (tap water matrix) to 58% for chloro-
methane in the industrial effluent with a median value of 19%.
The RSD-SA for prepared concentrations at 10 or 15 ug/L range
from 57, for benzene for the industrial effluent to 737, for
methylene chloride for the surface water matrix. The magnitudes
of the intercept term in the four regression equations for
methylene chloride are responsible for the wide range of values
for RSD-SA. Some of the greatest P.SD-SA differences at the
low and high levels are observed for methylene chloride. Single-
analyst precision for chloromethane is relatively poor at both
concentration levels with RSD-SAs ranging from 337, to 587,.
EFFECTS OF WATER TYPES
The comparison of accuracy and precision across water types was
presented in Table 8-1 through 8-28 and is summarized in Table
10. The observed F values are entered for each of the 28 vola-
tile organic analytes. The F-test suggests a possible effect
due to water type in 4 of the 28 cases. Although statistical
significance is indicated by the F-test, the null hypothesis
test for two of the four compounds indicated that a significant
effect due to water type has not been established because zero
is contained within the confidence intervals for both the dif-
ferences between intercepts and the differences between slopes.
Practical significance was based on an examination of several
factors in addition to the results of the statistical tests.
These factors included the regression equations for accuracy
and precision, the statistical summaries of the data, and the
point estimates of accuracy and precision at low and high levels
of prepared concentration. A practical effect due to water is
indicated from the analysis and examination of these factors for
both chloroform and methylene chloride. The slope and intercept
101
-------
TABLE 10. SUMMARY OF THE TESTS FOR DIFFERENCES
ACROSS WATER TYPES
O
ho
F-TesL
Significant
Observed
at the 5%
Compound
F-Value
Level?
Benzene
0.83
No
Bromodichloromethane
1.90
No
Bromoform
1 .54
No
Hromomethane
1.17
No
Carbon tetrachloride
0.70
No
Chiorobenzene
1.83
No
Chloroethane
0.43
No
Chloroform
2.66
Yes
Chi oromethane
1.37
No
CIS-1,3-dichloropropene
0. 79
No
Di bromochloromethane
0. 56
No
Ethyl benzene
0.59
No
MeLhylene ehlo ride
2.45
Yes
Tetrachloroethene
4-27
Yes
Toluene
0.80
No
Trans-1,2-di chloroethene
0. 78
No
Trans-1,3-d1chloropropene
1.32
No
Trichloroetliene
1.51
No
Tri chLorofIuoromethane
2.12
No
1,1-Dichloroethane
0.52
No
1,1-Dichloroethene
0.45
No
1,1,1-Trichloroethane
2.15
Yes
1,1,2-Trichloroethane
0.79
No
1,1,2,2-Tetrachloroethane
1 .58
No
1,2-I)iehlorobenzene/1,4-Dichlorobenzene
0.45
No
1,2-Dichloroethane
1.22
No
1, 2-Di chl oro pro pane
1 .91
No
1,3-Dichlorobenzene
0.95
No
Statistical
Significance
Established
by the 95%
Confidence
Limits?
Signi fleant
Wa ter
Typg
PracLical
Signi fi cance
Yes
Tap
Yea
Yes
No
Surface
Yes
No
-------
estimates for chloroform in the tap water matrix were significantly
different from the estimates for the distilled water. For methy-
lene chloride, the intercept estimate for the surface water matrix
was significantly larger than the intercept term for the distilled
water. A review of the point estimates, statistical summaries
and regression equations for accuracy and precision indicate the
following:
• the recovery at low level concentrations are high
for both analytes,
• the overall RSD for chloroform in tap water
is high at all concentration levels, and
• the single-analyst RSD for methylene chloride
in surface water is high at low level concentra-
tions .
High recoveries and precision values for methylene chloride and
chloroform (in tap water) may be due to background contamination.
Relatively high recoveries for the low level Youden pairs would
be expected as a result of low level sample contamination. High
blank values for methylene chloride also indicate the probability
of sample contamination for that compound (see Appendix C, Tables
C-83 thru C-88).
COMPARISON OF PUBLISHED METHOD PERFORMANCE DATA TO INTER-
LABORATORY STUDY DATA
Table 11 compares the accuracy and single analyst precision re-
sults from this interlaboratory study to the method performance
results for Method 624 [8]. The accuracy and precision values
listed for the method performance data represent the results
103
-------
RADIAN
CORffOflilTIOM
TABLE 11. COMPARISON OF ACCURACY AND PRECISION OF INTERLABORATORY
STUDY DATA (FOR A PREPARED CONCENTRATION OF 100 Ug/L)
AND PUBLISHED METHOD PERFORMANCE DATA
Compound
Data Source
Reagent
Water*
Wastewater
% Recovery
% RSD-SA
7c Recovery
% RSD-SA
Benzene
Method
Perf.
99
9
98
10
Inter.
Study
95, 96
24, 20
96, 91
14, 13
Bromodichlororaethane
Method
Perf.
102
12
103
10
Inter.
Study
101, 104
16, 18
99, 93
18, 23
Bromoform
Method
Perf.
104
14
105
16
Inter.
Study
100, 112
14, 32
96, 93
18, 28
3romomethane
Method
Per f.
100
20
88
23
Inter.
Study
71, 68
26, 28
68, 75
24, 37
Carbon Tetrachloride
Method
Perf.
102
16
104
15
Inter.
Study
100, 105
11, 22
101, 94
17, 20
Chlorobenzene
Method
Perf.
100
7
102
9
Inter I
Study
100, 104
16, 20
104, 94
18, 23
Chloroetnane
Method
Perf.
97
22
103
31
Inter.
Study
93, .93
16, 23
92, 94
22, 14
Chloroform
Method
Perf.
101
10
101
12
Inter.
Study
96, 90
43, 43
111, 102
37, 58
CIS-1,3-dichloropropene
Method
Perf.
105
15
102
19
Inter.
Study
123, 121
19, 21
116, 120
26, 15
Dibromochloromethane
Method
Perf.
103
11
104
14
Inter.
Study
101, 107
17, 23
101, 106
20, 18
Ethyl benzene
Method
Perf.
100
8
103
10
Inter.
Study
100, 102
15, 23
105, 105
15, 24
Methylene chloride
Method
Perf.
96
16
89
28
Inter !
Study.
83, 79
20, 23
89, 74
27, 35
(Continued)
104
-------
RADIAN
C04K^0im^0M
TABLE 11. (Continued)
Compound
Data Source
Reagent
Water*
wastewater**
% Recovery
% RSD-SA
% Recovery 2
: RSD-SA
Tetrachloroethene
Method
Perf.
101
9
100
11
Inter.
Study
107, 99
13, 23
104, 89
18, 28
Toluene
Method
Perf.
101
9
98
14
Inter.
S tudy
100, 101
14, 19
102, 95
15, 21
Trans-1,2-dichloroethene
Method
Perf.
99
12
101
10
Inter.
Study
98, 105
16, 17
98, 96
16, 21
Trans-1,3-dichloropropene
Method
Perf.
104
11
100
18
Inter.
Study
80, 82
19, 14
90, 82
15, 18
Trichloroethene
Method
Perf.
101
9
100
12
Inter.
Study
106, 105
13, 23
106, 101
15, 23
Tr ic hlor of luoroaie thane
Method
Perf.
103
11
107
19
Inter.
Study
93, 98
30, 19
86, 100
28, 23
1,1-Dichloroethane
Method
Perf.
101
10
104
15
Inter.
Study
99, 101
15, 16
100, 104
12, 23
1,1-Dichloroethene
Method
Perf.
102
17
99
15
Inter.
Study
102, 96
23, 18
96, 86
15, 23
1,1,1-Trichloroethane
Method
Perf.
101
11
102
15
Inter.
Study
107, 110
12, 20
101, 100
23, 17
1,1,2-Trichloroethane
Method
Perf.
101
10
104
15
Inter.
Study
97, 104
14, 13
106, 101
16, 18
1,1,2,2-Tetrachloroethane
Method
Perf.
102
9
104
14
Inter.
Study
95, 93
17, 16
100, 89
15, 36
1, 2-Dichloroethane
Method
Perf.
100
8
102
10
Inter.
Study
102, 106
17, 18
102, 101
16, 15
1,2-Dicnloropropane
Method
Perf.
102
8
103
12
Inter.
Study
120, 118
13, 11
121, 122
13, 14
* The two values given for the reagent water validation data in each column represent
the distilled and tap waters, respectively.
** The two values given for the wastewater validation data in each column represent
the surface water and industrial effluent, respectively.
105
-------
from two to four laboratories. The values listed for the inter-
laboratory study were computed at a prepared concentration of
100 pg/L after removing approximately 157c of the reported values
as outliers.
REVISED EQUATIONS
A review of the data remaining after the IMVS outlier screening
indicated some potential problems with the data for nine of the
volatile organic compounds. For these compounds, results for
ampule four were out-of-line (usually due to extremely low re-
coveries) with the remaining data. It is suspected that during
production of ampule concentrate four, these volatile compounds
were lost. The data for these medium level ampules were eli-
minated, and the equations revised. Table 12 presents the re-
vised equations and Table 13 presents the revised accuracy and
precision estimates for these compounds.
Four compounds in addition to those listed in Table 13 had ques-
tionable regression equations although the equations were not
revised. These were bromomethane, cis and trans 1,3-dichloro-
propene and 1,2-dichloropropane. Bromomethane exhibited poor
recoveries which may have been due to its extreme volatility or
to its reactivity. The dichloropropenes are known to be unstable
and to form dichloropropane upon decomposition. Problems with
these compounds were also encountered with EPA Quality Control
Samples and in the Interlaboratory Study for Method 601 - Halo-
genated Purgeables by GC.
RESPONSES TO QUESTIONNAIRE
A questionnaire for Method 624 was provided for all participating
laboratories. Each of the 15 laboratories responded to the ques-
tionnaire. The responses are summarized below.
106
-------
TABLE 12. REVISED REGRESSION KCJUAT TONS FOR ACCURACY AND PRECISION
Water Type Bromoform Carbon Tetrachloride Chloroethane
Applicable Cone. Range (}jg/L)
(9.
0 - 400)
(S
~ .0 - 400)
0
'.3 - 488)
Distilled
Single-Ana 1 yst. Prec i s ion
SR =
0.12X
+
0.36
SR
=
0.12X
+
0.25
SR
=
0.14X
+
ro
00
Overall Precision
S -
0.17X
+
1.38
S
=
0.11X
+
0.37
S
-
0.29X
+
1.75
Accuracy
X =
1 .18C
-
2.35
X
=
1 .1 0C
+
1.68
X
=
1.1 8C
+
0.81
Tap Water
Single-Analyst Precision
SR =
0.23X
+
2.06
SR
=
0.18X
-
0.53
SR
=
0.29X
-
0.52
Overall Precision
S -
0.33X
+
1.01
S
0.20X
-
0.61
S
=
0. 34X
+
0.13
Accuracy
X =
1.32C
-
2. 74
X
=
1..18C
-
2.66
X
—
1.17C
-
0.3/
Surface Water
Single-Analyst Precision
SR =
0.14X
+
0.38
SR
0.15X
+
1.07
SR
=
0.25X
+
1.37
Overall Precision
S -
0.24X
+
1.08
S
0.18X
0.98
s
=
0.28X
+
1 .46
Accuracy
X =
1.10C
-
1.80
X
1.07C
-
0.73
X
=
1.12C
+
1.63
Industrial EffluenL
Sing1o-Ana 1yst Precision
SR =
0.18X
+
0.65
SR
-
0.19X
-
0.23
SR
=
0.32X
+
0.25
Overall Precision
S -
0.25X
+
1.02
S
0.19X
+
0.59
S
--
0.40X
-
0.37
Accuracy
X =
1.06C
-
2.67
X
-
1.00C
-
1.07
X
=
1 . 24C
-
0.4L
X
C
(Continued)
-------
Water Type
Applicable Cone. Range (pg/L)
Distilled
Single-Analyst Precision
Over a 1.1 P rec i s io n
Accuracy
Tap Water
Single-Analyst Precision
Overall Prec* i sion
Accuracy
Surface Water
Sing 1e-Analyst Precision
Overall Precision
Accuracy
Industrial Effluent
Single-Analyst Precision
Overall Precision
Accuracy
X = Mean Recovery
C = Prepared Concentration
(Continued)
Methylene Chloride Trans-1,2-Dichloroethene
(7,
.2 - 480)
(4.5 - 300)
SR =
0.15X
+
1 .07
SR
= 0.14X + 0.09
S =
0.32X
+
4.00
S
= 0.19X + 0.17
X =
0.87C
+
1.88
X
= 1.15C + 0.03
SR =
0.20X
+
4.96
SR
= 0.11X + 0.49
S =
0.38X
+
5.19
s
= 0.15X + 0.60
X =
0.78C
+
5.66
X
= 1.11C - 0.40
SR = 0.27X + 8.17
S = 0.29X + 7.48
X = 0.83C + 8.40
SR = 0.30X + 3.56
S =. 0.42X +2.06
X = 0.80C + 2.50
SR = 0.17X + 0.04
S - 0.15X + 0.40
X - 1.02C + 0.05
SR = 0.26X - 0.29
S - 0.19X + 0.22
X 1.02C - 0.23
(Cont inned)
-------
TABLE 12. (Continued)
Water Type. Trichl .orof 1 uorome thane 1,1-Dichlo roe thane 1 , I-Di chl oroe thene
Applicable Cone. Ranj;e (}jg/l.)
(7
. 2 - 480)
(10.8 -
480)
(7
.2 - 480)
Distilled
Single-Analyst Precision
SR
=
0.33X
-
1.48
SR
=
0.13X
-
0.05
SR
= 0.17X
•f
1.06
Overall Precision
S
-
0.34X
-
0.39
S
-
0.16X
+
0.47
S
- 0.43X
-
0.22
Accuracy
X
=
Q.99C
+
0.39
X
—
1.05C
+
0.36
X
= 1.12C
+
0.61
Tap Water
Single-Analyst Precision
SR
=
0.17X
+
0.80
SR
=
0.14X
-
0.08
SR
= 0.12X
+
2.08
Overal 1 Pre.ci si on
S
=
0.29X
+
0.04
s
=
0.14X
+
0.82
S
= 0.24X
+
0.53
Accuracy
X
—
1.05C
-
0.19
X
=
1.07C
-
0.53
X
= 1.02C
-i
1.43
Surface Water
Single-Analyst Precision
SR
=
0.33X
-
0.57
SR
-
0.11X
+
1.08
SR
= 0.16X
-f
0.87
Overal1 Preei .si on
S
=
0.31X
+
0.03
S
0.1 2X
+
1.12
S
= 0.24X
+
0.51
Accuracy
X
=
0.87C
+
0.50
X
=
1.02C
+
0. 76
X
= 1.01C
+
0.91
Industrial Effluent
Single-Analyst Precision
SR
=
0.27X
+
1.62
SR
=
0.23X
-
0.27
SR
= 0.24X
-
0.39
Overall Precision
S
=
0.26X
-
0.43
S
=
0.21X
+
1.12
S
= 0.20X
+
0.39
Accuracy
X
=
1.07C
0.29
X
1 .09C
0.12
X
= 0.93C
+
0.94
X = Mean Recovery
C - Prepared Concentration
-------
TABLE 13. REVISED ACCURACY AND PRECIS TON ESTIMATES FOR
100 ppb CONCENTRATION LEVELS
CIS7ILL5C LATFP TAP WAT'F
1 7
1 no
i
?*•
Tlir.H rRCFLUCOO^Th^NF
C r
: 4
3?
1 Of
2^
1*
87
31
32
107
2 6
1 c
1 «1-C1 CM OP ZZ THA-r
i
16
1 3
1 36
1 C
1 <»
103
13
1 2
1 0 9
22
? 3
1 * 1-LI CM. tR :i IHL' F
11 3
* *
1 o
1 C1
2 f
1 *
1 0?
25
1 7
2 r
>6
-------
METHOD 624
Instrument and calibration parameters are summarized in Table
14. Of the 15 participating laboratories, 11 used Finnigan
GC-KS systems. The models used were: OWA 20; OVA 30; OWA 30B;
OVA 1020; 3200; 4021; and 4023. Four labora tories used
Hewlett-Packard instruments (Models 5981, 5985, and 5985A ) .
Ages were in the range of one to five years for 10 of the in-
struments and six to 12 years for the remaining 5. Two labora-
tories specified commercial purge and trap apparatus, a Tekmar
LSC-3 and an HP 7675A. With one exception, 1% SP-1000 columns
were used. Carbopack B was specified as the solid support by 10
of the laboratories. One laboratory used a 0.37o Carbowax 20M on
80/100 Carbopack C column. The temperature programs used were
typically 45°C for 3 to 4 minutes and 8°C/minute to 220°C with
exceptions as noted in Table 14.
Calibration standards were obtained primarily or exclusively
from Supelco by 10 of the laboratories, with some laboratories
specifying additional sources such as Aldrich, J. T. Baker and
Chem Service. Four laboratories prepared standards from neat
compounds. Three specified Chem Service as the supplier. In-
formation on standard sources was inadvertently omitted by one
laboratory. Calibration curves contained three points for 10
laboratories while four-point and five-point curves by 2 labo-
ratories each. All laboratories used the internal standard
technique.
Seven laboratories encountered no problems with the calibration
procedures. Four laboratories reported difficulties in meeting
bromofluorobenzene (BFB) instrument tuning criteria. One of
these laboratories recommended using FC-43 for tuning. Five
laboratories, including one of the above, had difficulty meeting
111
-------
TABLE 14. SUMMARY OF INSTRUMENT AND CALIBRATION PARAMETERS
t.;ib
Code
Inst runcnt M.ike
Age
(Yr)
Col unui
Column Cuud.lt Ions
Primary Source
ol bljudjids,
C.11 11; rn I ion P<> i«t •
(UB/l.)
10
12
13
IS
Kinnlftan 0WA-20 2.5
Kinnlp.nn OWA 1020 1
t*lnnif»an 4023 5
Ilculeit-Fackard 4.5
'>SH')A + lb A
purfv and rrap
sample r
Hewlett-Packard 8
VJHl
Fimilyju 4021 5
Finnlgan OWA-30B ?
Kl.u.ltju J200 5
Hi-wltMi P.irk;ird 5
598!) A
t'lmilgju QUA-JO
F(nn1j>nn 4021
Hewlett Packard 6
5985 + Tekmiir LSC-J
Flnnlgan 3200 7
Kind 1 ti OUA 1020 1
Flimlgan 3200
2.5
6*; 1Z SP-LOOO on 60/rtO
C.trbopack R
6*x2 mm ID; U SP-1000
on 60/80 Carbopack B
\Z SP-1000 on 60/80
Carl>opack B
8'xl/8" 0D sr>; 12 SP-
1000 in 60/80 Carbopack
B
6 1 x2 ran ID glass; 12
SP-1000
6'x2 nm ID SS; 12
SP-1000
b'x'.' ma ID gl.n;i;; 12
SP-1000 on 60/80 Carbo-
pack B
6'; 12 SP-1000 on Carbo-
pack B
f>'x2 im ID 12
SP-1000 on 60/80 Carbo-
pack B
12 SP-1000
0.32 Carhowax 20 M on
80/100 Carbopack C
12 SP-1000 on Carbopack
C'r.2 on ID glass; 12
SP 1000
6' glass; 102 SP-1000
on Carbopack B
102 SP-1000 on Carbo-
pack B
45"C for 3 mln; 8"C/mln ro
2?U*C; hold at 220°C
4'>°C for 4 nln; B°C/raln to
220°C
Ambient for 4 mln; 50"C -
200°C al 8*C/roln; hold at
?00°C
45°C for 3 Bin; 8°C/nln ro
220*C; 220*C for 15 mln
45*C for 4 mln; 8*C/min to
22(>#C; 220°C for 30 mln
45*C for 3 mln; 8°C/mln to
??0°C
45*0 for 3 rain; 8'C/mln to
220*C; 220*C for 25 mln
50*C: 10*C/nln to 220°C
45"C for 3 mln; 8'C/mln to
220°C
65*C for 3 nln; 8aC/mlu to
245°C
30°C for 2.5 mln; 10*C/min
to 220*C; 225*C for 5 mln
45*C for 3 mln; 8°C/mln to
220°C
Ambient for 1 mln; 60®C for
1 mln; 8-C/toln to 220*C
45°C for 3 mln; 6*C/nln to
220°C
45QC for 3 mln, 8"C/aln to
220*C; 220«C for 15 nln
Supclco (purR<.*abl«'
K«)»us prepared In-
linusr)
Suptrlco
Prepared inhouse
Supclco
Supclco
Not specif led
Prepared I n ho use*
Supelco
Supclco
Supclco
10. 40. 120
40, 80, 160
10. 50. 100
20-50. 250. j00
30. 45. 60. 90
25. 100. 200
25, V), 100
10, 50, 200
2. 20. 50. 100. 200
10, 20. 200
Supelco
Prepared 1 nhou:;«'
Supelco and Analabs 2-200 (5 points)
10. 10. 100. ¦«)«
Assumed 3 points
Prepared Inhouue J.2-/4, 6.3-141, 6.3-1410
Chro Service Compounds 320-701O
Supclco
20, 50. 100
'(Questionnaire stated dilution# were performed ae specified In tlie method.
-------
daily linearity criteria. Two laboratories reported difficulty
in calibrating for the dichlorobenzenes (DCB) due to coelution.
QA/QC measures are summarized in Table 15 and included surrogat
control charts (seven laboratories) system blanks using reagent
water (all laboratories), duplicate analyses (seven laboratorie
replicate injections (three laboratories) and check standards
(eleven laboratories).
Additional QA/QC measures included statistical data comparisons
comparison of surrogate recoveries to predetermined control
limits (two laboratories), additional sample spiking (two labo-
ratories) and spiking of all samples with BFB.
No QA/QC problems were encountered by 11 of the laboratories.
One laboratory complained of an insufficient volume of spiking
solution for duplicate analyses. One laboratory found that
surrogate recoveries varied due to on-column injection varia-
bility of standards and recommended spiking surrogate standards
into reagent water. One laboratory reported the loss of the
highly volatile gases in standards. One laboratory reported
background problems with methylene chloride, benzene, toluene
and tetrachloroethene.
Six of the laboratories reported difficulties with sample purg-
ing and concentrating. These included:
• The loss of 2-chloroethylvinyl ether in the
Tekmar purge and trap apparatus, remedied by
replacement of a six-port valve;
• Contamination by the sample for false positives
and false negatives and high-level surrogates
requiring extended system bakeout;
113
-------
TABLE 15. SUMMARY
Surrogate
Lab Control
Code Charts System Blanks
1 NP Daily
2 Each sample Daily
3 Daily Twice daily
4 NP Daily
5 Da ily Da i1y
6 NP After standards and
high samples
7 Each sample Daily and after high
samples
8 NP Each shift
9 Daily Daily
10 NP 3/day
11 On-going Daily
12 NP Daily
13 NP Daily and as required
14 Daily Daily
15 NP After standards and
high samples
NP = not performed
1 Specified new curve daily
OF QA/QC PROCEDURES
Duplicate
Analyses
Replicate
Injections
Check
Standards
10% of samples
NP
As required
NP
NP
As required
NP
As required
NP
NP
NP
NP
NP
Da i 1 y
Daily
Daily
NP
Dai ly
15% of samples
NP
Quarterly
NP
NP
Daily
NP
20%
NP
NP
10%
As required
(2-3 times)
NP
NP
NP
NP
NP
Daily
NP
Each shift
Daily
Weekly
NP
Da ily
Daily
NP1
Each 8 hours
-------
• Foaming of the "hard-to-analyze" sample (two
laboratories); and
• Loss of the early eluting gases (three labora-
tories) .
Instrument problems were restricted to short downtimes exper-
ienced by two laboratories with no subsequent effects on analyses,
and saturation of the electron multiplier experienced by two
laboratories, requiring sample dilution.
A number of laboratories experienced difficulties with inter-
ferences including:
• Methylene chloride interferences including a
high concentration in the industrial effluent
requiring dilution, a concentration in the
surrogate solution at a level of approximately
107o of the surrogate concentrations and as an
interferent in all analyses (three laboratories);
• Background levels of compounds of interest in
the different water types;
• Interferences with the second and third internal
standard peaks in high level samples;
• High concentrations of unlabeled compounds re-
sulting in high recoveries of their labeled
analogs and vice versa.
Problems with peak identification included difficulties in re-
solving the DCB isomers (seven laboratories) and difficulty in
115
-------
detecting 2-chloroethylvinyl ether (five laboratories). Two
laboratories reported that 2-chloroethylvinyl ether coelutes
with 2-bromo-l-chloropropane, an internal standard. One labo-
ratory detected the compound in standards but not samples, while
one laboratory could not detect it in standards or samples.
One laboratory reported a low intensity of m/e = 106 and inter-
ference at ra/e = 63 as the problem. One laboratory also re-
ported difficulty in identifying tetrachloroethene in the pres-
ence of high tetrachloroethane.
Miscellaneous analytical problems included the absence of one
or more key ions in low-concentration samples, high surrogate
concentrations requiring dilution and compound responses above
the linear range of the instrument.
Recommendations were made by 12 laboratories for improving
Method 624. These included:
• Using a fused silica capillary column instead
of the specified packed column to increase
sensitivity and improve chromatography (two
laboratories);
• Using FC-43 to tune the GC-MS system;
• Restricting the analysis of dichlorobenzenes
to Method 625 (three laboratories);
• Preparing surrogate solutions and standard
dilutions in methanol to diminish stability
problems by allowing freezer storage (two
laboratories);
116
-------
Starting the spectral scan at 35 amu rather
than 20 amu since the range of 20 amu - 35 amu
does not provide useful da.ta;
Dilution of high concentration samples rather
than extending calibration ranges (two labora-
tories) ;
Running low- and mid-level calibration standards
daily in place of the three-point curve with
daily verification and subsequent quantitation
of samples according to the standard closest
to their concentrations with dilution of high
concentration samples if necessary;
Doubling the temperature program rate of the GC
to reduce analysis time;
Computing the results for Youden pairs using the
isotope dilution method to determine the accuracy
of isotope dilution.
Determining which of the Youden pairs have
quantitative ions that contribute to each other
and verifying that proper deconvolution of these
pairs is performed using the 1624/1624 formulae;
Increasing the allowable relative standard
deviation from linerity for the volatile gases
to 20% due to greater inherent variability for
these compounds;
Adding charcoal to the trap to increase trapping
efficiency for highly volatile compounds;
117
-------
Using n/e 62, m/e 83 and m/e 166 for quantitation
of 1,2-dichloroethane, tetrachloroethane and
tetracnloroethene, respectively. These are based
on the greater abundance of the first ion allowing
increased sensitivity and improved accuracy when
the latter ions are used; and
Using a sample size of 25 mL to increase
sensitivity for low-concentration compounds.
118
-------
SECTION 7
EVALUATION OF SURROGATE COMPOUNDS
In order to examine the relationship between surrogate and spike
recoveries, surrogate recoveries were correlated with the recov-
eries for each priority pollutant.
Table 16 presents the correlation matrices for the volatile
organic compounds. Potential outliers were not discarded from
the recovery data in performing the correlation analysis. The
influence of outliers in the data were minimized by using Spear-
man's coefficient of rank correlations [9], which are correla-
tions of the ranks of the variables. Approximately 350 data pairs
were used to calculate each of the coefficients.
The correlation coefficient is a measure of the strength of the
linear relationship between two variables. A correlation of one
indicates that the two variables are perfectly linearly related
and that one increases as the other increases. A correlation of
minus one indicates that a perfect linear relationship exists,
but that one variable decreases as the other increases. A corre-
lation of zero indicates that there is no linear relationship at
all between the two variables. The square of the correlation
coefficient is interpretable as the fraction of the variability
in one variable that can be explained or predicted in terms of
the other.
Statistical significance is important because even if two vari-
ables have no true or repeatable relationship, a correlation
coefficient computed from a finite sample would not be expected
119
-------
TABLE 16. CORRELATION COEFFICIENTS OF SURROGATE
RECOVERIES AND SPIKE RECOVERIES
COMPOUND
HE TEN! I ON
1 1 ML
(WINUTLS)
, V-01( HLORO
BEN/LNE D4
(RT NO)
surrogate
1 , 4-DICHLORO-
butane do
(RT ND)
2-BROMO-I-
CHLOROPROPANE- 06
(RT-ND)
8R0M0CMI OHO-
ME THANE"D2
(R T-9.3)
hLOORO-
SENZCNfc
( R T = 1 8 . 4 )
4-BROMOHl.UOHO-
BENZENE
(RT-20.3)
ro
o
LHlOROME1 MANE
2 .
3
-I)
7 24
0 .
1 IB
-n.
097
• 0 .
100
• 0 .
1 6b
-0 .
249
BHOMMMf- THANfc"
3 .
1
0 .
209
0.
150
0.
090
-0 .
1 38
-o.
166
-o.
. 265
CHI OKOE THANE
4 .
6
0 .
1GB
0 .
156
-0
034
-0 .
10B
-0
162
-0.
263
METHYLENE CHL OR IDE
6
4
-o.
009
0.
191
0
060
u.
014
-o.
024
-o
031
TR I CHLCROhLUOr 1
1 . 1-01 CHI OROE THhNh
9 .
0
u.
164
-0.
007
-0 .
1 30
3 .
072
-o.
262
-o
. 199
1 , 1 - IJ IC HI OROETHANE
10
1
0 .
28b
0 .
087
-o.
.181
0 .
006
-o.
247
-o.
. 300
TRANS"1,2 D1CHLOROETHENE
in.
8
-o.
? 0 7
0 .
100
-o
096
U.
006
-o
1 77
-o.
2 16
CHLOROFORM
11.
4
-o.
1 2 1
n
1 50
0
. 032
-1).
OH7
0
. 053
-o
.12 1
1.2-1)1(HLOROEiHANh
1 2
1
-u
1 53
0
. 163
0
. 032
0
002
0
.033
-o
. 1 f>6
1 . 1 . 1 1 R 1 CHLOfcOF' 1 MANF
1 3
4
0 .
1 06
0 .
077
0.
.075
-0.
039
-o.
163
-o.
. 224
C.ARDON TCTRACI-LORIOC
1.1
7
• 0
163
0 .
. 1 76
0
.11?
-0 .
034
-0
.141
-o
. 193
BROMOOICHl OROME TrtANE
1 4 .
3
-0
089
u
196
-0
. 046
0 .
004
-o
096
-o
. 1 b 1
1.2-01C.HLOROPROPANF
lb.
I
D .
144
0
111
0
. 2 50
0 .
Ort /
0
. 1 78
0
Ob /
IKANS 1.3 OIU-I CJHOPROPLNL
1 b
9
[).
1 00
0 .
. 279
0
. 206
•o.
034
0 .
.110
-o
.090
TR I Ci 11 OROE TIU. NC
16.
f>
0
. ooa
0
.022
0
. 089
0.
009
0.
. 000
0.
.02 1
UlNZENF
1 7 .
0
-o
. Ob 2
0
.098
(J
. 0 / H
-1.).
09B
-o
. ObO
-o.
. 1 6b
DI BROMOC.HLOROWt 1 HANfc
1 I .
1
0
021)
0
. 163
0
. 036
0
0/6
-o
.02b
-o
.01 /
< I S- 1 . 3-OiCML (.-MOPWORFNt
1 / .
2
-II
1 J J
0
. 153
-0
. 139
-o.
146
u
. 10/
-o
. 095
1.1.2 TR1(HLOROETMANC
1 7 .
2
0
. Ob 7
0
. 1 20
0
. 107
-0 .
.093
-o.
. 005
-o
.05 1
BROMOFORM
1 9 .
B
-o
0 11
0
. 189
-o
. 023
0
.09 7
-0
.013
- 0
. 034
1 . 1 .7, 2-TET RAC'Hl OROET HANE
2 2 .
1
0
119
0
142
0
. 095
11 .
2 1 0
0
. 095
u
. 1 /O
1 1- I RAC.HLOROL 1 MFNF
7 2
2
-o
.012
0
.14/
-0
. 032
0
.0 16
0
.02 1
0
. o ;i f>
101 OfcNL
23
5
0
. (JU4
0
. 103
0
.062
0
.0 14
-o
.017
0
. 044
CHlORODCN/JNL
24 .
G
0
. 050
0
.096
-~
. 053
0
.017
0 .
.02 1
0 .
.059
CtHYL BENZENE
26 .
4
0
02 1
0
. 1 26
-o
.019
u
. 006
-o
. 003
0 .
. 060
1 . J-OICHLOROBfcN/fNr
Nf
0
M 9
n
.0 75
0
. 025
-o
0 2 3
0
. 06 1
0
. 11) 1
1 .7-/ 1 .4-DICH1 OHOH F N / F Nt
Nl)
0
. .-15 to
0
. 038
0
. 1 74
0
1 29
0
. 1 74
0
.22 1
NO NOT nETFKMINKl
K1 : Rfc1fcNT ION M Mt
-------
to be exactly zero. For the data presented in the table, a
correlation coefficient is statistically significant at the 0.01
level if the coefficient is greater than 0.14 (or less than -0.14).
A significant correlation indicates a.real relationship between
the compound ana the surrogate. There is less than one chance
in 100 that a particular one of the significant correlations
could have occurred by random chance if the variables did not
have an actual relationship.
With the exception of the surrogate compound, 1,4-dichlorobutane-
g8, over one-half of the correlation coefficients are negative.
Of the 76 positive correlation coefficients, only 23 of these
(30%) are statistically significant at the 0.01 level. Figure
1 shows a typical set of data for a non-significant relationship.
The analysis of the surrogate recovery data from the interlabora-
tory study do not indicate strong relationships between the
recoveries of the surrogates and the recoveries of the compounds
of interest. For only one compound (1,2-dichlorobenzene/
1,4-dichlorobenzene) was a surrogate identified that could explain
greater than 10% of the variation in the recoveries of the
compound.
These results do not inply that surrogate/compound relationships
do not exist. As long as the recoveries of a compound remain in
a state of statistical control, then the variations in recoveries
are expected to be random. The variation of the test methods
(coefficient of variations generally greater than 20?o) make it
difficult to observe surrogate relationships with a "narrow"
range of recoveries. In order to establish and quantify surro-
gate relationships, it is necessary to purposely decrease and
increase the compound recoveries. This, of course, was contrary
to the objectives of this inter laboratory study. Further inves-
tigations of various statistical approaches for the evaluation
121
-------
SPIKE RECOVERIES VS SURROGATE RECOVERIES (•/„)
VOA FRACTION
hO
ro
CM-
1««-
e
H I
L.
o
n
o i
eo-
o-
r = 0.096
**
C K * K
V5* %
—1
CEB
969
—r
•400
I , 4»P2CHLOAO0UTANK**Ot
FIGURE 1.
-------
of surrogate compounds will be implemented and reported in a
separate report at a later time.
For volatile organic compounds eluting up to 15.7 minutes,
4-bromofluorobenzene tends to have the highest correlation
coefficient. For compounds eluting after 14.3 minutes,
1,4-dichlorobutane-d3 generally has the highest correlation
coefficients. Correlation coefficients for compounds eluting
between 14.3 and 15.7 minutes are not significantly different
for the two surrogate compounds, 4-bromofluorobenzene and
1,4-dichlorobutane-ds.
123
-------
REFERENCES
1. Youden, W. J. Statistical Techniques for Collaborative Tests.
Association of Official Analytical Chemists, Inc., Washing-
ton, D.C., 1969. 64 pp.
2. Outler, E. C. and McCreary, J. H., Interlaboratory Method
Validation Study: Program Documentation, Battelle Columbus
Laboratories, 1982.
3. ASTM D2777-77, 1980 Annual Book of ASTM Standards, Part 31,
pp. 16-28. American Society for Testing and Materials,
Philadelphia, Pa.
4. ASTM #178-80, 1980 Annual Book of ASTM Standards Part 41,
pp. 206-231, American Society for Testing ana Materials,
Philadelphia, Pa.
5. Youden, W. J. "Statistical Manual of the AOAC," The Associa-
tion of Official Analytical Chemists, Washington, D.C., 1975.
6. Thompson, W. R. "On a Criterion for the Rejection of Observa-
tions and the Distribution of the Ratio of the Deviation to
the Sample Standard Deviations." The Annals of Mathematical
Statistics, AASTA 6 (1935) pp 214-219.
7. Britton, P. W., "Statistical Basis for Laboratory Performance
Evaluation Limits." Presented at the 142nd Joint Statistical
Meeting, Cincinnati, Ohio, August 17, 1982.
124
-------
"Methods for Organic Chemical Analysis of Water and Wastes
by GC, HPLC, and GC/MS." U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio 45268.
Johnson, N. L. and Leone, F. C., "Statistics and Experimen-
tal Design," Volume I, 2nd ed., John Wiley 6c Sons, Inc.,
New York, 1977.
125
-------
APPENDIX A
STUDY ON FALSE POSITIVES AND FALSE NEGATIVES
A small study was conducted on a very challenging sample to deter-
mine the extent of false positives and false negatives. An
industrial effluent water was supplied to the participants in the
study by Radian. The sample contained both priority and non-
priority pollutants. Table 1 shows the number of false positives
and number of false negatives for the hard-to-analyze sample using
the following definitions:
1) A compound is considered present in the sample if one-half or
more of the laboratories (seven or more) quantified the compound
at greater than 1 ug/L- (For these compounds there is potential
for false-negatives.)
2) A compound is considered not present in the sample if less than
one-half of the laboratories reported the compound at greater
than 1 pg/L. (For those compounds, there is potential for
false-positives).
3) A reported value is only considered a false-positive if it was
reported at greater than 1 ug/L.
Using these definitions, eight volatile organic compounds are
present in tne sample. For these compounds, there are a total of 24
false negatives (twenty percent of the possible results). There are
also eight compounds which were reported by less than half of the
laboratories (but reported at >1.0 gg/L by at least one labora-
tory). For these eight compounds, there were seventeen false
positives (14 percent of the possible results).
126
-------
TABLK A-l.
FALSE POSITIVE AND FALSE NEGATIVE STUDY
SAMPLE RESULTS FOR THE VOA FRACTION
LABORATORY
COMPOUND
10
I 1
1 2
1 3
1 A
I 5
BtN/hNE
CHLOROFORM
c i S - i ,:rni(.iu OKOPHOPtNt
Me I HVl ONE C.MLOR IDC
TOLUCNC
1 . 1 - D I CHI OHUfr H-tNE
2-CHLCRtTHYLVlNYL hlHhH
-------
TABLE A-2.
STATISTICAL SUMMARY OF THE FALSE
FALSE NEGATIVE STUDY FOR THE VOA
POSITIVE AND
FRACTION
QUAi I TAT IVE
PERFORMANCE~
NO. Oh VAllltS I,(J . Oh VAIUI-S
(.{'IMPOUND D fc r L (. T fc- IJ NO I UMhClhD f- A I ^ t* hAlSt
POSI T I VE:-> NLCiA 1 I VL S
BENZENE
CHI ORUf-OKM
c: I s - 1 . li "D I (' ML OHO PROP J-Nh
METMVlENE CHLORIDE
TOLUENE
1 , 1 DICMLUWOE THENt
2 CMLORtIHYLVINYL fclHLN
0
b
I 4
1
0
14
1 4
00
* IF MORE THAN half Oh Hit LABORATORICS QUANTITATED THE COMPOUND AT >10 UC./I . THEN ThE COMPOUND
IS CONS I Of" RED PRhSENl IN THE SAMPLE (POTbNJIAL FOR FALSE NEGATIVES). OTHERWISE ImL" COMPOUND
IS NOI CONSIOhMeD PRE SEN 1 IN Ihh SAMPl h (POTENTIAL HOW hALSt POSITIVES).
-------
APPENDIX B
RESULTS OF GC/MS FEASIBILITY STUDY
To prove the feasibility of the study, Radian analyzed the Youden
pair ampules spiked into water using the same procedures for the
participating laboratories. Figure B-l presents the total ion
scan for the 1-2 Youden pair sample. Retention times for the
sample and the masses used for both qualitative and quantitative
analyses are given in Table B-l. As shown, the total ion scan
provides well resolved peaks with little difficulty in inter-
pretation with the exception of 2-chloroethylvinyl ether which
decomposed in the solution and 1,2- and 1,4-dichlorobenzene
which coelated 1.
129
-------
FIGURE 3-1. TOTAL ION SCAN OF THE 1-2 YOUDEN
PAIR FEASIBILITY SAMPLE
SAMPLE! METHOD 624,SPIKING C0MPDS*1-2C5UL/'5ML)TOTAL RUN TIME CMINU
35
FRNt 10875 TOTAL NUMBER OF SCANS* 750
LARGEST PEAK SCAN NO, t 283 LARGEST PEAK ABUND.s 14884$
LARGEST PEAK RET# TIMECMIN)t 13.36 TOT. RUN ABUND.I 8.82122E+06
100
100
10
20
14
16
18
20
22
24
26
30
32
34
38
40
Retention Tim#
-------
TABLE 3-1. RETENTION TIMES AND MASSES FOR VOLATILE COMPOUNDS
(1-2 YOUDEN PAIR FEASIBILITY SAMPLE)
Compound Retention Time m/e
3romodichloromethane •
10.5
127
3romoform
15.7
173
3ronomethane
1.6
94
Cnloroethane
2.5
64
2-Chloroethyl Vinyl Ether*
14.5
63
Chloromethane
1.2
50
Dibroraochloromethane
13.1
127
1,1-Dichloroethene
5.8
96
1,1-Dichloroethane
6.8
63
1,2-Dichloroethane
8.5
98
1,2-Dichloropropane
11.9
63
cis-1,3-Dichloropropene
13.3
75
trans-1,3-Dichloropropene
12.2
75
Ethyl Benzene
22.5
106
Methylene Chloride
3.8
84
1,1,2,2-Tetrachloroethane
18.0
83
Tetrachloroethene
18.2
164
1,1,1-Trichloroethane
9.7
97
1,1, 2-Trichloroet'nane
13.3
97
Trichloroethene
12.7
130
1,2-Dichlorobenzene**
30.3
146
1,3-Dichlorobenzene
29.4
146
1,4-Dichlorobenzene**
30.3
146
Trichlorofluoromethane
5.3
79
Benzene
13.2
78
Carbon Tetrachloride
10.1
117
Chlorobenzene
20.7
112
Chloroform
7.9
83
Trans-1,2-Dichloroethene
7.6
96
Toulene
19.5
92
^Decomposed in the solution mixture
**Compounds co-eluted from the GC column.
131
-------
APPENDIX C
RAW DATA
(Corrected for blank values for each laboratory)
132
-------
TABLE C-l
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE: OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PUNGtAtfLES **
RAW DATA FOR BENZENE ANALYSIS BY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER
TAP WA TE R
SURFACE WATER INDUSTRIAL EFFLUENT
AMPUL NO:
TRUE CONC;
1
1C.8
2
12.0
1
1:.?
12.0
1
IC.fl
2
12.0
1
10.*=.
4.
12.0
u>
LU
LAR NUMBER
10.7
1.9*
9.6
1T.1
11.0
12.2
9.9
11.1
15.0*
U.7*
13.9*
15.9*
11.8
16 .?
1?.?*
17.?*
11.6
12.2
11.3
12.8
13.4
12.9
9.4
3 9.5*
11 .a
10.7
7.2
15.9
14.8
12.3
17.9*
13.3
9.7
11.3
11 .8
1C.0
ft. 9
11.1
0.0*
O.C*
9.0
12.1
9.9
11.4
11.0
10.C
8.8
10.7
9.7*
7.6*
6.5*
11.9*
10.0*
11.0*
R.T*
9.5*
12.7
14.3
13.2
12.2
13.2
12.5
14.8
15.6
14.1
14.1
13.4
14.7
12.5
14.0
12.8
14.9
10.3
13.3
12.C
1 1.3
11.3
11.5
10.6
11.6
13.3
11.6
12.®
10.8
1C .6
11.7
11 .4
11.1
12.2
14.1
12.2
12.4
12.2
14.8
10.S
12.5
12.3
17.6
12.9
2 4.3*
19.7*
16.7
10.9
11.8
35.7*
13.3
36.4*
5.4*
14 .5
15.3
10.5
13.1
5.1*
17.2
14 .4
15.1
9.3
11.8
9.0
12.5
-------
AMP
TRU
LAB
1
2
3
4
5
6
7
3
9
13
11
12
13
14
15
TABLE C-2
environmental monitoring and support laboratory
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEABLtS **
R A l» DATA FOR BFN2ENE ANALYSIS BY WATER TYPE
MEDIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
34343434
114.0 120.G 114.0 12C.0 114.C 12C.0 114.C 1*0.0
114.0
136.0*
117.7
109.3
105.1
107.3
76.8*
123.9
1 3 A . 3
108.3
127.1
14 7.0
112.4
? 0 7 . S
31.0
i:6.i
14 4.7*
126.5
129.6
96.8
S9.3
99.5*
117.9
146.C
106.4
1C3.4
141 .0
*
125.0
153.1
132.1
131.6 *
122.8
100.1
96.1
94.7
88.3*
1C7.7
139.0
92.7
124.9
90.0
313.4*
155.9
155.7
11C.C
169.3*
122.1
145.5
101.5
96.8
91.0*
14C.9
1 46.0
11C.3
127.1
14 4.0
12C.5
91.5
1 Lt .2
113.C
133.4
121.3
2C6.8*
102.1
92.8
8 6. 7*
148.3
126 .C
91 . 4
97.4
127.C
158.7
134.3
83.3
119.C
135.7
13C.8
15 8-1
114.0
113.3
92.7*
122.6
132.0
10?.°
10C.2
146.0
148.9
147.7
102.9
10? .7
135 .8*
125.7
120.fi
76 .8
98.1
103.0 *
144.8
144 .0
106.3
74.3
104 .0
1u8.fi
122.3
113.3
114.3
153.9*
146.3
15C.fi
V 3 . 8
77.5
97.7*
135.2
1 4 9 . C
99.7
97.2
147.G
0.0*
113.7
96.9
-------
1
2
3
4
5
6
7
8
9
10
It
12
13
14
15
TABLE C-3
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OfFICC Or RESEARCH A NO DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGE ABLE S **
RAW DATA FOR B EN Ifc N| ANALYSIS BY WATER TYPE
HIGH YOU D EN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EffLUtNT
5 6 5 6 5 6 5 6
480.0 43?.C 4SC.C 432. Q 480.0 4 32 .0 480.0 432.C
4 46.0
640.5 *
412*5
511.7
416.1
3 3 3.3
136.0*
405 .3
383.0
335.7
5 70.0
511.0
222.1
5 36.0
598.6
409.0
715.7*
361.9
43C.4
329.0
244.3
166.0*
396.7
397. C
283.3
406.0
466.0
282.1
358.5
145.7
*28.C
671.5*
3 9 5.5
444 .C
3 89.8
? 41 • 0
161.0*
3 54.?
35°..C
294 .2
5 07.0
516. C
429.9
471 .9
384 .7
37C.D
569.8*
BBC.7
523.0
427.8
243 .0
185.C*
428.8
35 w .0
256.7
483. 3
52C.0
366.9
394.0
6 6 8.4
443 .C
714.2
398.2
524 .5
424 .0
222 .3
238.0*
425 .7
266 . 0
274 .1
414.0
538 .0
332 .6
263.9
346.1
382.0
569.4
381 .0
2&G.5
366.G
35 2.3
188 .0*
451.8
2 7 7.0
270.8
362 .0
427.0
3C7.6
48C.5
444.6
428.7
745.5*
388.8
465.8
446.R
298.0
185.0*
443 .2
288 .n
289 .7
422.0
dco.r
**53.5
4 43 .1
370.8
41 C. 3
6 J 4 . 9 *
362.1
6u 3.9*
27 6.8
291 .8
181.0*
415.2
296.0
247 .2
361.0
441 .C
265.5
3G4 .C
307.5
-------
1
2
*
4
5
6
7
8
9
10
11
12
13
14
15
TABLE C-4
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAliLES **
RAW DATA FOR bROM0DICHLOROMETHANE ANALYSIS PY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
12 12 12 12
8.0 9*2 8.C 9.2 8.0 9.2 8.0 9.2
0.3
0.1*
7.4
9.3
9.1
4.7
6.5
7.3
9.9
6.3
7.2
4. 4
9.8
10.4
19.9*
5.6
12.1
6.3
7.5
5.6
4.2
3.9
6.5
8.1
8.0
6 . d
6.5
11.2
8.2
9.3
2.9
O.C*
2: .e
15.9
r .9
4.6
«• P
7.6
9.7
8 .2
r .r*
20.0
11 .3
c .c*
8.7
12.5
If.4
2C .6
14.8
S .4
8.1
7.2
7.5
t.7
7.4
4.3
17.0
1*.7
C .0*
1C.6
6 .C
5.1
7.1
5.4
8 . 3
6.5
5.6
7.6
3.9
8 .8
7.3
7.8
15.2
8.8
13.4
2.0
4.3
6.3
9.0
3.8
8.2
5.1
5.7
8 . 0
7.7
6.6
6.1
9.2
8.3
9.1
6.3
3.4
6.6
11 .8
6.9
6.3
5 .0
9.8*
9.1
9.0
8.3
6.5
8.0
7.3
30.2*
4.5
3.8
1 1 .6
13.7
9.3
4.8
5.1
7.6*
8.7
7.5
6.C
3.9
7.2
7.0
3.5
-------
1
2
3
I,
5
6
7
8
9
10
11
12
1 3
14
15
TABLE C~5
DISTILLED WATER
3
4
12?.0
114.0
156.0
77.6
1 43 • 0
75.9
124,6
102.C
139.7
89.9
144 .0
76,6
66 .6 *
6 3.0
92.2*
111.0
132.4
9 3.9
144.0
112.Q
140. n
132.1
117.6
97.fi
166.0
132.0
137.4
146.3
146.3
134.7
129.6
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** fcPA METHOD 624 VALIDATION STUDY - PUR6EAPLES **
RAW DATA FOR BROMOD1CHLOROMETHANE ANALYSIS BY WATTR TYPE
MEDIUM YCUOEN PAIR, UNITS - U6/L
TAP WATER SURFACE WATER INDUSTRIAL EFFlULNT
3 4 3 4
<*
12C.C 114.3 120.0 114,0 120.0 114,3
177.5
75.9
137.C
91.1
125.0
74.2
141.2
84.1
157.3
70.1
122.7
56.4
146.S
11C.fi
129.8
120.7
111.*
82.9
122.2
65.1
130.0
70.6
62.*
113.9
116,7
62.4
74 .3
111 .0
129.0
112.0
1CP.C
75.8
112.6
64.3
0.0*
50.6
104.C
92.3
105. C
96.4
119.C
92.4
151.2
7$.2
145.4
71.4
151,1*
143.5*
143.C
12:.3
127.C
122 .D
151 .0
125.2
124.4
124.9
129,4
105.4
137.7
105.1
96.0
9C.5
112.8
9?.4
83.2
99.2
97.6
133.0
137.0
131 .C
1C5.0
151 .C
3 60.3*
104.7
194.5
122.7
124.6
G.C*
14 2.3*
15.9*
153.8
131 .3
135.7
102.1
1 £9 ,6
1t5.5
120.6
143.6
94.3
125.4
-------
r« r
RU
AB
1
2
3
4
5
6
1
P
9
10
11
12
13
14
15
TABLE C-6
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 6 24 VALIDATION STUDY - PURGEA13LLS **
RAW DATA FOR DRCM0DICHL0 ROMETHANE ANALYSIS BY rfATEk TYPt
HIGH YOUCEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUtNT
5 6 5 6 5 6 5
(*12.0 A 80 * C 43?.0 48C.0 432.C 480.0 432 . 0 48C.0
443 .0
7 02.1
415.2
365 .9
485 . 0
459.0
279 .0
717.3
403 .0
528 .3
424.0
459.0
264 .4
4 5 3 .2
5 32 .1
473.C
723.4
451.5
472.1
333. 0
443.C
361.0
535 .6
601.0
516.2
463 . 0
519.C
386.3
417.6
389.1
468.8
66? .6
421 .5
3 69 .2
380.7
4 22 .0
33C.0
5 36 .5
5Q2.C
5 75 .1
685 .2
4 28.:
5 39.7
3 5 2.8*
408 .9
474 .7
63C.9
493.4
53E.5
361.7
5 2 9 .0
37C.0
6C1 .4
48 5.0
497.3
794.2
6 5 C . 0
47?.2
3 3 4.9*
593 .3
448 . 0
666 .6
404 .0
271.9
256.C
384.0
4 76 .0
414.3
390.C
53C.2
399.C
4 54 .C
3 82.0
260 . 2
5 55 .6
483 .0
723 .7
5 08 .5
319.8
522 .0
4C9.C
402 .0
577 .7
443 .0
519.9
430.0
475 .0
475 .2
510.2
559.7
412.0
737.3*
382 .6
262 .7
473 .C
331 .(?
345 .C
581 .1*
378 .T
482.3
402.0
531 .0
379 .1
^76.7
439.9
379.0
648.4
495 .1
477.2
35 8 .0
5-3 .0
367 . C
597.C*
5 4 8 . C
627.7
4 31.0
448.C
361 .3
329 .3
739.5
-------
r. r
RU
AB
1
2
4
5
fc
7
8
9
10
1 1
1 2
13
n
15
TABLE C-7
ENVIRONMENTAL MONITORING AND SUPPORT LAPORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAbLfcS **
RAW DATA FOR 8R0P0F0RM ANALYSIS BY WATER TYPE
LOW YCUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
1 2 1 2 1 2 1 2
9.0 1C.G 9.0 10.G 9.0 1C.0 9.0 10.0
7.6
9.5
P .2
10.3
10.8
7.0
9.2
8 .9
9.9
13.1
6.C
14.6
7 . C
12.9
7.5
13.4
7.6
7.2
6.2
8.0
5.7
6.2
6.0
3.2
3.9*
6.6*
4.6*
3.4*
10.1
9.4
6.6
7.4
4.?
7.4
6.4 .
6.2
6 .0
5.4
2.9
6.9
r.o*
2.8
O.C*
C.C*
3.6
C.C*
C.C*
2.9
5.1
3.7
3.4
3.6
2.3
1.9
2.3
3.9
5.9
e.1
5.9
9.3
9.6
8.1
7.0
7.3
9.5
11.5
7.5
19.7
9.0
9.7
¦2.5
12.2
8.5
U.1
e .7
9.7
13.1
11.4
9.2
14.5
8.1
9.1
5.2
6.0
8.4
8.3
8.®,
8.9
11.3
1C.8
14.7
12.2
9.5
11.2
7.3
12.4
11.1
1C.8
11 .C
24.3
9.1
8.5
6.2
4.9
11.5
13.5
4P .3*
11.3
10.8
1C.G
7.3
9.8
5 6.1*
5 4.3*
7.3
24.4
12C.4*
15.4
67.8*
4 . 1
-------
1
2
3
4
5
t
7
8
9
10
1 1
12
13
14
15
TABLE C-8
ENVIRONMENTAL MONITORING AND SUPPORT LAPORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL"PROTECT ION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEA&LES **
RAW DATA FOR BROMCFORM ANALYSIS BY WATER TYPE
MEDIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
3
4
3
4
3
4
3
4
95.G
ico.r
95 .'T
1CC.C
95 .C
1GG.C
95.0
1 G C . C
46.3
121 .4
49.1
134. C
42.9
1G2.C
4 8.9
104.7
4 fc . 2
85.5
63.6
1C7..8
54.6
1 2 C . 3
47.9
115.4
44 .C
113.7
37.4
1C7.6
65.2
6 0.1
17.6
33.4*
39. C*
59.8*
2 7.2*
£6.8
44.9
73.8
133.3
ICfe.G
41 .8
95.9
35.7
7C.4
46.8
85 .8
4 5.K
2 9.1*
14.C
72.6
35.1
62.6
23.9
8 7.2
14.1
77.6
1 16.0*
95.9
35.8
88 .5
51.5
94 .8
49.5
115.1
56.2
164.?
42.3
149.6
46.8
120.8
116.6
138.0
54.7
192.2
55.1
101.0
46.7
101 .0
60. 7
112.3
53.6
Rfi .3
79.9
83.5
44.3
105 .0
39.6
97.6
61.4
81.9
42.4
1 C 3 . 1
72.8
68.3
78 . C
123.0
73.2
69.1
& 4 . 9
104 .C
81.7
77.9
97.4
127.3
*
375.7*
5C.1
134 .2
51 .6
94.5
27.2
91 .P
75.8
?ie .9
fcC .3
111.5
84 .7
112.0
47.1
121 .9
29.C
13 6.:
89.5
125.6
75.2
65 .6
2 1 8 . C *
-------
nr
R U
A 8
1
2
3
4
5
6
7
8
9
10
11
12
15
14
15
TABLE G-9
ENVIRONMENTAL WONITORING AND SUPPOPT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
E N V IROMMENTAL PROTECTION AGENCY
EPA METHOD 624 VALIDATION STUDY - PURGEABLtS **
RAW DATA FOR OROWQFQRM ANALYSIS BY WATER TVPE
HIGH YOU D EN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE MATER INDUSTRIAL F F FLUE KT
56565656
4,0 0.0 360.0 40C.C 36C.C 400. 0 360.0 400.0 360.C
4:,».0
564..5
470.4
29 2 »3 *
39E.0
58C.0
532.0-
1603.2*
374.Q
1 SO. 6
4 34 .0
407.0
3s:.o
4 4 R . 9
49S.4
3 74 .0
564 .9
439.1
3 64.3*
305.0
519.0
530.0
495.9
459. C
373 .9
361 .C
34b.C
424 .2
3 6 5.9
6 £ 4 . 7
4 05 .C
5C6 .4
46! .9
296.3*
362.C
69F.0
604.0
750.1
818.2
453 .2
443 .2
415.0
726.C
416.2
4 55 .f
371.7
493.2
445.6
299.4#
314.0
6 8 5 .0
4 81.0
583.8
364.2
307.8
46 7 .2
565 .0
443 .5
3 4 5 .0
72 2 .6
469 .C
593 .7
479.3
355 .2
271 .C
473 . C
1025.0*
4E7.C
3C7.0
3C4 ,1
411.0
411.0
466 .8
28C.8
797.6*
3CC.0
572 .4
45? .9
254.5
361 .0
530.0
605 .0
508.5
3 34 .0
29* .g
348.Ch
338.0
437 .8
4C5 .2
417.5
425 .C
*04 .6
4 34 .3
3C1 .r
391 .0
657.1
584 .C
683.2
341 .0
40^ .3
4C5.0
408.0
2 70 .1
3 6? .5
'26.1
395 .0
515 2 . C
285 .7
469.6
29 5 .0
%08.0*
494 .C
463 .2
44 5 .C
290.9
319.C
357.0
341.6
299.5
2 317.1*
-------
RU
AP
1
2
3
4
5
6
7
8
9
10
11
12
1 3
14
15
TABLE C-10
ENVIRONMENTAL K-CMT0K1NC AND SUPPORT LAEORATGRY
OFFICE CF RESEARCH AND DEVELOPMENT
environmental protection agency
** EPA KETHOD 624 VALIDATION STUDY - PURGEAtfLES *•
RAW DATA FOR BRCNOHETHANE ANALYSIS BY WATER TYPE
LOU YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
1 2 1 I 1 2 1
1 r. 1 9.1 1C • 1 <5.1 10.1 9.1 10,1 9.1
3.7*
1C.4
6.6
4.:
4.9
0.0*
4.4
4.4
6.5
4.5
6.3
8.4
7.5
7.2
21.3*
2.9*
e.fi
6.2
2.9
7.4
24.5*
2 . C
16.4*
5.3
6.3
4.9
7.2
21.9*
4.6
1C.Z
3.6*
9.C
6.2
3 .S
3.5
47.9*
2.3
4 .3
6.3
8.7
0.9
7.4
7.6
2 3.4*
11 .1*
2.6*
7.6
5 .8
4.1
4.1
37.9*
3.*
3.0
7.3
6.4
3.1
C.O*
1C-.3
4.9
€ .3*
3.9*
9.0
6 .r
3.3
4.4
43.6*
3.8
8.8
6.1
7.4
5 .8
8.2
16.0*
6.0
7 . C
2.9*
1C.5
6.1
6.4
2.5
14.3*
2.2
10.1
5 .4
5.7
5
7.1
6.4
5 .C
3.4
3.5*
6.5
c p
^ • .
< .1
9.0
3. 0 *
7.1
17.3*
5 . F,
8 .4
5.1
5 .6
7.5
? .7
5 .0
4 . 2 *
8.5
13.4
fi.C
0.0*
30.1 *
2.6
4.3
6.7
5.0
4.7
f.
C.O*
4 .
9.3
-------
TABLE C-ll
£NV IRCNWEN7AL KGNIT0R1NG AND SUPPORT LAE'CRATGKY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
* EPA METHOD 624 VALIDATION STUDY - PURGEAOLES **
RAW DATA FCR EROWOMETHANE ANALYSIS PY WATER TYPE
MFDIUf YOUDEN PAIR, UNITS - UG/L
AMPUL NO:
TRUE CONC:
DISTILLED water
3
152,0
4
14 4 .0
TAP WATER
3
15 2.0
4
144,1
SURFACE WATER INDUSTRIAL EFFLUENT
3 <.
3
152 .C
4
14 4.0
152.0
144 .
LAP NUMBER
1
56.1*
4 2.5*
84.4*
47.5*
68.5*
38.8*
5? .5*
4 4.1*
2
157.3
7C.S
141 .2
65.6
12 2.0
£5.5
1 55.6
4 9.P
3
111.3
70.7
119.1
62.9
118.2
83.0
1C6•9 *
28?.C
4
64.6
84.3
77.7
64.0
164 .6
131.9
87.7
94.7
5
104.0
51.5
61 .9
49.2
56.3
£6.6
51 .6
67.6
6
426.
5 C. 1
718 .n*
456.:*
4 C 7 . 6 *
5 01.0*
675.0*
35 5 . C
7
67.7
PI .2
70.C
65.8
72.9
55.0
95 .8
6C.9
R
157.3
6 C. 5
£3 .7
63.9
89.4
1 £ 9 . C *
77.9
2t? . C
9
96.9
95.9
111
97.9
?5 .4
95.3
109.r
112.C
1C
120.»
75 .8
114.?
95.6
107.9
9 £ . 9
107.1
113.4
11
123.8
£3.7
12?.0
69.1
58.6
93.4
77.7
87.7
1 2
149.0
9 6.7
57.8
1 c 6. r
123.C
1C2.C
53 .C
10 7.0
1 3
105.7
*
3 6 C . 6 *
8 4 .
133.C
o £ . £
13 0.9
72.3
14
12 0.4
55.2
145.4
6C .3
116.2
77.4
111.?
44.9
1 5
152.2
76.7
167.1*
125.9*
62.4
133.3
2 08.5*
53.4
-------
1
2
3
4
5
6
?
8
9
ir
11
12
13
U
15
TABLE C-12
ENV1RON^ENTAL MONITORING AND SUPPORT LAfiQRATOPY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALI DAT I ON STUDY - PURGE AbL£ S **
RAW DATA FOR E ROMO*!£ THANE ANALYSIS 3Y WATER TYPE
HIGH YOUDEN PAIR, UMtS - UG/L
DISTILLTD WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
5 6 5 6 5*56
546.0 6C 7 ~ 0 546.C 6C7.Q 546.C 6C7.G 546 .0 607.0
24 8.3*
424 .4
382.7
416.4
4*6.3
2366.0*
c 11 . J
322.«
302.0
415.6
466.5
413.3
498.3
506.9
436. n
277.t*
681.1
468.2
8 C 6 . 5
296.C
375 .C
326 .C
126*.8*
461 .0
325 .8
563.0
453 .0
492.9
483 .1
75 j .0
£82.0*
554 .4
381.7
664 .1
2 84 .C
33! 0.0*
272 .0
3 CO . 2
391 .0
345 .9
177.C
511 .0
609 .9
367 .6
6 91.7*
27C.C*
382.9
468.4
1021.0
2 8 7.0
2 8 1 C «1 *
290.0
774 .6
3 6 8 .0
4 3 5 .5
279.0
439.0
671,C
52 1.1
689.0*
228.0*
427 .7
4C4.4
386.7
243 .0
2270.0*
331.0
741.2 *
*G5 .0
401 .?
417.0
392 .C
327 .1
259.6
607.3*
217.0*
702.4
*25.8
395 .9
483 .0
1230.0*
3 34 *0
746 .1
331 .0
4G&.0
425.0
4 6 4 . C
463 .0
58C.7
260.5
223.0*
4 21.5
397.5
661.6
456 .0
272 .9
335 .0
351.4
?92 . 0
3£2.7
462 .0
483 .0
425 .7
3S9.3
633 .$
c 7 6 . 0 *
575.9
1991.?*
64 C .8
3G0.G
5241.0*
314.0
1087.1*
4 i 9 . 0
568 . 5
44 2 .0
466.C
5 34 .3
346.4
26 3 .3
-------
MP
RU
AO
1
2
3
4
5
6
7
b
9
10
11
12
13
n
1 5
TABLE C-13
LNVl RONMfNTAL KOMTOHING AND SUPPORT LAPORATORY
OFFICE CF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAGLES **
RAW DATA FCR CARBON TETRACHLORIDE ANALYSIS BY WATER TYPE
LOW YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EMLULNT
1
2
1
2
1
2
1
2
9.3
tc.c
9.0
1C.0
9. C
1 0. C
9.0
1C.G
7.5
9.3
S.1
6.6
8.4
9.7
7.4
8.9
12.3*
U .9*
12.5*
U.1*
6.2
14.0
10.3
11.9
8.?
9.C
7.5
9.1
8.0
9.1
3.5
8.2
8.0
9.A
7.8
9.4
?.1
13.7
6.4
t • 9
9.5
a .9
4.6*
9.1 *
7.4*
3.4*
7.7
9.9
6.1
9.7
6.1
e .9
8.2
8.7
6.0
6.5
4.9*
4.2*
3.3*
* .4*
5.6
5.7
4.3
5.8
6.5
a.b
9.3
9.7
7.5
8.4
12.3*
1 C • 4 *
5.6
1 C . 9
IP.4
13.2*
9.3
11.1
10.0
12.1
6.2
9.5
7.6
7.9
8.3
8.9
8.2
8 .4
P.7
10.2
6.9
7.8
9.4
10.5
8.7
8.9
11.0
13.4*
10.R
8.6
11.3
12.7
9.6
14.C
8. 1
1.5*
e .t
1? . 7*
14.8
10.8
7.1
7.8
10.9
10.2
35 .r*
9.6
11.fi
1C .9
9.3
10.2
1 9 .3 *
12.6*
7.^
9.9
7.0
P .5
10.1
6.5
-------
1
2
I
4
5
t
7
8
9
10
1 1
1?
13
1 A
15
TABLE C-14
tKVlRCNMENTAL MONITORING AND SUPPORT LAPORATOPY
OFFICE OF RESEARCH AMD DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PUWGEAbLt S **
RAW DATA FOR CARDON TETRACHLORIDE ANALYSIS PY WATER TYPt
* E D I UM YOUDEN PAIR, UMTS - UC/L
DISTILLED WATER TAP WATEP SUPFACE WATER INDUSTRIAL F F F L U t % T
34343434
95,3 1GC.G 95.0 ICC.3 95.u 100.0 95.0 10C.0
109.0 62.8
137.9* 7 2.2*
97.7 58.4
111.6 76.6
104.0 44.4
52.9* 53.C
67.8* 78.7*
115.7 73.8
112.1 90. C
107.5 81.5
101.4 86.9
12 2." 86.6
97.0
105.9 69.9
151.9* 98.4*
1C7.3
6 7.6
150.9*
fc9.1 *
1C7.C
52.9
98.4
54.3
79 .9*
33.5*
84.7
6?.7
66.5*
59.3*
1 34 .9
6 4.9
121 .0
94.6
£6.1
U8.2
1 13.4
67.7
86.6
1L2.G
2 8 8.5*
14.5
172 .4
69.8
151.1
8 4.1
1C6.C 6 7.9
117.2 61.5
1C5.4 9 C . £
1 3 3 . 5 6 C . 1
39.3* 67.1 *
fc 9 . 7 5 5 .1
71.9 66.4
124.7 70.2
92 .2 107 . C
95.1 87.9
110.1 96.8
1G3.0 £5.?
146.6 105.:
126.9 110.4
93. C 91.8
90
.7
61 .8
96
.3
6 0 .6
15*
.6*
9 8.8
6r
.7
91 .9
94
.2
6 3.0
80
.0
35.5
87
.4
71 .£
151
.4*
15 6.2*
117
• L
loC.C
U6
.4
6 5.8
74
.3
89.2
95
.2
84.9
93
.1
tO.5
116
.9
69.3
82
.2
105.1
-------
RU
AB
1
2
3
4
5
6
7
£
9
10
1 1
12
13
14
1 5
TABLE C-15
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** FP* METHOD 6 24 VALIDATION STUDY - PURGEAHLtS **
RAW DATA FOR CARBON TETRACHLORIDE ANALYSIS E Y WATER TYPE
HIGH YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
5 6 5 6 5 6 5 6
400.0 360.0 400.0 3 6 0 .0 400.0 360.C 400 .0 360.0
397. n
333.r
366 .r
32 1 .C
391 .0
¦ 332.0
37? .0
339 .0
706.5*
666.6*
87".6*
559.6*
597.9-
6 01 . C
831.1*
513.3
443.3
388.6
431.5
431.1
4 5 0.5
428 .4
4 06 .7
594.9-
395.8
<.cn.2
36C .8
521 .3
361 .2
221 .1
394 .4
378 .1
446.0
265.C
3 4 S . C *
18 9.0*
164.0*
338.0*
401 .0
3 0 3 .0
468.0
323 .0
400 .C
4 2 7.0
3 66 .0
367.0
2 37 .8
398 . 0
?24.n*
238.0*
2 4 5. r *
2 5 5.0*
380 .0
280. C
?01 .0
271 .0
739.0*
473 . 1
561 .9
5 77 .6
451.5
467 . g
t89.3*
562 . 7*
376 .0
<21 .0
4 96.0
3 5 3 .0
351 .C
305 .C
341 .0
3 99.0
498.9
382 .2
5 5 5 .4
377 . v
482 .9
400. 2
460 .?
4 S 0 . 8
4 3 5 .0
4C2.C
3 79 .C
3E2.0
427 .0
3 5 3 .0
4 19 .C
315.C
398.0
372 .C
4 77 .0
4 13.0
3 73.0
3 5 0 .0
5 05 .0
401.0
236.4*
3CG.6
502 .5
38C.5
377 .3
361 .6
3*0.2
284.7
517.6
490.C
4 41.0
4 3 4 .6
314.8
526 .0
4 22 .9
57.9*
522.5*
447.9*
36 7 .6
554.3
428 .7
344 .5
313.3
5^6 .9
-------
1
2
3
4
5
6
7
8
9
U
11
1 2
13
1 A
1 5
TABLE C-16
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRCNfEKTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAfcLE S **
RAW DATA FOW CHL0ROBEKZENf ANALYSIS BY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
12 12 12 12
13,5 15.: 13.5 15.C 13.5 15.0 13.5 15.0
U.I
15.8
15.3
1 5.4
15.2
13.5
1£ .7
15.0
17. 4
10.6
15 .4
14 .C
16.9
17.7
2 8.3*
20.3
20.6
17.2
14.7
14. fc
14.6
11.2
17.6
16.6
16.8
15.2
16.2
19.9
16.6
31.4*
2?.4
13.4
13.3
16.9
17.4
11 .6
10.6*
15.8
16 .n
15.2*
14.3
17.C
IS.1.
5 3 . C *
14.P
It. 9
22.2
15.6
16.5
16.3
13.6
1 2.9*
13.1
25.7
13.3*
13.5
14.4
3 8.6*
15.0
25.9
16.6
11.1
16.9
15.C
14.2
16.4
10. P*
19.7
15 .C
16. ?
14.3
14.6
22.9
17.7
20.2
25.9*
19.5
1 e .7
45 .1 *
17.1
15.5
13.4*
16.7
1 5 .6
17.8
19.1
17.4
17.5
2 0.4
2 0.9
21 .0
12.5
11 .9
12.6
19.1
11.0
?.7
15.*
14.3
12.C
16. *
12 .*
14.9
13.5
2 0. 7
15.8
21.4
17.4
15.6
13.1
13.4
16.C
18.4
17. j
16.1
16.3
13.4
21.6
16.4
11.3
-------
n r
RU
AB
1
2
3
4
5
6
7
8
9
10
11
12
13
1 ^
15
TABLE C-17
ENVIRONMENTAL MONITOR ING AND SUPPORT LAP OR A TO R Y
OFFICE OF RESEARCH AND DEVELOPMENT
ENV1RONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAi'LLS **
RAw DATA FOR CHL0ROREN2ENf ANALYSIS bY W AT t R TYPE
MEDIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUlNT
3 4 3 4 2 4 3
142.0 15:. C U2.C 150.0 142.0 150.C 147.0 1 b 0. C
222.9
161.2
156.0
160.1
H6.0
137.0
83.4
155.1
171.0
97.3
151.7
183.0
132.5
176.0
211.5*
199.9
193.8
182.2
2C1 .0
133.0
128.G
11*.0
157.3
17 0.0
1 C 3 . 5
139.7
1 9 7 . G
159.C
14 7.4*
116.8
131 .4
161 .C
6* .8
138.0
111 .C
98.0*
123.C
227 . C
91 .1*
143.3
127. C
579.4*
2G7.C
161 .7
18 8.0
212.0
15 2.8
137.8
168.0
12 2.0
£9.0*
163.2
1 7 7 . C
124.9*
1 5C .9
167.0
146.1
154.4
172.6
164.C
187.0
18 9.3
207 .5
155.4
147.2
92 .4*
212.0
164 .C
1C0.C
124.2
149.G
2C3.4
164 .8
151.8
2 3 3 .0
1 71 .5
199.0
14.8*
160.3
160.0
108.0*
15 3.6
143.0
113.0
131.9
174.0
155.9
166.5
154.7
1 7 r>. 0
1 75 .7
193.5
36.1
141.0
12C.0
90.9
174 .5
172.0
116.3
1 J 7. 6
1 6 ? . 0
134.3
136.3
113.6
18 2.0
P2C.7
119.C
155.2
143.0
73.9
99.7
177.S
1 7F .0
90.3
127.C
2 5 0.0
195.1
12 9.6
165.7
-------
1
2
3
4
5
6
7
&
9
1 0
11
1 2
1 I
1 4
1 5
TABLE C-18
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 6?4 VALIDATION STUDY - PUR GE A 5L E S **
RAW DATA FOR CHL0ROOENIENF ANALYSIS PY WATER TYPE
HIGH YOUDEN FAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACF WATER INDUSTRIAL EFfLUtNT
56565656
frj0.0 540.C 6C0.C 5 4 C . ? 600.C 540.0 60C.0 540.C
690.9
*5?.?
716.6
263 .4
6 5 5.0
536 . n
2 8 4.0
6 JO. 3
547 .0
287.7
717.3
457 .0
420.2
6 76 .6
729.4*
586.9
931.8*
5 5 6 .6
616.1
5C2.C
398 .r
385.C
513.4
3 3 6 . L
2 57 .7
53?.C
5 96 .C
4 6 8.9
576 .5
679.2*
451.0
7 fc £ » 8
572 .5
330.2
564 .C
3 84 .0
321 .0*
461 .r
5 4 5 . C
314.5*
6 4 C . 0
492 .C
1 C 61 .1 *
5 89. C
425.9
765.0
745 .4
569 .3
556 .2
6 3 5 .0
*<77. J
371.3*
565 .1
499.0
243.5*
797 .0
74?.:
771.6
477.6
697 .9
604 .C
9L8.8
765 .?
493 .C
660.C
394 .C
567.C*
246 .6
191 .0
259 . 2
5 6 7 . C
613.0
472 .3
334 .3
6CC.1
789.0
822 .9
621.3
683 .7
5 3 6 . C
5 2 2 . 0
389 .0*
63 2 .1
22C.C
271 .1
4 99.0
4c8.G
439 .7
662 .8
529.2
74 4 .0
949 .3
494 .6
220.2
656 .0
3 11 . 0
3 35 .0
636 .C
19 8.0
276 .*
620.0
642 .0
791 .4
515.6
4 17.5
6 5 7 • G
869 .3
43 1.4
444 . C
417.0
451 .C
3 7 3 . G
54 2 .5
2C2.0
24C.5
500.0
4 5 3 .0
442 .5
6 J 5 . 6
5 5 3 .0
-------
1
?
"?
L
5
ft
7
8
9
1C
1 1
12
1 3
1 4
15
TABLE C-19
ENVIRONMENTAL K0NIT0R1NG AND SUPPORT LAP ORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTICN AGENCY
** fcPA METHOD 6 24 VALIDATION STUDY - PURGtABLLS **
raw data for chlcroethane analysis er water type
LOW YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
1
c
1
2
1
2
1
2
8.1
7.3
* .1
7.3
8.1
7.3
9.1
7.3
5.6*
5.C*
6.7
3.6
6.5
3.4
6.0
7.7
19.1
12.2
13.3
6.9
1C .4
22.9
1C.7
U .0
6.2
£ .£
11 .«
3.6
13.6
6.8
6.3
20 .8
11.3
8.0
8 .4
7.1
5.9
15.5
9.2
12.7
9.5
5.7
1C.0
6.9
6.7*
2.5*
9.3
7 .C
5.9
6.7
1C.1
6.9
5.9
6.8
6.?
7.3
6.1
3.6
3.9
6.3
6.1
4.4
5.2
4.4
6.2
17. Q
6 .8
4.7
- 10 . C
11.7
19.8*
6.2
U.I
E.C
13.6
14.C
16.C
14.0
8.5
I7 .6
6.6
7. 8
9.9
8.4
9.2
7.6
9.4
t .0
7.8
f .C
c.o*
c.c*
6 .1
C.C*
0. c*
4.7
10.6
8.7
0.6
c. c *
14.5
11.9
11.1
13.7
1C.6
16.5
11 .6
11.1
U . 1
11.3
10.7
7.1
10.3
7.1
39.6*
7.5
11.8
8.5
6.9
7.9
? 3 • 7
11.0
13.5
1C.5
6.C
11.9
5.6
11.5
-------
1
?
3
4
5
6
7
8
9
10
11
1 2
1 3
14
15
TABLE C-20
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PUR6EABLES **
RAw DATA FOR £ HLO ROE THA N£ ANALYSIS BY WATER TYPE
MEDIUM YOUDEN PAIR, UNITS - UCi/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
34343434
122.C 116.G 12?.0 1 16.: 122.? 116,0 122,0 116.0
76*1*
6 C . 6 *
1 16.7
72.2
U7.0
47.4
61 .C
57.6
2 16.6
9C.4
231 .7
7 F * 2
163.5
115.G
?G1 .1
74.1
152.9
87.7
13C.6
152.2
123.1
119.9
335 .3
3 7 0.2*
21.4
1C3.C
123.?
7^.9
121.3
2 57.1
122.3
106.0
71.a
91 .4
64.1
78.6*
71 .9*
1 18.0
73.4
99.8
SO.4
1 71 .C
94.3
107.7
90.7
135 .0
64.7
91,1
91.4
95. e
ec.?
93.2
74.1
na.o
ac.o
173.0
66.9
104 .2
83.1
110.C
189,5
102 .9
? G 2 . 0 *
131.0
UC.C
127.D
11 9 . C
115.0
107.0
132.C
118.3
152.6
97.6
144.1
127.1
143.2
118.9
134.1
12£.C
18 6.6
9&.1
165.6
b 6 .2
137.4
113.4
11G.2
1u* .1
222 .0
144.C
121 .r
19$.n
177.C
156.0
124.*
13 2.0
145.7
*
? 61 • 5 *
97.4
180.9
12 2.?
168 .9
o4 .6
179.8
72.4
23? .7
81.3
171.1
134.1
15C.9
79.G
169.5
87.9
199.C
16 r. i
141 .3
145.3
2 37 .5
52.7
-------
* n
1
2
7
4
r
6
7
£
9
10
11
1?
1?
14
1S
TABLE C-21
ENVIRONMENTAL rOMTORING AND SUFPO f- T LA Ef. ORATORY
OFFICE OF RESEARCH AND OF VF LOP^E NT
ENVIRONMENTAL PROTECTION AGENCY
*• EPA PETHOD 6 2 4 VALIDATION STUDY - PURGEAtiLES •*
RAW DATA FOR C HL 0 ROE THA N E ANALYSIS BY WATER TYPE
HIGH YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
5 6 5 6 5 6 5 6
4*7.3 488.C 447.0 4££.0 447. 0 4£?.0 4 47.0 48?.R
301 .0*
561.5
501 .6
554 .7
43? .0
5 4 5 .0
267.0
350.4
364 .C
562.4
693.0
594.0
64 3 .4
666 .6
601 .6
434 .C*
849 .3
497.7
5 6 1 . C
426 .C
5 84.0
35C.C
13 61.2*
382 .C
451.1
562 .0
769 .C
646.9
610.4
747 .1
3 7? .C
857 .6
311.7
5 CP .5
3 91.0
7 23 .0
327.C
364 .2
42C.C
4t2.fi
223 .C
8 34 .0
5 8^.5
474 .9
7 33 .6
359.0
5C2.3
1504.9*
516.2
367.0
63C.0
7 £ 4 . C
971.5
4 17.:
574.5
3 2 ?.
6 6 6 . C
772.?
74 5 .8
737 .0
5 57 .6
211.2
584 .2
28 2.0*
4 34 .6
414 .C
7 7C .6
34C.C
5 31.3
421 .0
6 5 3 .0
4 6 £ . 1
3C9.6
6C9.5
284 .0
907.1
676 .1
416.8
3 V 3 . C *
52? .6
431 .0
£31.3
382 .0
562 .5
4 3 5 .0
686.C
6 0? .9
784 .3
767.5
7 46 .n
5 £ 4 . ?
4 19.*
946 .3
4C9.0
5 93 .9
414.0
436 . 5
337 .C
439 .7
456.:
752 .0
490.4
4 92 .F.
7SS . 7
369. C
762 .7
2 510 . C *
843.4
3 6 £. :•
664 .:
3v4.0
1112.6
4 \j 1 . G
6 2 4.6
r,
~ > - • w
9£fi.O
691 . 4
4 4 8.5
271 .6
-------
TABLE C-22
ENVIRONMENTAL KONITOR1NG AND SUPPORT LAFiORATOfif
- OFFICE OF RESEARCH AND DEVELOF^tNT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 62A VALIDATION STUDY
PURCEAfcLES **
RAW DATA FOR CHLOROFORM ANALYSIS BY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER
TAP WATER
SURFACE WATER INDUSTRIAL EFFLUENT
A-lPUL NO:
TRUE CONC:
1
5.0
1
5.0
£
4.5
1
5.C
2
A .5
1
5 .0
2
A.5
L A Li NUMBER
1
3.9
3.a
C.O
1.7
5.3
A.3
A .0
3.7
2
6.6*
7.5*
8.6
7.3
A.6
6.3
< .1
5.9
¦*
5.A
A.7
A 3 . £ *
A 1 . 9 *
5.3
5.1
7.**
13.8*
A
6.6
5.5
31 .A
A5.3*
A .9
9.9*
1 2 . r» *
13.1*
5
A.5
A.C
C.O*
1C.6
3.6
1.2*
e.r*
C. G*
t
A.2
5.6
5.3
5.8
5.C
A .2
1 .9
2.5
7
A . 1
2.A
P.C*
1C.A
O.C*
C.O*
3.7
3.2
R
A.9
A.6
5.A
3.9
A .9
A .2
7.?
6 . w
9
5.7
5.C
5 .A
5.0
5 . C
A .7
5.2
5 . 3
1C
A .7
A.3
3.1
C.9
3. A
3.7
A .9
2.9
11
5.1
A.5
c.r*
3.0
5.1
A .6
7.6
5 .ti
12
3.7
A.5
19.7
26.7
A.3
A .5
5 .*
A.C
13
6.1
8.9*
17 .1
19.2
8.5
5.9
5.1
5.2
1 A
A.A
A.5
o.r*
C.j*
7.3
5.3
A . ?
6.c
15
S.Q
3.7
c .c* .
c.c*
C.C*
C.C*
O.C*
0.0*
-------
i*. r
RU
AB
1
2
t
4
5
6
7
8
9
10
11
12
1 3
14
1 5
TABLE C-23
ENVIRONVENTAL komtoring and support laporatory
OFFICE OF &LSLARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENClf
** EPA METHOD 6 24 VALIDATION STUDY - PURGEABLfcS **
RAW DATA FOR CHLOROFORM ANALYSIS BY WATER TYPt
MEDIUM YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAF WATER SURFACE WATER INDUSTRIAL FFFLUtNT
3 4 3 4 3 4 3 4
75,0 71.C 75.C 71.C 75. C 71. G 75 .0 71 . C
68.6
98.8*
75.7
59.2
72.2
63.6
5 C • 5
75.3
eo.4
61.0
79.0
94.4
77.0
SI .7
66.3
A 7. 1
6C.5-
53.2
59. 2
4C.1
56. C
63.5
54.8
88.3
54.4
63.2
65.1
~
96.2
58.9
75.6
112.6
117 .4 *
92.9
58.3
7 4.4
55.1
6 * . 6
76 .1
5C.7
54.5
75.4
2 th .5*
92.3
C.O*
38.5
69.6
7 6.1*
62 .4
5.7
59.9
54.8
62.2
8? .8
58.2
49.9
99.4
tf .6
15.?
O.G*
7 0.7
85 .C
78 .4
114.3
39.7
68 . 1
58. r
86. C
69.4
54.9
74 .5
79.5
138.5
92.9
3 6.0*
56.4
54 .9
68.6
5C.0
55.3
57.7
50.4
5 4.8,
75.4
54.C
65.4
65.2
66.2
61.fi
33.0*
59.7
70.3
124.2*
68.2
46 .4*
69 .6
72.0
83 .8
*5.*
59.7
57.C
76 .5
76 .7
87.4
2 S . 5 *
49.5
46 .9
13 2.4*
6 5 . c
28
33.1
5P .2
9C.9
88 .3
'57.7
e5 .C
6 0. C
6 4 . C
4' . ?
-------
TABLE C-24
ENVI RCN^ENTAL MONITORING AND SUPPORT LAR0RAT3RY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** L P A tfE THOD 624 VALIDATION STUDY - FURGEAbLES **
PAW DATA FOR CHLOROFORM ANALYSIS BY WATER TYPE
HIGH YOUDEN PAIR, UNITS - UG/L
AMPUL NO:
TRUE CONC;
DISTlLLfD WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLL'LNT
5 6 5 6 5 6 5c
270.0 3CC.C 27C.C 3CC.0 270.C 30C.0 270.: 3GC.0
Ul
LAD NUMBER
263.9
245 .9
? 5° .9
227.5
246 . r
260.C
2 22 .7
2 5 ? . 6
409.5*
4 4 6.1*
464 .2
41C.3
362 .7
41:. 3
4 6 6.9*
366 .7
264 .?
3CC.2
2 9 5.1*
361.5*
2 73 .3
? 26.5
2 5 8.9*
6 C 7 . 3 *
240.5
268 .6
260.2
3 7 6.0
1£2 .5
265 .3
2 4 5 .1
2S>6 . 2
272.0
221 .C
222.3
165.3
142.7
26? .7
245 .6*
2 C 6 . 6 *
289.0
263.C
260.0
3 4 7 . 0
240. 8
2 77 .8
197.2
302 .6
Ufc.O*
2 2 C . 0
194.0
2 C 4 . 0
24P .0
248 .0
231 .r
224 .C
254.3
2ED* 9
2 2 5 .0
32C.5
225 .C
319.8
?C6 .6
346 .0
235 .0
354.0
2 79 .0
? 9 1 . 0
2 2 5 . C
247.0
222.0
3 2 6. C
218.4
203.6
214.5
192.7
2 o C . 2
212.6
195.1
2*6.4
301.0
375 .C
592.3*
7 u 2 . 3 *
2 66 .0
283.C
295 .3
3 09.0
24 5 .0
325 .0
331.0
3 C C . 0
26C.0
289. C
311 .0
3 3 1 . C
230 .3
4 5.1*
£6.2
7f .2
48.?
346.3
3 24 .R
3 0 6 . C
68* .4*
354.6
257.9
3 32 .5
2ca.9
3 8 2 .1
285.1
2 e> 5 . 5
292 .6
223 .5
197.8*
253.8*
216.3*
259.4*
155.?*
87.4*
-------
TABLE C-25
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEA0LES **
RAW DATA FOR CHLOR0*ETHANE ANALYSIS BY WATER TYPE
LOW YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER
TAP WATER
SURFACE WATER INDUSTRIAL EFFLUENT
AMPUL NO:
TRUE CONC:
1
7.3
2
7.
1
7.8
c
7.0
1
7.8
2
7.0
1
7.8
I
7.0
LAB NUMBER
1
2.9
3.7
4.4
2.2
2.5
3.0
1.8
2.9
2
14.4
10.4
18.6*
1 C. 2
12.4
12.9
9.6
1C .0
r
7.7
6.6
6.6
6.6
7.2
6.9
9.1
c 4 • 5 *
4
K .8
6.5
P .C
* .4
5.5
12.7
1C.2
3.2
5
4.7
5.2
6.3
4.7
4.6
1.3
5.3
4.9
6
Q. 0 *
C.C*
O.T*
C.C*
O.C*
C.C*
0.?*
O.C*
7
6 .?
3.9
4.2
6.6
8.0 '
4.2
5.3
3.8
3
5.6
27.C
6.3
3.9
10.8
14.2
26.?*
5.0
9
0.0*
32.6
c.c*
15.5
2 6.1*
37.1*
0.?*
43.5*
10
3 .6
7.3
*
6.6
5.2
2.9
*
5.0
1 1
0.0*
8.1
C .0*
C.C*
8.4
9.3
8.5
7.2
12
6.4
O.C*
7.4
1.0
3.7
O.C*
9.?
1P.1
1 7
9.4
n.c*
7.5
15.6
13.4
10.6
14.4
4.0
14
11.3
9.1
51.2*
9.1*
O.C*
9.6
0.0*
9.3
15
57.1*
26.5*
3 5.6*
2C.4*
2 5.7*
25.9*
12.9
52.4*
-------
HP
RU
AB
1
2
3
4
5
6
7
V
9
10
11
12
13
14
1 5
TABLE C-26
LWVJ ROME NTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
y .
** EPA METHOD 624 VALIDATION STUDY - PURGE AwLE S **
RAW DATA fOR CHLOROMUHANE ANALYSIS BY WATtR TYPE
MEDIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WAT fc R INDUSTRIAL EFFLUENT
3 4 3 4 3 4 3 4
117.0 111.3 117.0 111.C 117.0 111.C 117.0 111.0
81.9
72.7
62.7
72.4
5 5.2
56.0
69.1
35.1
217.8
9 3.5
2 70. 2
93.5
179.0
104.1
230.2
76.2
132.2
9 C.C
135.8
75. 3
126.0
94.3
511.n*
669.2-
109.4
73.5
135.3
73.1
292 .5
115.4
85.4
136.8
92.6
59.2
69.2
6 0.7
105.9
65.8
84.3
6C.7
0*0*
O.C*
0.0*
0.0*
0.0*
0.0*
e.o*
>*, „
. . V
96.4
86.9
1G1 .C
89.7
1 10. C
65. 8
117.0
60.0
218.4
60.7
99. C
77.7
122.6
306 . O
85.6
352 .4*
44.2
376.C*
111.0
94.3
296.0
44.S
7S .6
?c.e
2?.9
87.8
121 .C
1.3*
120.2
71s.1
1 17.9
1 • z
181.6
143.9*
1 71 .6
*5.1
209.3
126.4
11C.2
13 9.2
11 3 . r
£1.2
1 13.C
1C 5 .0
114.0
96.9
139.0
?t .1
134.1
*
3 01 .0
73. 3
164.7
117.8
201.8
C. 0 *
251 .C
97.8
I S1 * £ *
99.1 *
2C5.8
e.o*
2C1 .1
8.6
*58.7*
12 5.2*
3 4 3.3*
42*.8 *
251.7*
422.4*
717.4*
138.6
-------
1
2
3
4
5
6
7
b
9
10
11
1 2
13
1 4
15
TABLE C-27
EIWIRCNMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE Of RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA KETHOD 624 VALIDATION STUDY - FURGEAULfS **
RAW DATA fOR CHLOROME THANE ANALYSIS BY UAThR TYPE
HIGH YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL F F F L U fc N T
5 6 5 6 5 6 5 6
422-0 469.C 422 *0 469.9 422 .C 469.0 4 22 .r 469 .0
234 .0
2 3 5 . C
26C.C
3C1 .0
184 .0
3C2.0
256.0
204 .0
515.2
917.3
1 C 2 2.8 *
559.7
669 .5
8 59 .2
605 .1
8 16.0
49 8.0
526.4
419.G
4 9 6.8
492 .1
A 9 6 . 6
5 58.3
2256.7
564 .2
590.4
4?£ .8
63?.3
697.8
498 .2
9 8 5 .0
1186.5
361.0
327 .C
294 .0
40C.0
377. C
364 .C
T37.r
34 5 .0
0.0*
0.0*
C.C*
0.0*
0.0*
C.O*
o .r*
0.0
18 9.0
266.0
279 .0
2 6 7.0
289.C
344 .0
294 .0
222 .0
314.3
1794.1-
3 51 .4
9C7.9
118 9.3
1028.2
4 03 .7
1515.9
184.0
53.7
92.4
174.3
736 .0
163.C
195.?
5 6.6
fOC.5
302 .4
4.2
5 D £ . 4
847.4
434 .0
4 CP .1
37.5
6 9 7.0
922.0
77.0
2C3.0
462 .C
6 6 2 .0
741 .0
5 5 7.0
296.0
469.G
5C9.C
368.C
389 .C
388.C
5 C 9 .9
665.9
7.5
668 .4
5 52 .C
6 53 .5
463 .C
547.1
2 39 .4
777.4
809.4
772 .C
570. 2*
101C.6*
334 .6
134.5
6 21.0
66.9
9 6 5.9*
1913.1*
1727.9*
1511.5*
18C2.7*
2087.2*
2^71.7*
633.8
-------
MP
RU
AP
1
2
3
A
5
&
7
6
9
1U
11
12
1 3
U
15
TABLE C-28
ENVIRONMENTAL MONITORING AND SUPPORT LAUORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 62A VALIDATION STUDY - PURGEABLES **
RAW DATA fCR C I S -1 , 3 - D I C H L 0 R 0 P R 0 P E N E ANALYSIS H Y WATER TYPt
LOW YOUDEN PAIR, UMTS - UG/L
SURFACE WATER INDUSTRIAL EFFLUENT
12 1^
3 • C 8.9 fi.C £.9
DISTILLED WATER TAP WATEK
I 1 Z
fc.9 6.? 8.9
6.A
10. 5
19.1*
12.1
10.8
c.o*
5.5*
8.2
12. n
A. 3*
7.2
8.3
8.7
11 .C
32.9*
9.6
15.1
17.8*
7.1
9.1
6. A*
A.I*
11.1
U.5
6.A*
8.6
8.5
1C.3
6.7
2A .7*
8.5
6.1
17.6*
5.2
7.7
5.2
3.3*
R .9
11 .8
5 .5*
7.1
9.3
1 C . 8
31 .1*
12.8
1C.C
15.2
19.1*
e.2
9.2
C.O*
6.5*
9 . C
12.5
A .9*
6.9
9.2
19.9
6.9
1 A . 3
9.9
8.9
16. A*
10.9
11 .1
6.6
A.9*
11.2
11.9
6.3*
7.7
8.2
1C.3
9.2
AO.A*
8.7
1A .A
16.9*
1C.3
2.8
A.5
5.7*
9.7
13.0
5.3*
8.5
9.6
9.1
12.8
18.2
9.2
9.5
13.7*
11 .7
9.6
5 .3*
A.2*
1C .6
11 .6
5 .9
7.7
11.2
6.3
6.7
1C .6
9. A
1 A . 5
33.A*
9 . 3
10.9
7.2*
5.7*
1C.3
15.9
5.1
7.8
8.5
7.7
10.8
10.A
-------
LAP
1
2
3
A
5
t
7
a
9
10
11
1?
13
u
15
TABLE C-29
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE Of RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA hETHOD 624 VALIDATION STUDY - PURGEABLES **
RAW DATA fCR C1S-1 , 3-D I CHLOROPRCPENE ANALYSIS BY WATER TYPE
MEDIUM YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EffLUtNT
34343434
85 .0 69.G 85.0 E9.0 fe 5.C 89.C 85.0 o9.C
12A.0
1 13.C
1 <6.5
1C5.0
126.C
134.C
106 .C
125.0
145.8
138.7
133.3
158.6
135.C
145.9
1 34 .4
14 6.6
217.6*
227.3*
212 .8*
2 3 8.7*
2C7.4*
239.2*
17!.4*
299 .6*
101.3
12C.1
94 .7
1C7.1
168.6
110. C
104.5
13 6.7
130.0
9t .2
1 05 .C
74 .3
4C.8
137. C
1 13.0
128 .C
79.5*
39.3*
74.2
79.5
54.5
61 .1
70.2*
58.8*
6 2.5*
85.6*
70.3*
86.5*
72.3*
64.9*
80.3*
S 1 . 9 *
120.7
156.7
126.5
124.1
149.8
126.5
126.2
131.8
121.0
n?.c
116.0
134.:
116.C
114.0
12 3.0
151.0
85.6*
63.3*
70.4*
95.7*
64 .6*
93.2*
84 .9
97.7
9C.7
100.c
63.6
94.0
92.6
97.3
64 .1
97 .0
93.5
91.2
80.8
95.3
76.9
94.6
1 06.0
99.6
91.0
*
440.5*
128.7
110.C
120.9
79.8
89.9
112.7
95.8
152.8
126.2
134.4
110.8
121.1
B7.S
151.2*
152.3*
131.4
133.9
117.2
133.7
135.6
111.6
-------
1*5 Ml
RU
AB
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
TABLE C-30
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PUR G E A 13 L E S **
RAW DATA FOR C I S-1»3-D I CHLOR0PR0PENE ANALYSIS BY WATER TYPE
HIGH YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
5 6 5 6 5 6 5 6
357.0 321.C 157.C 32 1 . 0 357.C 321 .0 3 57 .0 321.0
449.0
366 .0
4 44 .C
3 5 2 .0
4 64 .0
364 .0
444 .3
376.0
637.4
911.9*
1 C 6 7 .4 *
5 5 G . 6
687.5
759.0*
708 .4
743.C*
8 3 C • 2 *
747.2*
7 3 4.8*
8C9.3*
802.6*
8C5 .7*
884 . 2*
511 .3*
414.3
364 .0
5<5.2
363 .5
408 .5
2GO.9
4 4^.4
4 04 .9
495 .0
291 .C
424 .0
3C7.0
191.0
437.C
527 .0
324 .C
379.0*
131.0*
*10.0
319.0
314.0
2 3 3 .0
262 .4*
286.0*
1 5 C . 0 *
1 8 8 . C *
154 .C*
179.G*
238.0*
1£0.C*
277.0*
1 7 5 . G *
7K7 .1
435.3
5 10.6
47C.E
467.9
469.6
5 18.1
436.6
7 2 0 • C
448.0
? 91 . C-
334 .0
3 23 . C
3 38 .0
3 24 .0
393 .C
163. C*
149.4*
179.1*
12 0.8*
174.2*
114.8*
155 .6
1 d 3 .1
3 8 5 . C
344 .0
3*£.C
358.0
375 .0
326 .0
3 68.0
301 .C
3 2 6.0
283. r
3 ? 7 . 0
329.C
3 28.0
261.0
5 20.0
27G.C
? 38 .5
260.6
6 73 .3
3G4.4
13.C
278 .9
342 .6
223.8
35?.5
2 £ 6 . 4
294 .1
2 71.0
263 . 5
324 .3
3 4 C . £
221 .1
5 97.4*
591.1*
437.6
43C.5
515.1
463 .5
493 .2
428 .8
-------
1
?
3
4
5
6
7
8
9
10
11
12
11
14
15
TABLE C-31
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAbLES **
RAW DATA FOR D 1 HR0M0CHL0R0METHANE ANALYSIS BY WATER TYPE
LOW YOUDEN PAIR, UNITS - UC/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUfNT
1 2 1 2 1 2 1
8.1 9.0 8.1 9.0 8.1 9.0 8.1 9.:
7.5
9.1
5 .8
1C.4
9.5
8.3
P .5
8.5
7.8
1 ? . 2
6.7
12.7
7.3
11.4
6.9
12.5
7.7
8.1
1C.0
11.8
6.8
7.6
7.?
9.«
7.5
8.1
7.8
F .4
8.7
10.3
13.5*
11.0
9.7
7.8
5.7
8.3
8.5
5.4
7.?
9.9
4.1*
6.6*
5.7
7.5
7.8
7.3
5 .4
7.6
6 .?
4.2
4.6
5.6
3.9*
3.8
3.7*
5.2
5.6
a.2
6 ."
8.2
9.*2
7.8
8.3
0.9-
0.4
9.6
9.6
1 ?. 4
8.5
9.7
8.6
10.4
6.8
9.9
9.4
7.9
6.6
8.7
7.2
9.5
7.6
8.9
1 .C
6.6
8.3
8.7
8.7
8.3
9.8
10.5
14.2
13.5
9.9
11.1
3 . ?
9.4
9.6
11.2
11 .0
23.?*
11.3
8.9
6.3*
6.6*
11.6
12.C
11.7
r.o-
9.4
3.8
7.4
9.5
5.6
2 G . 2 *
f .4
14.8
38 .7*
12.2
16.7*
8.9
-------
1
?
3
4
5
6
7
8
9
1C-
1 1
1 2
1?
n
15
TABLE C-32
ENVIRON MENTAL MONITORING AND SUPPORT LAPORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONCENTAL PROTECTION A G F N C Y
** EPA METHOD 624 VALIDATION STUDY - PURGtABLES *~
RAW DATA FOR DIF.ROKOCHLOROMETHANE ANALYSIS RY WATER T Y I F
KfcDIUM VOUDEN PAIR, UNITS - UC/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
34343434
36.D 9 C • 0 £6.? 9G.0 86.0 90 .C 86.0 90.0
111 .0
67.2
117.7
72.1
117.C
72.2
99.7
74 . 1
97.3
71 .6
S1 .9
84.7
1C7.7
70.9
108.4
74.3
99.2
69.9
112.5
63.4
1C8.1
9 5.4
72.!
42.5
81.0
69.6
83 .4
38.1
144.7
68.8
93.7
14 2 . 3
113.0
57.2
87.2
44.9
61.3
78.0
93 .9
78.1
4 6.2*
45. O
81 .2
62.9
7 C.S
56.4
1C2 .0
42.0
69.1
97.C
83.2
58.4
77.4
66.5
8 5.9
61.7
97.n
83.5
1 17.1
64.e
128.7
66 .r
112.8
1 Of .8
99.4
68.4
1 15 .C
74 .6
95.1
65.1
1 1C.P
78.3
94.3
63.6
76.1
66.7
76. 1
61.0
92.1
5 5.C
95.6
SC.5
77.2
67.3
100.5
84.7
71 .0
8V. 3
11?.0
88.2
70.2
87.8
78."<
91
65 .<3
135. C
1C2.3
*
31# .6*
62.3
123.2
73.7
8 2.8*
0.0*
101 .3
97.6
132. £
59.4
1 C 4 • 1
92.5
103.4
67.7
65.5
104. 5
1 59.1
81.5
106.2
88.2
14C.3
128.4
-------
1
2
x
4
5
6
7
8
9
10
1 1
1?
1 3
14
1 5
TABLE C-33
ENVIRONMENTAL MONITORING AND SUPPORT LAPORATORY
OFFICE OF RESEARCH AND D E V E L 0 F * E N T
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAjiLFS **
RAW DATA FOR D I B R Of.O C HLO R 0 M E T H AN E ANALYSIS BY WATER TYPE
HIGH YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
56565656
360. C 324.0 3 6 0.0 324.0 36C.C 324 .0 360.C 724.C
42C.0
486 .7
406.3
361.9
440.0
414.0*
295 .0
8 6 2.4*
297.0
329.1
412.0
3 9 4 .0
216.7
3 5 6.2
707.5*
3 4 9.0
608.3*
3 38.0
329.6
?85.G
234.0*
319.0
362. fi
375 .C
291 . 2
3 79.0
341 .0
256.8
275.6
4 08. 8
3 fi 9 . 6
5 63.7
385.8
345 .2
347 .6
3 77 .C
3 49 .0
457 .6
41C.C
3 75 .3
641 .3
3 7f.O
469 .7
271 .1
396.5
35 7 .7
42 3 .3
3 71.0
117.2
284.6
35C.0
318.0
44 1.4
296.0
253.1
668.3
472.:
312.7
223 .2
72 2 .3
4 35 .C
541 .9
4 C 5 . 1
374 .1
2 54 .0
3 59 .0
5C2.C
385.9
276 .0
276 .1
411 .0
404 .0
293 . 5
217.7
537 .4
329 .G
573.1*
368 .0
2 1 S . 0
413 .C
?89 . 0
342 .C
4 QC . 6
273 .C
?63 .4
3 5 7 . C-
329.0
274 .5
3 2 0.9
397.5
397.0
527.?
377.7
469.9
4 50.^
3 36 .2
3 32 .0
5 08.0
288 .0
317.0
417.0
3 76 .0
2 7 3.3*
3 03 .6
44?.9
3 7 9 . C
5 74 .7
228.1
524 .6
2 7 9 .0
3 32 .G
300.0
386.7
322 .0
2 5 7 .3
? 4 ? . G
3<: 3. C
? 2 2 . 9 *
294.4
742.5*
-------
TABLE C-34
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DF VF LOPME MT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PU R 6 t AljLfcS **
RAW DATA FOR ETHYL BENZENE ANALYSIS bY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
AMPUL NO:
TRUE CONC:
DISTILLED WATER
1
15.0
2
17.0
TAP WA TE R
1
15.
2
17.0
SURFACE WATER
1
15.0
2
1 7.C
INDUSTRIAL i \ F L Ufc N T
1
15.0
L
17.0
LA H NUMBER
1
16.3
22.2
22.6
IP.5
18.7
2 6.*
23 .1
17.C
2
15. 9
25. C
U.7
2 7.0
13.9
23.3
15.2
25.5
7
1£.1
17.4
15.4
17.9
19.3
19.1
14 .F
14.5
L
17.fi
21.6
17.0
2 0.3
15.5
24.2
3T .1
17.9
c
15.6
16.4
2 n. ?
15.7
14.7
18.9
24 .0
2£ 0 . 6 *
6
17.5
17.4
12.7*
15.6*
18.7
15.2
11 .4 *
13.9*
7
21.2
11.2
11 .6*
12.1*
11.4*
14.2*
8 .7*
17.7*
8
15.1
10.4
17.0
15.1
21 .C
19.3
21 .0
U .9
<5
19.5
2 0.C
ie .9
25.6
1P . 1
1P.5
IP. .4
19. ft
1C
1 ? . 5
23.2
17.9
16.5
2C.1
22. D
15.3
19. S
11
17.2
17.S
15. P.
15.1
n .5
2 2.C
19.3
1 8.7
1 ?
16.2
19.6
18.9
16.4
16 .0
2 0.0
14.3
15.9
13
19.7
25.8
19.4*
39.0*
26 .<3
19.7
21 .1
3 5. 1
14
15.8
17.8
6? .6*
20.7
22.:
24.3
16.7
2 0.£
15
3 5.7*
37.5*
15.7
37.6
23.0
21.1
27.7
15.3
-------
6
7
c
9
10
11
1 2
1?
14
15
TABLE C-35
[NVlfiCK.HMAl MONITORING AND SUPPORT LAFORATORY
OFFICE OF RESEARCH AND CEVfLOPKLNT
ENVIRONMENTAL PROTECTION AGENCY
** E F A METHOD 624 VALIDATION STUDY - PURGEABLfcS **
RAW DATA FOR ETHYL PENZENE ANALYSIS PY WATER TYPE
MEDIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
3434343^
sJ
17C.C 162.C 17C.C U2.0 170.0 162.0 17C.
225.0
209.C
129.8
195.C
181.3
2 2 8 .0
185.0
19 8.7
179. n
215.6
157.6
2 34 . ?•
2 2C.2
185.1
198
246.C
164.1
187.7
191 .4
177.3
199.2
2 2 8 .3
?00.0
199.8
19 7.?
151.3
153.3
158.2
?C2 . ?
158.0
129.1
3 03.3
151.0
141.0
143.C
1 7 4 . C
176.8
15 4.:
14C.6
10 0.6
135.0
112.0
11. r *
12 5.0*
150.0
16C.C
122.0*
62.9*
77.0
125.0
98. O
7 8.6*
102.0*
113.0*
94 .7*
U3.0*
16 5.0
180.2
141 .1
n 3.1
2 36 .6
163.8
180.-*
18 5.3
187.0
178.0
? 31. n
17F.0
181 .0
17 3.0
19? .0
189.C
127.2
128.5
121 .4
152.8
129.9
140.G
153.2
113.8
173.2
158.3
165.1
164.4
14 3.9
14 9.0
117.6
14 2 . C
2C6.0
216.0
146 .0
181.0
165.0
1 9 2 . C
184 .C
?6fi.O
149.4
591 .6*
181.5*
241 .5
177.5
165.9
230.7
157.5
1 6 5 . 0
2 35 .9
174.8
192 . 1
187.4
161 .1
U7.S
207 .2
139.5
177.E
U1.D
181 .6
164 .8
U5.4
157.9
-------
1
2
T
4
5
6
7
P
9
10
11
1 2
i 7
1 4
15
TABLE C-36
I NW I RON CENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGLAbLES *-
RAW DATA FOR ETHYL BENZENE ANALYSIS bY WATER TYPE
HIGH YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUtNT
5 6 5 6 5 6 5 6
630.G 612.G 63C.C £12.0 6£C.C 612.0 6fc0.r 612.C
(H7.C
6 2 C . C
485 .r
P24.C
668 .0
813.0
8 2 5 . C
711.7
1T3S.6
1341.n
fi 65.3
**3.5
1102.0
925 .P
1160. £
975 .6
763.1
658 .2
6 3 3 .6
6 7 9.7
804 .7
745.4
591 .0
P. 2 2. 2
468. 9
4 P fi . 3
139.3
4 7 f. . e
49fi .0
511.5
116 .a
574 .C
5 5 3 .0
549.C
MP .0
6.P4.0
733 .?
5 3P.-r
5 99.6
441.6
63 8.0
3 e 7. :¦
4 6 2.0*
4 2 S • 0 *
559.0
503.0
261 .4*
4 7^.0*
2£5 .0
421.0
717.O
4CP.3*
6 B 4 . C *
46H.C*
3 7r.r*
42 1 .C *
732.6
587.C
tZ 3.6
63 1.3
662 . 2
735 .2
726 .1
59 9.2
56 4.0
874. C
969 .0
514.0
439 .C
530.0
741 .0
631.0
424 .4
362.6
462.6
7 7 0.4
374.2
385 .9
3 96 .1
75 5 .3
*13.0
6 1 6 . C
7C6.0
901.0
643 .0
5 6 3 . C
709 .0
5 4 7 . G
62 2 .0
683.C
557. C
£ i *. :¦
6£ J . 0
544 .C
736 .r.
513.C
546 .4
544 .?
1 f 3 7 . 4 *
8 5 8.5*
5 56.6
54 3 . P
951.2
540.1
760.2
646.7
6 61.7
536.1
393.3
742.4
5 PP. 2
677.5
726.8
752 .6
7 7» .5
76 3. S
706.7
529.3
4 30.9
4 7 3 .7
-------
r» v
RU
AP
1
2
3
4
5
6
7
8
9
10
1 1
12
n
u
15
TABLE C- 37
ENVIRONMENTAL monitoring and SUPPORT laboratory
OFFICE Of RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGlABLlS **
RAW
DATA FOR
METHYLENE
CHLOR!DE
ANALYSIS bY
water ty
LOW YOUDEN
FAIR, UNITS - UG/L
distillfd
WATER
TAP
WATER
SURFACE WATER
INDUSTRIAL
E F FLUENT
1
2
1
2
1
2
1
2
8.0
7.2
3 . C
7.2
8 .C
7.2
?.o
7.2
2.2
3.2
6.2
16.5
19.4
14.2
13.0
7.5
o.n*
23.£
5 7.1*
Z 5 • 9 *
2.5
4.1
0.0*
11.3
6.1
6.1
t .9
5.3
21.6
4.6
5.4
14. C
19.1
22.6
33 .6
2 2.6
27. «
36.7
21
13 6.6*
2.0
B.3
6.7
6.2
2.7
.C
•:.r*
0.0*
^.9*
5.0*
7.3
10.3
o.r-
4.8*
2.7
4.8
22.1
0. 0 *
0.0*
17.0
5.9
11 .f
10 .6
2. 1
9.7
6.2
16.7
12.5
13.7
5Q.5
9.7*
? 2 3 . 6 *
9.4
6.9
7.4
6.5
9.1
6.7
7.7
5.7
2.1
6 . C
7.4
2.?
*
4.8
0.0*
C.CJ*
7.2
6.8
5.7
4.4
7.6
9.2
12.4
12.7
5.2
5.6
6.7
29.3
C.C*
3.7
n.o*
2 . 8
3.4
5 0.2*
1 .5
C.O*
3.6
24.3
20.7
1 .fi
8. 4
8.2
3 *¦ . 0
7.3
4C2.9*
37.3
C .P*
2 . C
5.1
C..1
:.c*
134.9*
6 9 j . 6 *
C.O*
o.n*
1.5
-------
* I » F
TKU
LAB
1
2
*7
4
s
6
7
8
9
in
11
12
1 3
14
15
TABLE C-38
ENVIRONMENTAL MONITORING AND SUPPORT LAPORATuHY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** fcPA METHOD 624 VALIDATION STUDY - PUftGEAliLES **
RAW DATA FOR METHYLENE CHLORIDE ANALYSIS BY WATEk TYPt
MEDIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL E FFLUtNT
?434343<,
120.0 1H.0 120.? 1 U.j 120.0 1H.C 120.0 114.0
£1.1
54.9
91 .?
57.9
116.3
64.3
fc 2 . 4
6 3.0
164 .Q
75.G
? 79.P *
1 27.?*
139.9
94 .6
12^.4
57.9
113.1
63.4
105.C
6f .8
99.G
106.?
124.1
4 6.9
93.4
5 2.0
97.8
6 2.0
125 .8
104.7
16 5.7
33.2
63 .1
60.0
75 .3
54.4
P9 .4
66.5
r .c*
0. G *
28.6*
35.1-
46.?
43.4
62.4*
16.3*
36.2
22.2
73.1
1C6.0
5? .1
77. F
83.9
7 5.fi
96.5
6 6.5
113.5
83.5
£1.1
M .H
117.5
116.4
? 6 7 . 5 *
119.5*
116.4
104.4
1 C ft . 1
111.1
1C5.G
93.0
129.5
106.5
fiO.4
45.6
29.5
79.5
75.5
*
77.0
4 C . 4
1 3P .4
1G5.fi
166.3
106.1
134.3
112.1
95.1
110.5
14 3.0
96.4
119 .r
13 4.0
74.7
7 5
101 .0
74.0
.4
*
71.7
8 5.4
19 3.1*
107.5
15.4
14"? . 1
72.2
1=6.1
7 3.4
1 50.9
29 3.4*
124.4
54.7
71.9
43.9
636 .n*
32.5
o.r*
P. 0 *
77.0
22.6
-------
A8
1
2
•7
4
5
6
7
8
9
1C
1 1
1 2
13
14
15
TABLE C-39
ENVIRONMENTAL hOMTORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EFA METHOD 624 VALIDATION STUDY - PURGEAliLlS **
RAW DATA FOR METHYLENE CHLORIDE ANALYSIS BY WATER TYPE
HIGH YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
5 6 5 6 5 6 5 t
432 .0 480.C 4 32 .C 48C.G 432.0 480.0 432.0 4cC.C
62 1 .fi
660.4
341 .6
264 .9
277. 1
151.1*
2 3 2 .0
3 & 2 * 9
341 .4
290 .5
^52.0
392 .?
207.4
63 7
265.2
532 .8
939.9*
44 5 .4
336.5
321 .n
231.1*
309.0
416.1
5C1 .4
2 C1 . 0
574 . r
491 .G
354 .1
556.3
2 8 0.5
1C0? .4*
1C75.7*
340.7
1 £8 .4
'33.4
151.:
315 .C
294 .3
3 3 3.1
289.6
4 5 C . 0
4 5 2 . C
3 2 2 .8
469 .8
2 06 .5
1323.5*
7C9.6*
4&C.8
152.1
3 4 8.4
245.0
2 3 6 .0
4 fc 3 . 0
393 .1
111.3
5 4 5.0
48^.0
11 3 . Z
6 29.6
312.8
5 5 G • 3
476 .9
351 .2
242 .7
327.9
120.6*
363 .C
765.G
3C4.C
2421.4*
5C3 .0
4G9.0
778 .4
120.8
1216.2*
438.3
863.8*
4 73 .6
292 .1
279.9
262.6*
347.0
427.2
3 5 8 . n
305 .9
523 .0
529 . C
3 4 8.6
11G3.2*
o.r*
4 37 .0
737 .4
298.7
3 61.6
C.P*
1 6 5 . 7
318.0
439 .1*
2 3 6.5
248 .5
4 8 5 . C
4 3 5.0
33.2
4C8 .5
2 5 3 .1
613b . S*
711.1
351.5
56.2
C.O*
212.9
290 .0
618.8*
4 j 9 . 5
241 .3
516.G
577. C
3 9 7.8
364.1
147.3
-------
LAB
1
2
3
4
5
6
7
8
9
10
11
12
1 3
14
15
TABLE C-40
ENVIRONMENTAL MONITORING and SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEABLcS **
RAW DATA FOR TETRACHLOROETHENE ANALYSIS RY WATLR TYPL
LOW YOU D tN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
12 12 12 1
9.3 10.C 9.0 1C. C 9.C 1G.0 9.0 1C.C
L.
10.1
13.3*
10.2
9.9
9.9
9.1
7.S*
6.1
10.6
6.6*
10.1
11.1
12.4
9.2
24.6*
n .3
12.9*
1C.6
1C.G
9.C
11 .5
5.9*
11.7
10.3
11.8*
10.8
12.6
12.2
11.3
20.8*
12.2
9.4
9.1
P .9
9.6
7.2
5
9.6
1C.1
9.8
9.1
13.9
1 7.0*
37.P*
9 .8
10.6
14.9
1C.B
ir.2
8. ft
9 . G
7.9*
7.7
27 • 6*
8.4
8.9
7.6
28.6*
9.2
14.9
11 .4
7.6
11.5
8.1
10.4
11 .4
5 .C*
13.7
8.9
1C.C
9.7
11.1
32.7*
It! .6
1G.8
14.9
16.1
11.9
11.8
9.2
9.5
6.7*
12.7
10.6
11.3
10.P
13.1
1 ? . 1
12.8
12.5
12.9
8.3*
9.3
10.C
12.0
7.0
< .6
1 5 .n
9.8
7.1
10.5
9.0
10.1
8 .C
15.4
9.9
15.9*
1? .C
3.3
C.C*
8>.4
8.3
10.3
10.2
10.5
10.3
9.6
14.5
11.1
4.9
-------
i*. r
RU
AB
1
?
3
I
5
6
7
o
9
10
1 1
1?
17
1 A
15
TABLE C-41
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE Of RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAbLES * *
RAW DATA FOR T E T R A C H L 0 R 0 E T H E N E ANALYSIS BY WATER TYPE
MEDIUM VOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP UATEP SURFACE WATER INDUSTRIAL EFFLUENT
34343434
95.0 100.0 95 . H 100.0 95.C 1CG.0 95.0 100.0
127.6
118.6
71 .4
111.0
105. C
123.0
98.4
114.4
12 3.9*
12 3.9*
9 2.7
141.3
114.6
127.C
129.2*
142.5
99.4
1C3.6
1C0.7
96.8
107.2
124.5.
109.3
•
on
99.0
114.6
95.4
90.6
112.9
83.4
51 .T
121.7
96 .8
85.1
85.1
98.3
89.1
104. C
65.0
C.C
95.1
77.2
66.7
77.7
83.2
107.0
78 .5
3 0.6
5 9.4*
76.6*
63.2*
58.2-
58.3-
65.5*
73 .?
69.6
1G7.5
U4.5
75.9
1:7.7
152.5
111.3
104 .1
137.1
111.0
1C4.C
2CC.C*
110.0
97.6
100.0
116.0
11 2 . C
63.1 *
60.9*
5 3."
81 .6
62 .5
69.5
72.1
5 2.0
100.2
99.5
94.1
9 £ . 7
91 .6
94.4
68.9
6 8 . 0
136.0
14 2.0
7?.2
1C7.D
9^.2
128.0
91 .3
18H .0
98.0
A
413.6*
9 8.4*
297.5*
1G3.9
89.8
U5.5
117.fi
119.5
137.7
1C2.1
108.8
104.2
96.1
S3. 1
152.2
103.5
13 3.?
119.3
9? . 1
98.7
58.1
129.5
-------
LAB
1
2
3
4
5
6
7
5
9
1C
1 1
12
13
14
1 5
TABLE C-42
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAbLLS **
RAW DATA FOR T E T R A C H LO ROE T H E U f_ ANALYSIS 3Y WATFR TYPE
HIGH YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
56565656
400 .C- 360.0 400.C 36C.0 400. C 36C.C 4 00.0 360.C
416.6
364 .6
2 7? .0
476 .0
397. C
4 46.0
458.4
4U4 .4
531.3*
708.2*
562 .4
45^.2
538.6
671 .7
612.9*
662.0*
398 .3
343.4
3 57.8
35 1.4
434 . 2
381 .3
320 .3
224 .C
347.*
4C2.9
344 .6
375 .4
4 06.2
381.0
3 or. 6
341.9
4 41.0
313.0
3 84.0
367.0
397.G
359 .0
M9.0
23C.0
411.0
232.C
2 70 .C
243 .0
349.0
310.0
14?.?
272 . r.
206.0*
26C.0*
220.C*
274.0*
393.C*
262.0*
271 .0
2 7 7.0
424 .6
358.9
297 .1
360.5
408 .3
422.6
4 04 .6
411.2
339 .0
373 .C
6 76 .C
3C8.0
2 93 .0
279.0
288 .0
2 V 7 . C
133.?*
145.8*
2 03.5
142.7
1 50. 5
164.7
164 .7
134.6
4 79.0
3 6 5 .0
4 1C . C-
476 .0
377.0
3 31 .0
3 99 .0
315.:
3 74 .0
4 G 8 . 0
291 .G
4 9 C . 0
351.0
3 2 7.0
362 .0
2 7 2 .C
315.9
338 .1
7 6 4 . 9 *
551.2*
319.5
686 .5
497.2
308 .8
473 .6
40G.5
394 .1
35C.5
211.3
402.4
3 5 5 .9
353 .6
466.4
503.5
361.2
4 6 C • 5
790. 2
3 8 3 .0
269.0
4<.6.C
-------
1
2
3
4
5
A
7
8
9
1C
1 1
12
1 3
n
15
TABLE C-43
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DFVELOPN1ENT
ENVIRONMENTAL PROTECTION AGfNCY
** fc P A METHOD 624 VALIDATION STUDY - PURGEAbLES **
RAW DATA FOR TOLUENE
ANALYSIS
r?V WATER
TYPE
LOW YOUDEN PAIR, UMTS
- UG/L
DISTILLED
WATER
TAP
WATER
SURFACE
yATEP INDUSTRIAL
E F FLULNT
1
2
1
4
1
2
1
c
13.5
15.0
13.5
15.C
13.5
15.0
13.5
15.0
n.d
18.6
IB .6
14.5
14.9
26.9*
18.6
14.0
17.7*
19. fl *
16.1
2 2.2
11 .9
21.6
17.4*
2 3.0*
15.0
16.7
13.0
15.3
16.5
18.7
17.3
31.2*
16.6
16.3
16.5
20.9
1C.2
17.3
17.5
18.2
13.6
13.7
17.6
15.6
13.6
16.5
35.3*
o.:*
13.3
15.5
12.2
14.2
16.3
14.3
10.7
14.2
14.?*
9.2*
£.2*
12.3*
8 .6*
11.4*
F .?*
13.2*
15. 0
1R.C
16.C
14.4
17.6
16.5
2 C . ?
If . 5
1 £ . 4
17.5
16.5
25.7
15.6
17.2
15.7
17.7
12.0
1S.b
16.9
14.5
16.0
13.0
12.8
15.7
15.5
15.C
14 .6
13.7
14.3
16.6
15.7
15.0
13.7
17.2
13.C
12.2
14.7
17.6
12.2
10.9
14.2
19.7
16.5
3C.9
21.4
17.5
14.5
21.0
16.5
16.1
50.7*
U.9
16.4
19.3
12.4
15.6
2 3.9*
27.3*
15.4
21.5
16.2
1 ?.6
18.4
13.7
-------
TABLE C-44
ENVIRONMENTAL MONHOftlNG AND SUPPORT LAP O^ATOfrY
OFflCt OF RtStARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEABLES **
RAW DATA FOR TOLUENE ANALYSIS E> Y W A T F R TYPf
MED1UK YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER
TAP WATER
SURFACE WATER INDUSTRIAL EFFLUENT
AMPUL NO:
TRUE CONC:
3
H?.D
4
15C.C
3
142 .
4
1 5 0 . C
3
142.0
4
1 5 0 . C
u? .0
4
15C.0
LAE NUMBER
1
219.0
191 .C
1C9.6
182.9
153.C
241.0*
164 .6
177.2
?
171.2*
196.7*
153.5
2 2 3.6*
188.4
175.4
18 2.6*
223.6*
3
152.9
178.1
154.7
1 4 J* . 4
18C .7
191.8
214.4
135.1
4
150.9
184.4
13 5 .5
137.7
176.6
149.4
60.4
153.3
5
130.0
130. 0
1?7#:
159.0
157.7
137.0
146 .P
110.8
6
133.5
121.5
110.c
12C.0
139.8
155.1
122.4
74.3
7
86.4 *
114.0*
96.8*
8 9.1*
89.9*
96.8*
99 .4*
97.9-
8
150.4
162.3
131.8
165.2
188.2
147.2
165.5
181.8
9
175.0
172. 0
249.0*
179.0
155.0
158.C
178 .1
154.1
0
104.5
1C6.9
96 .7
132.1
106 . 1
119.6
122.0
96.5
146.4
130.8
139.9
142.6
117.1
124.9
97.5
119.5
185.0
195.C
123 .r
1 6 1 . C
153.0
173.0
158.0
215.0
118.4
¦*
4 64 ~ 6 *
161.2
2C5 .8
152.9
134 .0
191.7
16P.9
161.3
Z0C.5
15 1.6
166.4
161.1
139.3
126.7
191.0*
156.2*
US .4
166.9
148.9
141.3
1 24 .6
152.3
-------
TRU
LAG
1
2
3
4
5
6
7
*
9
10
11
1?
11
14
15
TABLE C-45
ENVIRONMENTAL momtoring and support laporatgrt
OFFICE CF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PUNGfcAULLS **
RAW DATA FOR TOLUENE ANALYSIS BY LATER TYPE
HIGH YOUDEN PAIR, UNITS - U6/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
5 6 5 6 5 6 5 6
13D.a 54a.C tzC.C 54C*C 6C0 * C 54C.0 6GC.0 540.0
6 4 6 • 0
*S2.3*
£86.4
204.6
485 .0
497.5
265 • 0*
562 .2
5£D.Q
? 5 8 . 4
6 7 7 .0
567.3
413.1
68 2 .7
7C1 * 7 *
541 .G
971.0*
542.6
590.!
4EG.0
3 74.5
355 . C*
4 8 4.6
618 .C
224.9*
525. C
559.C
4 34 .9
575 .6
633.9*
411.C
?lh .1
5 5 c . 5
494 .3
537.r
*74.C
3C4 .C*
475.9
£41 .0
2 7? .1
*76 .C
511 .r
BD7.5
573.2
4 2 7 .2
724.9
771.6
551,5
5 54 .6
5 9 6 • C
3 6 3.0
4 £ # u*
51? .5
5CC.0
?1?.8
6 2 P . C
6 P 4 . C
7 2 C . 0
476. 0
71 3.7
564 .C
935 .1
74C.3
557 .6
640.C
356.^
477.C*
535 .1
454 .C
2 2 £ . £
542 .C
622 .G
496 .1
326.9
518.£
794 .0
S26.9
613.C
576 .3
483.0
514.1
355.C*
564.4
447.0
? 44.7
474 .C
494 .C
4 35 .4
674 .C
5 76 . r
6 90.6
1CG3.7*
531.5
340.6
541 .8
"*27.6
331.0*
5 35 .6
4 8 2.1
230.5
572.0
6 76 .0
M2.5
515.4
45* .C
617.2
8 79.6*
494 .?,
4 34 .5
4 5 4 .8
421.4
34C.C*
562.9
5 u 4 « 1
202.1*
46*.0
45 3 .0
4 4 3.2
639.2
441 . 3
-------
1
?
3
4
5
6
7
B
9
1C
11
12
13
14
15
TABLE C-hb
ENV1 RCN^EMAl MONITORING AND SUPPORT LABORATORY
OffiCf OF RESEARCH AND DEVELOPMENT
environmental protection AGENCY
** EPA KETHOO £24 VALIDATION STUDY - FURGE A£>LE S **
RAfc DATA FOR TRANS* 112-0 ICH10R0ETHEN£ ANALYSIS BY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
12 1112 1,;
5.0 4.5 c .C 4.5 5 .0 4 .5 5 .0 4.5
2.9
5.1
4 * £
6 .3
5.5
4.7
4.3
5.9
6.1
4.4
4.1
5.1
6.2
5.3
10.6-
3.5
6.2
3.8
4.7
5.7
6.7
2.6
5.1
5 . C
4.9
3.7
5.5
6.4
3.7
5.7
4.2
4.5
4.3
5 .4
6.3
6.1
2.7*
6 .4
6.1
5.4
2 .9
4.5
5.5*
2C .4*
4 .7
3.0
7.2
3.9
6.4
5.2
5.1
4.0*
4 . P
5.4
4.5
2.5
1 .5
8.8*
5.0
4.8
4.0
4 .(
4.7
3 . £
4.C
6.6
4.4
4.4
5.7
5.6
4.3
5.5
7.7
7.7
4 . C
3.5
5.8
3.8
*.7*
3.6
4.7
3.3
4.1
5.3
4.7
3.6
6.0
5.5
5.2
6.2
3.9
5.1
3.6
37. 8*
13 .S*
5.0
3.5
7.7*
5.S
5.2
4 .3
6.4
4.7
5.7
1.5
3.6
5.3
4.9
3 7.9*
5.7
4.3
3.3
6.1*
i , 0
4.5
3.1
5.3
4.5
4.6
4.8
-------
AB
1
2
3
4
c
6
7
8
9
10
11
1 ?
13
14
15
TABLE C-47
ENV I RCNVEN7AL rONlTORING AND SUPPORT LABORATORY
OFFICE CF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA KETHOD 624 VALIDATION STUDY - PURGE ABLE S **
HAW DATA FOR TRANS-1,2-DICHL0ROETHtNE ANALYSIS BY WATER TYPE
MEDIUM YCUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
34343424
75.0 71.C 75.0 71.3 75.C 71.C 75.0 71.C
.9
4 9.0
72 .5
.7
5C.7
1 j? .1
.4
45.6
7« .r
.5
68 ~ C
81.1
.9
49.?
7C
.1
51.0
7F .0
• 1
68 .0
62.6*
.1
54.9
92 .8
.1
82.1
92.4
.6
6C.4
66 .C
.0
41.1
91 .2
n
• 'j
64.4
62.6
.5
*
248.2*
.3
37.4
121 .1
• -
54.4
94.6
52.3
71 .4
51.0
67.0
48.0
63.2
86.5
48.6
75.5
39.5
41.9
74 .7
62.9
97.5
75.9
7 5 • 7
135.4*
62.4
102.5*
117.3*
56.5
82.2
58.3
92 .4
60.8
56.1
65.1
59.4
79 .8
33.8
51.6*
66.4
49.6
78 .8
57.2
73.7
95.9
57.4
103.2*
1 C 5 . 4 *
6 7.8
79 .8
81.1
1G0.C-
94 . 1
71.2
69.C
64.0
78 .7
63.4
36.6
77.7
45.0
57.9
48.8
77.5
89.4
72.3
69 .7
64 . 0
58.0*
1C5.3
56.9
73 .6
61.6
51.0
95.1
78 .1
86.5
57.3
5T. 3
5C.8
42.9
78 .5
19.9
-------
1
2
?
4
5
6
7
8
9
10
11
1 2
1 3
14
15
TABLE C-48
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAtJLES *•
RAW DATA FOR TRANS-1 , 2 - D1CHL0R0ETH£NE ANALYSIS BY A T E R TYPE
HIGH YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
56565656
270. 0 3CL.0 27r.f 30C.0 270.C 300.0 270.0 30C.0
220.0
412.9
259 .3
332 .3
293.0
336 .3
15 8.0
2 7 9.3
267,0
277.2
311.0
274 .G
206.6
348.9
28fi. 8
269.C
43C.3
302 .2
353.2
307.0
2 6 1 . C
249.C
365 .8
383 .C
265 .9
3 3 2 . 0
343 .C
294 .7
3 C 1 .1
214.3
22?. .0
425.3*
2 57 .9
702 .5
283 .0
262 .C
214.0*
317.1
1 21 .0
274 .6
? 12 . r>
31 c. r
4 5 C . 6 *
? 7 H .6
290.7
2 5 0 .3
416.4
319.0
43*.3
317.0
344 .0
243.0*
4 36 .1
3 1 7 . r
2 5 8.0
324 .0
312.0
464.9*
349 .1
345.2
230.0
404.1 *
268 .3
194.7
281.0
278 . C
274 .r
268 .3
264 .0
259 .C
27C.C
276 .0
253 .8
192.2
2 36 .4
249 .0
396 .5
31C.8
407.5
3 06 .0
282 .0
282.C
384 .4
284 .0
267.9
286 .0
3G9.0
340. 1
397.7
341 .6
2 36 .C
473 .7*
235 .2
341.8*
282.0
2 C1 .8
2 5C.T
4 GO. 0*
2 59 .0
253 .1
279 .0
316.0
3 56 .Z
2 70.1
313.1
261 .0
369 .7
4 4 9 .0
4C1 .8*
277 .0
319.0
250.0
414.9*
396.0
297.5
2 £ 2 . C
330.0
305 .7
266 .7
1C8 .6
-------
1
2
3
4
c
>
6
7
8
9
1C
1 1
1?
13
14
1 5
TABLE C-49
ENVIRONMENTAL MONITORING AND SUFPOR T IAftORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA KFTHOD 624 VALIDATION STUDY - PURGfcA&LES **
R*W DATA FOR TRAKS-1t3-DICHLOR0PR0PEbE ANALYSIS 8 Y WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACF WATER INDUSTRIAL EFFLUENT
12 12 12 12
9.4 1C.4 9.4 1C•4 9.4 1C.4 Q.4 1C.4
4.1*
8.3
17.1 *
6.3
7.9
0.0*
9.6
5.5
7.6
4.3
8.8
9.0
10.9
14.3*
7.0
5.4*
10. C
2 0.2*
4 . P
6.8
8.6
7.1
7.3
8.2
6.4
10.1
9.7
13.1
1C.6*
8.9
5.4*
7.1
18.4*
4.8
5.7
6.?
6.3
5.7
6.9
5.5
£ .8
7.8
11 .C
30.9*
1 1 .0
5.5*
1C.1
21.3*
7.0
6.7
7.3
11.8
6.3
7.6
4.9
8.3
9.5
2 2.8*
11.3
5.1
6. C *
6.3
18.4*
7.9
6.9*
9.2
9.4
7.2
6.9
6.3*
9.4
9.1
14.0
12.6
12.5
5.6*
9.7
19.6*
6 .t
3.4*
5.7
1 l.b
6.4
6.0
5.3*
1C.5
9.6
12.2
12.7
9.1
5.3*
6 .8
14.4*
9.1
6.6
7.3
7.5
7.4
6.9
5.9
9.?
6.8
8.4
9.4*
8.9
6.2*
1C.C
37.4*
7.9
7.4
9.1
9.7
6.6
8.7
5.1
9.2
9.2
9.7
12.3*
8.7
-------
1
2
r
4
5
6
7
8
9
10
11
12
13
14
15
TABLE C-50
ENVIRONMENTAL MCMT0R1NG AND SUPPORT lAeORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA KETHOD 624 VALIDATION STUDY - PlJRGEAbLtS **
RAW DATA FOR TRANS-1f3-DICHLOR0PRCPENE ANALYSIS »Y WATER TYPE
* I DIU vi YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
3434343A
99.0 104.0 99.C 104.3 • 99.0 1C4 .0 99 .0 104.0
65.5*
82.9
198.4*
79.2
77.6
87.9
97.2
77.3
77.1
85 .6
109.5
97.9
103.3
142.1 *
40.1*
62.2*
75.8
24C.6*
74.3
67.9
13.C*
125.0
£9.4
5C.1
£3.1
112.9
94.4
*
149.0*
82.6
74 .4*
80.1
237.5*
58.3
68 .2
81.3
1C8.0
72.9
74.5
7C.4
1 or .6
52.9
312. **
163.2*
9C.2
65.4*
97.2
234.4*
66.6
56.2
81.9
122.0
77.7
77.0
95.7
108.7
91.8
102.2
146.7
126.9
71 .9*
78 .4
228.7*
79.5
45.9*
62.9
109.C
94.7
71.9
64.6*
1C8.3
65.9
138.C
141.2
97.S
67.2*
82.3
259.6*
84.1
80.1 *
96.8
125.C
7 5.0
72.1
93.2*
110.1
98.5
131.7
15C.1
50.7
62.0*
85 .8
199.3*
65.1
72 .7
84.3
125.0
77.H
82.2
84.9
78."i
59.9
95.3
134.7*
107.9
71.2*
SC.2
24C.6*
108.5
71 . 1
65.7
1 U . C
83.8
62.0
97.7
1G7.C
94.2
64.5
U8.9*
8 3.6
-------
1
2
i
4
5
6
7
8
9
1C
1 1
12
13
14
1 5
TABLE C-51
ENVIRONMENTAL MONITORING AND SUPPORT LAt'uRATUhY
OFFICE OF RESEARCH AND DEVFLOPMENT
ENVIRONMENTAL PROTtCTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAbLES **
RAW DATA FOR TRANS-1 f3-D I CHL0R0PR0PEhE ANALYSIS faY WATER T*Pf
HIGH YOUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
5 6 5 6 5 6 5 6
416.0 374.C 416.0 374 . C 416.C 374 .0 4 16 .C 3 74 .0
2 4 5.0*
2C 7 . C *
2 1P . C *
2C5.C*
262 .C*
194 .0*
247.0*
223.C*
392.5
36?.9
4 28.5
346 .2
4 CO • 7
353 .0
427 .2
359 .4
8 86.6*
678.9*
874.1 *
815.8*
863.3*
8 8 4.7*
9 S 5 . 7 *
» fa 5 . 8 *
? 5 4 • 1
265 .8
2 53 .8
253 .9
312 .0
239 .6
300 .?
35 5 .9
2 S 6 . 3
204.C
263 .r
226 .0
191.C*
210.0*
3 30 .0
201 .0
426.0
46.8
3 4 5 .r
313.0
342 .C
215.C
282.3
314.0
338 .G
328 .C
365 .r
334 .0
472 .C
351.0
372 .0
3 4 G . 0
413.5
285.C
2 9 c . 3
287.4
305 .0
311.8
323.0
289.7
250.0
3 1 :. C
? 9 3. c
2 38 .C
26C.0
221.0
244 .0
2 7 7 .0
163.0
149.4
179.1
12C.8
17 4.2*
114.8*
155.6
183.1
453.0
398 .C
442 .C
426 . 0
4 24 .0
372 .0
431 .0
356 .C
39G.0
32C.C
388 .C
363 .0
3 8 5 .0
320.0
112 .0
319.C
250.6
287.9
4 77 .9
24 3 .4
2 27 .8
320.6
7 b4 . 7
25 9 .2
4 67.8*
363.1*
406 .8
337.9
272 .8
447 .7
416.6*
426.7*
315.2
126.9
4 24 .2
232.3
285 .9
270.5
378 .2
232 .7
-------
AMP
TRU
LAB
1
2
3
4
5
6
7
e
9
10
11
12
13
14
15
TABLE C-52
ENV I&ONKENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** fc P A METHOD 624 VALIDATION STUDY - PURGEAbLES **
RAW DATA FOR TRICHL0 ROETHENE ANALYSIS RY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
1
2
1
2
1
2
1
c
6.0
5.4
6.C
5.4
6 . G
5.4
6 . C
5.4
7.3
9.4
£.3
7.8
9.C
7.0
8.6
12.5
9.8*
13.2*
7.1
11 .8
7.r
13.6
7.9
10.6
8.3
7.1
7.1
7.2
7.4
7.4
6.6
16.3
8.1
7.4
6.4
9.2
11 .4
10.3
105.0*
76. 1 *
6.9
7.4
6.2
5.8
8.2
13.5
0.0*
C.O*
9.9
6.1
5.9
6.1
8.5
5.4
6. C
6.9
4.6*
3.3*
3.3*
5.3*
5.2*
2.2*
4.4
4.6
5.7
7.0
6.5
4.7
8.1
6.3
P .8
5.7
fi.6
7.3
7.3
9.7
6.8
3.6
7.0
7.2
5.4*
7 . C *
6.8
6.?
6.4*
6.1*
6.1
6.5
6.7
6.3
6.1
5.6
6.7
6.1
7.0
5.6
9.9
9.a
9.9
e.2
7 . C
10.3
6.7
8.C
9.3
1C.9
9.5
2 C . 4 *
12.?
10.9
7.1
8.0
12.3*
19.1*
5 3.3*
6.7
13.6
10.C
18.2*
16. 3*
6.0
11.3
8 .4
1C.1
6.7
4.6
4 .6
2.2
-------
9
MP
RU
AB
1
?
3
4
5
6
7
8
9
10
11
12
11
14
15
TABLE C-53
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPvENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD beA VALIDATION STUDY - PIJRGEABLES **
RAW DATA FOR TRICHLOR0ETHENE ANALYSIS BY HATER TYPE
MEOIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUtNT
34343434
90.0 86.C 90.0 66.0 9C.G 86.0 90.0 £6.0
111.0
96.6
1 C4 .6
97.6
106 .C
95.3
107.G
165.0
119.4*
1G6.8*
69.6
1 £9.5
1C7.5
106.5
129.9
136.4
94.8
93.6
98 .5
£9.2
97.9
95.5
98 .P
113.7
91.2
91.7
P5.4
1 CO.2
146.5
132.9
14 2.5*
227.1*
104.0
76.1
79.7
75.9
81 .8
101 .0
74 .6
75.9
96.4
94.9
75.5
6 8.9
66 .C
93.1
8C .4
45.1
6 r. s *
70.7*
6P.6*
63. D*
70. G*
65.9*
83.4
68.1
101.8
86.1
7 C .6
90.0
132.8
91 .C
91 .5
113.4
105.0
89.9
12?.0
97.0
94 .4
85.6
1C6.0
97.4
71.5*
6 2 • £ *
58.6
71 .a
60.C*
61.1*
74 .5
57.6
9ft. 4
85.6
9? . 1
£7.8
89.C
83.6
66.4
81.8
132.0*
113.C
71 .9
9E.1
1G9.0
1 16.0
61 .4
140.0
131.7
*
322.9*
t 1 .5
125.3
1C4.fi
85.5
78.5
217.0*
98.3*
1 5 C.. 6
76.2
108.7
127.1
212.8*
192.9*
3 7.7*
114.0
13?.C
126.9
73.3
74.4
74.3
80.6
-------
TABLE C-54
environmental monitoring and support laporatory
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGIAULES **
RAW DATA FOR T R I C H L 0 R OE T H E N E ANALYSIS PY WATEit TYPE
HIGH YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER
TAP WATER
SURFACE WATER INDUSTRIAL EFFLUENT
AMPUL NO:
TRUE CON C:
5
324.0
6
3 6 0 • C
5
324.C
t
36C.0
324.0
6
36C.C
5
3 24 .0
6
J 6 C . C
h- LAP NUMBER
1
3b4 .0
394.G
3 5 9.0
413.0
3 61.0
3 8 0 . C
378 .C
64 8 .0
2
4 4 8 . 6 *
642.4*
393 .3
542 .4
476 .5
576.6*
5 33 .4
561 .2
3
317.1
339.2
3C0.C
342 .5
3C4 .6
344 .7
306 .5
3 9 C . 5
4
357.3
358 .9
323 .9
401.3
348.3
26C.5
383.5*
513.8*
5
352 .0
297.0
272 .C
359 .0
276 .C
382 .C
395 .2
25C.2
6
34 2.9
23.7*
240.C
259 .0
283 .5
279.5
184.9
270 .C
7
16 5.3*
219.C*
192.C*
241 .0*
282 .C*
259.0*
237.0
2 5 5 .0
8
331.7
362 .1
255.5
58C.0
342 .7
4 24 .3
343 .1
434 .0
9
306.0
421 .C
4 6 2 . C
342 .0
2 8 5 . C
309. G
271 .0
392 .C
1?
19 5.1*
195.1*
194.1
180.1
158.6*
191.1*
182.4.
170.5
11
365 .0
374.C
329 .0
389 .0
3 21.0
330 .0
321 .0
323 .C
12
366 .0
395.C
343 .0
53C.0
373 .C
376 .0
377 .0
306 . C
13
1 6 1.. 2 »
261.1
395 .7
347.6
22C.3
262 .3
2 39 .8
221 .9
14
629.1*
3 61.9*
214.7
298 .7
19C.4
403 .9
7 24.7*
4 3 8.3*
15
383 .4
163.2
2 68 .2
551.1
249.8
351.4
238 .6
330 .C
-------
TABLE C-55
ENVIRONMENTAL MONITORING AND SUPPORT IA l"> ORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 6 24 VALIDATION STUDY - PURGfcA&LES **
PAW DATA FOR TRICHLCR0FLUOROKETHANE ANALYSIS OY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER
TAP WATER
SURFACE WATER INDUSTRIAL EFFLULNT
AMPUL NO:
TRUE CON C
1
3.0
2
7.2
1
8.C
2
1.2
1
E . 0
c
7.2
1
8 .?
2
7.2
00 LAB NUMBER
4.8
4.2
4.8
4.2
5.2
4.9
4.7
4.7
23.6*
2 3.6*
24.4*
22.7*
19.6*
22.7*
19.1*
17.6*
7.0
6.9
6.2
6.0
7.4
6.0
7 . f
7.4
7.7
5.1
7.0
5.6
3.5
7.7
7.5
7.1
10.8
7.1
5 .4
8.1
8 .4
3.4
8.3
f . 1
1Q.5
11.3
9.4
1C.5
11.8
7.7
9.0
7.3
3.1*
2.2*
2 .r*
3.3*
3.6*
2.3*
2.8*
1 .9*
6.8
5.2
1?.3
7.2
5.6
4.4
9.5
ft . 0
10.6
a.7
10.1
9. 0
10.C
8.1
1C.1
9.3
2.8*
2.9*
4.4*
3.8*
3.4*
3.3*
4.1*
2.6*
*
*
*
*
*
*
+
10.8
10.5
9.7
C.D*
10.3
9.9
9.4
9.9
7.9
9.4
5.7
12.3
1C.8
6.6
7.1
5.9
8.0
7.0
29.9*
7.4
8.2
7 . C
6.5
6.8
23.3*
4.6
9.2
7.2
5.9
5 . C
9.4
8.0
-------
1
2
7
4
5
6
7
8
9
1C
11
1 2
13
14
15
TABLE C-56
E N V 1RCNMENTAL MONITORING AND SUP POUT LABORATORY
OFFICE. OF PESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA KETHOD 624 VALIDATION STUDY - PURGEALaES - *
RAW DATA FOR TR I CHL0RGFLUORO*ETHANE ANALYSIS BY WATER TYPE
MEDIUM YCUDEN PAIR, UNITS - UC/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUt^T
34343434
12C.0 114.C 12C.C 114.0 120.C 114.0 12C.0 1U.0
84.1
51.3
£7.9
56.1
57.4
60.3
70.4
54.4
3 4 5.5*
225.2*
3 6 2.3*
196.3*
360.4*
159.5*
? 5 9 . 5 *
192.1*
193.6
75.8
111.6
59.E
113.0
96.7
165.0
63.6
79.8
79.6
92.6
49.3
92. S
41.7
126.3
101.0
151.0
74.8
12 3.0
59.5
64.1
107.C
151 .0
95.1
144.0
104.0
15 5.0
13C.0
115.6
123.0
155.0
72.6
50.6*
5 C . 0 *
5 0.2*
47.5*
61.5*
36.1*
61 .2*
3 5.1*
97.6
44.9
1 5 C . 2
13C.9
116.5
69.9
152.2
132.C
167.0
157.0
166.0
138.0
145 .C
132.C
175 .0
14 8.0
45.S*
4 C • 9 *
56.4*
47.7*
52.C*
4 0.4*
4 8.1*
51 .6*
*
*
*
*
*
*
*
*
14 9.0
112.C
97.1
1C6.Q
137.C
1C3.C
1C? .0
92.6
9R.6
*
315.6*
84.4
143.2
72.7
104.3
74.0
127.7
74.9
184.8
77.4
13 5.5
92.1
138.0
65.3
211.0
62.4
135.5
7C.D
65.3
ec.i
163.5
88.9
-------
TABLE C-5 7
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAULES **
RAW DATA FOR TUICHLOR0FLUOROMETHANE ANALYSIS BY WATlR TYPE
HIGH YOUDfcN PAIR* UNITS - UG/L
DISTILLED WATER
TAP WATE R
SURFACE WATER INDUSTRIAL EFFLUtNT
oo
vO
AMPUL NO:
5
6
5
6
5
6
5
6
TRUE CONC:
432.0
480.0
432 .C
48C.C
432 .0
4.80.0
432 .0
480.0
LAB NUMBER
1
282.0
287.C
267.C
283 .0
284.0
312.C
259 .0
3C9.9
2
1 5 8 £ . 9 *
17C4.1*
1442.8*
1 2 3 4 . 8 *
13 91. 8 *
15C9.0*
1409.n*
1478.2*
3
437.7
428 .C
3 73 .0
449.4
380 .7
4 7 8 • ij
383 .7
8 6 2 .4
4
298.9
348.3
279 .2
275 .4
163.7
3C2.5
3 76 .2
419.1
5
5 5 8 .0
431.0
4 58 .r
3 48.0
24.7
557 .0
5 05 .0
5 33 .C
6
74.1
526.0
603 .C
7 3 8.0
557.0
47C.C
369 .6
674 .0
7
14*.0*
19 5.0*
1 9 9 . C *
19 r. o *
196.C*
273.0*
?1r. c*
174.C*
8
3 1 C . 2
3CC.9
507.3
733 .0
310.8
445 .1
654 .1
5 j0.4
9
475 .0
776.0
5 89.0
525.0
430. C
525 .0
431 .C
612.0
10
16C.8*
176.3*
186.C*
2 2 3.1*
161.8*
200.0*
159.0*
262.5*
11
*
*
*
*
*
*
12
412.0
5 9 3.3
458 .C
464 .0
447.0
462 .0
4C9 .0
521 .C
13
3Z1. 7
418.2
621 .1
663.7
327.7
487.9
425 .3
3 8 C . 8
14
491,8
5C8.7
410.8
494 .3
271 .0
576.2
4 02 .5
337.0
15
3 5 5 .*
8 54 .8
295 .7
5 52 .1
418.6
3C5.2
526.4
467.6
-------
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
TABLE C-5 8
ENVIRONMENTAL MONITORING AMD SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
environmental protection agfncy
** EPA METHOD 624 VALIDATION STUDY - PURGEAULIS **
RAW CATA FOR 1 , 1 - D I CHLOROETHANE ANALYSIS BY UATLR TYPE
LOU YOUDtN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
1
2
1
2
1
2
1
2
10.8
12.0
1G.fi
12.0
10.8
12.0
10.8
1 2.C
9.8
9.7
9.2
1C.1
9.9
12.2
8.9
11.4
18.0*
21.8*
3C . 9 *
21.7*
12.3*
19.4*
16.3
17.3
11.2
12.3
11 .C
12.4
10.9
12.5
10.P
20.7
13.3
12.5
12.3
16.1
6.8
17.2
i r • 3
6.8
13.0
12.7
9.1
12.2
11.9
9.5
15.6
15.6
10.5
13.7
1C.5
1 4.1
11 .8
12.1
10.C
11.6
1C.0
7.3
6.3*
11.5*
9.8*
9.9*
8.2
9.2
13.?
15.9
13.7
11.9
11.3
11 .6
19.^
16.5
14.5
14.8
H .7
15.3
13.2
14.2
13.2
16.3
7.5
9.8
8 .9
8.7
8.9
9.1
9.2
8.1
11.6
13.C
1C.9
11.2
11.9
13.1
12.2
11.7
9.9
14.0
8.3
6.9
11.9
13.8
11.1
13.5
13.7
21.9*
15.0*
26.2*
18.1
14.4
11 .9
13.4
12.7
13.4
30.5*
13.3
16.1
14.6
1 1.7
13.6
17.5
13.7
11.2
16.7
10.5
14.6
3.0
12.C
-------
1
2
3
4
5
6
7
8
o
10
1 1
12
13
14
IS
TABLE C-59
ENVIRONMENTAL K0NIT0R1NG AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA rETHOD 624 VALIDATION STUDY - PURGfcABLtS **
RAW DMA FOR 1, 1 -D1CHLOROETHANE ANALYSIS BY WATER TYPE
MEDIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUtNT
3 4 3 4 3 4 3 4
114.0 120.C 1H.C 120.0 114.0 120.0 114.C 120.0
126. j
78.7
138.1
9C.5
126.0
1C4.0
99.?
o 5 .2
206.8*
121 .9*
293 .6*
145.9*
159.2*
100.3*
117.1
10 2.0
122.5
82.1
129.1
75.6
12 3.4
110.8
174 .3
124.3
119.1
118.1
118.5
1G7.7
148.8
92.2
1 IP .5
137.2
121 .0
83.3
115.0
76.7
122.4
111.C
128.0
106.C
98.1
86.0
1 2 G . C
1CC.0
111.5
96.7
121 .0
68.8
S3.4
113.:
9 7.1*
91 . C *
1C2.G*
8 7.2*
117.C
96.6
139.1
89.9
118.5
114.2
140.7
95.5
123.4
179.1
14 8.0
149.C*
144.0
162.0*
132.C
140.0
160.0
166.0
1 1 1 . B
93.1
94 .3
1C3.0
98 .0
93.6
107.C
99.C
132.4
110.0
133.4
105.2
12f .6
117.3
93.2
114.6
132.0
96.6
91 .8
125.0
121.0
107.C
1G4.0
77.2
126.4
*
395.9*
1 1C.5*
155.9
1C8.9
127.1
119.4
82.8
81.7
196 .6*
84.3
14b.C
133.C
14 0.1
90.7
58.fi
94.4
141 .9
1G3.2
68 .7
65.4
147.2
47.3
-------
1
2
3
4
5
6
7
8
9
10
11
1?
13
14
15
TABLE C-60
ENVIRONMENTAL MONITORING AND SUPPORT LAPORMOM
OFFICE Of RESEARCH AND DFVELOPKENT
ENVIRONMENTAL PROTECTION AGfMtT
** £ P A R £T H 0 0 62* VALIDATION STUD* - PURG£ABLES **
RAW DATA FOR 1 .1-0 ICHLONG£THA Hi ANALYSIS b* WATER T*Pt
HIGH YOUDEN PAIR • UNITS - UG/L
DISTILLED MATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
56565656
430.0 432.C 480.G 432.0 460.0 432 .0 480.0 432 .C
527.0
987.?*
479.1
562.7
570.0
5 5 7,0
205.0*
461 .8
4 78 ,0
5 39,3
578.0
451.0
420.?
659.8
5 31.6
368.0
939.6*
454.P
521.3
410,0
419.0
292.G
487.3
547.C
*91.3
509.C
480.C
468.2
528 .5
34C.3
461 .0
1666.4*
48? .3
513.2
489. C
423 .C
2 89.0*
443 .2
552.C
463 .4
519.0
614.0
P83 .P*
5-3C.0
513 .6
357 .0
S25.2*
484.6
547.9
378,0
497.0
271.0*
541.5
488,0
?79.8
502.0
3 5 5 .0
717.7*
574 .1
5G5. 5
483 .C
793.3*
496.6
367.5
399.0
391 ,0
366.0*
4 54 ,9
411 ,0
468.S
527.0
5C2.C
475 .1
380.?
487.7
429 .0
680.7*
463.2
525.6
428.0
421.0
319.0*
518.2
413.0
398.2
438 .0
442.0
521 .G
6 5 2.8*
469.7
423 .0
1190.5*
417.5
549 .%
597.0
411,9
339, r
595 .2
460.C
435.6
527 .C
636.0
7 04 . **
533 .9
5 30 .3
4 06.0
560.9
799.8
528.4
424 ,C
443 .0
289.3
607,3
519,0
473.5
44 1 .C
502.0
481 .1
4G8.2
22 5. G
-------
1
2
3
4
5
6
7
8
9
10
11
1 2
1 3
14
15
TABLE C-61
ENVIRONMENTAL MONITORING AND SUPPORT LAPORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAbLES **
RAW DATA FOR 1 ,1 -D1CHL0R0ETHENE ANALYSIS BY WATtR TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
12 12 12 1 2
a.O 7.2 fi.c 7.2 8.0 7.2 8.0 7.2
5.4
13.?
7.4
1«.1
10.3
8.7
6.4
8.1
14.5
6.1
6.6
9.3
8.3
8.1
25.1 *
4.2
12.5
5.8
7.2
9.6
12.1
3.8
12.4
16.7
6.9
5.6
1 D.C
1C.4
7.3
26.5*
9.C
11 .9*
6.5
9.5
10.0
9.6
4 .:;*
9.6
16.1*
7.7
3.4*
9.0
8.C
44 .9*
9.9
5.4
18.3*
6.0
20.4
9.7
9.9
5.7*
6.4
13.4
6.1
4.5
C. 0 *
13.1
7.3
11.2
7.7
7.7
7.1
9.8
9.6
13.9
6.3*
1C.1
17.4*
7.5
6.1
11.1
11.7
9.1
8.3
7. C
12.4
5.9
7.1
6.8
7.7
4.9*
4.1
14.3
6.3
5.5
10.3
7.3
6.R
11.3
9.7
17.3*
5 .?
17.0*
8.7
9.0
5.4
21.5*
14.9*
7.4
6.2
9.1
7.7
7.3
6.8
13.3
11.3*
7.4
9.2*
8 . h
8.4
4.8
8.7
11.7
5.8
4.6
9.3
6.9
6.4
11.7
-------
1
2
3
4
5
6
7
8
9
1 0
TABLE C-62
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION A6ENCV
** EPA METHOD 624 VALIDATION STUDY - PUNGEAtiLES **
RAW DATA FOR 1 , 1-DICHLOROETHENE ANALYSIS BY WATER TYPE
MEDIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
34343434
120.0 114.0 120.C 114.0 120.0 114.G 120.0 114. C
107.3 60.1
209.4 83.ft
89.9 52.4
133.5 9?.5
122.3 69.8
64.9 58.C
74.7 89.6
198.7 77.2
8 9.0 8*.a
103.9 69.4
117.1 76.4
141.0 90.6
sr.o *
1 3 E . 1 6 2 .1
132.6 88.2
113.6 65.6
222.1* 123.7*
93.7 44.P
136.0 98.7
119. C 81.6
132.C 84.9
8?.6* 59.4*
1C2.1 92.9
96.9 83.5
88.8 88.7
143.5 67.0
9 3.8 93.2
290.9* 68.5
151.1 62.3
176.6 96.1
1C2.0
71.5
130.6
71.1
93.8
81.0
138. ft
99.1
116.9
93.5
98 .8
88.8
85.0*
60.2*
196.1*
106.1
90. 7
84.9
87.5
72.3
116.0
63.5
121 .0
91.1
130. f
63.9
128.3
92.1
99.8
96.0
89.4
02.3
144 .9*
115.5*
U2.fi
18.1
133.7*
157.7*
12C.C
92.3
122.0
47.7
111.0
70.5
123.4
2 9 6.0*
1C2.0
85.6
9 7.2
72.8
77.1
82.6
92.2
77.8
107.1
6 7.2
121.1
62.8
2 CO . 6 *
46.1
-------
1
2
T
4
5
6
7
8
9
10
11
12
13
n
1 s
TABLE C-63
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAtlLfcS **
RAW DATA FOR 1,1-DICHLOROETHENE ANALYSIS BY WATER TYPE
HIGH YGUDEN PAIR, UMTS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
56565656
432.0 460.0 432.C 4 8 C . 0 432.C 480.0 432.0 480.0
401 .?
870.6
364 .1
1045.2
520.0
656 .0
200.0
541.0
286 .0
376 .6
433 .0
417.0
321.0
495.1
560.6
471 .C
1129.4
454 .8
1257.3
550 .C
42C.C
324.C
881.2
328.C
359.4
496.C
529.C
447.5
505 .0
634.3
379.C
1 C 8 8 . C *
3 72 .0
1C 1 5 .0 *
476 .C
495 .0
271 .C*
4 29 .6
340 .0
3 78 .2
297.0
4 58 .C
6 59 .8
4 04.4
5 23 .2
412.0
1 C 3 2 .5 *
475 .9
2C03.2*
576 .0
64 2 .0
291.0*
636 .8
3 56 .0
347 .4
417.0
468.0
68 7.7
4 9 8.2
761.1
401.0
643 .7
340. 2
1116.8*
499.0
531.0
3 5 C . C *
575 .0
295 .0
351.7
351.0
445 .0
362 .2
247 .8
571.7
473 .C
824 .5
475 .8
2172.9*
561 .C
483 .0
349.0*
822 .9
3 3 0. C
358 .7
386.0
4 69.0
493 .3
584 .7
665 .9
379.0
1161 .S*
340.2
1356.0*
5 35 .0
381 .1
333.0
561 .1
27? .0
339.8
399 .0
569.0
461 .1
*90.1
687 .7
471 .0
789.1*
513.1
1473.6*
525 .C
596 .0
327.0
1161.8*
424 .0
410.4
T E 8 . 0
500. C
462 .5
406 .5
32 5 .5
-------
LAB
1
2
3
4
5
6
7
8
9
10
11
1 2
13
14
15
TABLE C-64
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEABLES **
RAW DATA FOR 1 , 1 , 1-T R I CH L 0 R 0 E T H A N E ANALYSIS BY WATER TYPE
LOW YOUDfcN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EfFLULNT
1
2
1
2
1
2
1
2
9.0
10.0
9.:
1C.0
9.0
10.0
9.0
10.C
7.5
9.8
P .9
9.1
8.6
9.8
9.3
10.5
11.6
14.9
11.7
14. 3
9.0
13.0
9.4
11.9
8.C
9.7
7.6
P.9
8.5
9.2
22.0*
37.1*
12.3
12.2
i:.3
14.3
7.3
15.2
12.3
11.1
11.9
12.3
4.7
1C.0
8.7
3.?
0.0*
0.0*
8.3
1 1.9
7.6
11.8
8.9
9.4
7
7.9
6.8*
5.5*
4.4*
8.6*
7.4
8.1
6.2
7.7
10.2
10.1
11 .4
1C.4
8.7
9.9
14.2*
13.1*
12.1
12.6
11.4
U.7
10.5
12.9
11 .0
13.6
7.0
10.5
8.5
P.7
9.8
10.0
1C.8
9.7
10.2
11.3
9.1
9.4
10.4
11.7
13.1
12.C
10.3
12.4
10.2
9.3
21.4*
24.6*
10.7
11.9
11.2
15.G
9.4
24.1*
18.9*
14.6
9.2
1C.8
10.0
9.5
3:.7*
9.0
11.5
11.5
P .9
10.8
21.0*
13.1
9.6
1 1 .6
9.3
1C.2
0.0*
C.O*
-------
1
2
3
4
5
6
7
8
9
I u
TABLE C-65
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPKfcNT
ENVIRONMENTAL PROTECTION A 6 F N C Y
** EPA METHOD 624 VALIDATION STUDY - PURGE AbLE S **
RAW DATA FOR 1 f 1 f 1 - T R 1 CH L 0 R 0 E T H A N E ANALYSIS OY WATER
MEDIUM YOUDFN P A IR « UNITS - UG/l
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
34343434
9 5•0 100.C 95.0 1CC.C 95.C 100.C 95.0 1CC.C
I o ^
103
.8
77.fi
111.0
83.9
104.0
82.4
96 .5
73.4
.9
84.6
136.3
92.4
129.7
67.4
95.0
62.7
.3
63.4
97.7
56.7
V 5 . 1
88.5
182.4*
1 b 7. 2 *
.0
98.C
1C3.5
85.2
121 .6
67.5
67.2
1*1.2
.0
59.1
91 .C
44.7
4C.4
83.8
8 6.4*
O.C*
.7
70.C
9: .1
77.9
79.3
70.3
£6.0
5C-.C
• 6 *
8 4.9*
7C.C*
7 8.1*
76. 1
81.7
90.9
S6 . S
.0
79.6
122.2
97.9
113.5
85.6
135.1*
142.3*
• 0
12 8.0
143.C
127.G
K4.C
138.0
134 .0
135.C
.7
106. C
98 .t
128.8
112.7
124.5
118.1
121.9
.6
£8.2
117.8
t2.0
101 .8
94.3
75 .9
9C.6
.0
95.4
37.1
1C9.C
116.C
106.C
98 .C
9C.5
.6
*
316.2*
1 C 1 . 6
146.3
129.5
92.8
10 3.1
.0
71.8
15C.3
76.8
126.5
1 L»8 . 9
118.3
77.9
.7
120.6
13 3.7
1C6.2
1C3.8
108.7
67.3
6 9.5
-------
1
2
3
4
5
I>
7
P
9
1 0
11
1?
1 3
1 4
15
TABLE C-66
ENVIRONMENTAL MONITORING AND SUPPORT LAHGRATCRY
OFFICE Of RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PUKGtABlfcS **
RAW DATA FOR 1 , 1 , 1 - T R I C H LOR 0 E T H A N E ANALYSIS BY WATER TYPE
HIGH YCUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUtNT
56565656
A 00 • 0 360. C 400.C 36C.0 40C.C 360.0 400.0 36C.0
4 07.3
692 .6
385 .9
476.7
470.0
446 .0
213.0*
467.5
414 .C
586.7
466. o
399.0
215.6
5 02 .1
4 64.2
363 .8
560.5
340.3
396 .3
300.C
3 1 7 . 0
239.0*
411.7
4 7 3 . C-
434 .2
399.C
374 .0
266 .9
476.9
303.2
4 C8 .C
720 .7
3 77 .5
427 .8
1 71 .C
790.C
2 49.0*
464 .8
570.0
*27.1
409. C
481 .0
471.1
44C.9
352 .2
34C.0
5C5.7
374 .1
471.4
217.0
447.0
2 4 9.0*
529.2
362. 3
436.6
4 0 6 • 0
391. C
33P.7
3 3 2 .8
5 8 3 .4
398.0
660.9
389. C
3C8.4
161 .0
3 61 . C
363 . C
1 Cfc . 3
399.n
6C7.G
4 23 . C
421.0
3:6 .9
3 32 .9
365 .3
336.C
52 5 .8
376.9
257.9
359 .0
303 .0
276.C
421.9
337.0
469.6
351 .C
376.0
3 2 5 .:
5 5 3 .0
353 .5
4Q4.0
770.6*
4K.3*
377.7
357.4*
2 59 .T
3 03 .0
587.8*
390
526 .8
4 54 .0
548 .0
371 .1
448.4
290 .8
347 .0
4>4 .4
P58.6*
43C.9
3C1 .4*
391 .C
273 .0
4 7 7.7*
4 3 6.0
588.6
369 . C
404 .0
2 3 3 .3
376.9
346 .3
-------
1
2
i
4
c
6
7
8
9
10
11
1 z
13
14
1 5
TABLE C-67
ENVIRON MENTAL KOMTORING AND SUPPORT LAFORATOM
OFFICE OF RESEARCH AND DEVELOPKENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PUR6EABLES **
RAW DATA FOR 1 ,1 , 2-TR I CHLOR0ETHANE ANALYSIS BY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
12 12 12 12
10.8 12.C 1C. 8 12.C 10.8 12.0 10.8 12.G
10.6
12.7
12.9
12.9
13.1
9.5
13.0
11.2
11.5
8.6
11.7
13.9*
16.5
1 1.7
3.7*
13.C
15.7
14.4
13.1
9.9
13.8
7.8
13.6
12.9
11.1
13.3
15.5*
16.6
11.1
49.5*
11.7
9.P
12.9
10.2
11.5
11 .4
7.^*
1C.9
12.1
3 . 8 *
12.2
14.1
15.2
4r .4*
12.4
12.5
16.4
14.9
13.0
1C.3
14.8
11.3*
9.0
14.1
9.3*
1C.8
15.4
25.7
14.?
22.9
13.2
10.C
12.2
15.9
12.9
12.9
9.7*
14.7
11.4
9.8*
12.2
12.4
20.3*
14.9
75.2*
12.4
16.0
13.3
14.5
11.0
11.3
5.6*
10.6
12.3
9.5*
13.1
14.3
IP .5
15.3
26.5*
13.C
9.0
10.9
17.9*
9.9
11.0
8 .C*
13.6
11.1
8.4*
11 .8
10.4
12.0
10.4
11 .8
13.5
17.2
19.4
10.9
14.4
13.C
11.0*
13.0
13.2
10.1*
12.3
15.4
12.3
12.fi
10.6
-------
1
2
3
4
5
fc
7
8
9
10
11
1 2
13
14
15
TABLE C-68
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD b2U VALIDATION STUDY - PURGEABLES **
RAW DATA FOR 1 • 1 , 2'TR I CHL0R0ETHANE ANALYSIS BY UATlR TYPE
MEDIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
34343434
114.0 120.0 114.0 120.C 114.0 120.0 114. C 120.C
129.0
133.4
123.8
114.5
144.0
12 0.0
73.6*
113.7
122.0
113.0
129.4
156.0*
129.1
122.C
38 .6*
127.C
139.0
145.2
124.8
11 4 . C
9C.3
11 4 . C
120.3
12 5.0
111.2
133.7
142.C*
*
113.3
124.5
132.7
116.7
136.5
1 OS .4
1 u 9 . ¦ j
103 .C
35 .4*
89.7
13 2.0
94 .0*
123.1
88 .7
3 33 .7*
166.7
135.6
12€.:
151.9
139.4
117.7
106.0
124.3
98.0*
126.6
138.0
112.®*
135.5
153.0
127.1
125.7
128.7
137.0
135.5
133.5
197.4
101 .4
94 .8
91.4*
153 .6
116. 0
87. 1 *
12 5.4
139 .0
158.fi
129. 1
1C7.4
13 2.0
135.6
140.0
156.2
152.0
123.0
108.0*
109.2
116.0
97.6*
129.1
163.0
164.6
144.7
122.1
126.0
139.5
108.?
99.3
114.0
110.0
95.9*
125.4
12 7.0
100.?*
95 .8
117.0
112.5
1 16.8
108.?
144.C
143.4
12C.1
1 e 4 . 3
155.2
100.0
104.0*
127.6
139.0
98.5*
128.1
1 ti 8 . 0
1 J8.1
112.C
99.3
-------
1
2
3
4
5
6
7
ft
9
1C
11
1 2
13
1 4
1 5
TABLE C-69
ENVIRONMENTAL MONITORING AND SUPPORT LAPGRATORY
OFFICE OF RESEARCH ANO DEVELOPMENT
ENVIRONMENTAL PROTECTION A6ENCY
** EPA METHOD t2U VALIDATION STUDY - PtJRGEAfiLES **
RAW DATA FOR 1 , 1,I-TR I CHL0R0ETHANE ANALYSIS BY WATER TYPE
HIGH YOUDEN PAIR, UNITS - U6/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
5 6 5 6 5 6 5 6
480.0 432.C 480.0 432.0 48C.0 432.0 480.0 432.0
512 . C
556.9
493.5
446 .9
535.0
475 .0
165.C
470 .6
354 .0
353 .4
534 .0
565.0*
252.6
474 .8
5OP . 1
44 5 .0
729.4*
396.8
403.9
37C.C
25 7.0
2 3 0 . G
352.1 '
4 56 .0
334.2
5 34 .C
4 6 7.0*
3 0 5.5
304.5
272.3
4 6° .C
701 .8*
4 68 .9
408 .3
4 36 .0
392 .0
194 .0*
331.3
467 .0
3 3 2.3*
538 .0
5 43 .0
413 .4
421 .6
475 .5
446 . j
5 06.1
441.2
4G7.7
4 5 3 .3
3 9P.0
19 9.0*
439.1
339.:
266.5*
569.0
6 2 2.0
3 6 C . 1
35C.1
489.1
5 3 7 . C
598 .0
4 78 .0
440.8
417.0
418.0
2 78.0*
391.2
334 .0
284.3*
5 65 .0
5 57 .:
337.6
263 . 5
4 39 .1
422.0
671.7
417.7
232 .8
506 .0
316.0
210.0*
447.2
331.0
281 .1 *
453 .0
463 .0
312.0
459.8
397.1
513 .0
615.6
4 49.7
431 .0
623 .0
3 8 7.8
193.0*
477.7
3 2 7.0
33* .7*
558.0
542 .0
319 .0
401 .9
3 59.1
495 .C
7CC.1
191.0
508 .C
3 31 . C
350.0
2C8.0*
418.1
38 2 . C
264.4*
4 5 3 . C
487.0
26 5 .1
301.1
331.7
-------
1
2
3
4
5
t
7
8
9
1C
11
12
1 3
14
15
TABLE C-70
ENVIRONMENTAL MONITORING AND 5UPP0RT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAblES **
RAW DATA FOP 1 ,1 , 2 , 2-TETRACHL0R0ETHANE ANALYSIS BY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
1
2
1
2
1
2
1
2
15*0
17.0
15 .C
17.3
15.0
17.C
15.0
17.0
14.5
16.2
17.3
16.5
18.7
23.1
19.9
10. 7
13.3
13.5
e .2
15.9
7.9
15.2
10.8
17.7
18.8
17.5
18.0
19.5
16.4
15.8
1 5 . T
1C.0
14.4
17.4
16.8
15.8
12.1
16.3
22.8
6.5
15.9
16.8
18.5
15.3
16.C
5.5
15.5
14.9
6.6
17.6
12.4
2:.4
15.4
17.7
13.0
13.4
22.3
13.3
11.5
15.0
13.0
13.4
11 .6
17.5
14.3
IP.7
15.7
15.6
21.3
15.9
19.2
18.0
18.8
18.1
2 0.2
25.8*
17.8
16.1
17.7
20.5
13.9
27.6*
15.7
16.0
27.7
24 .n
16.9
23.4
21.4
17.8
18.2
U .6
17.3
19.1
23.1
22.5
12.0
12.6
14.6
12.2
12.4*
14.2*
9.7
10.6
2 5.6
21 .6
2? .7*
29.9*
23.9
19.1
21 .6
20.3
10.2*
8.1*
37.2*
11.9
12.5*
13.1*
7.4*
1 C . 5 *
14 5.1*
131.8*
11 .7
97.8*
268 . 2*
44.1*
91 .2*
1.7
-------
LAO
1
2
3
4
5
6
7
8
9
13
1 1
1?
17
14
15
TABLE C- 71
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGtAtBLtS **
RAW DATA fOR 1 , 1,2•2-TETRACHLOKOETHANF ANALYSIS BY WATER TYPE
NEDIUK YOUDEN PAIR, UMTS - UG/L
DISTILLED WATFR TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
3 4 3 4 3 4 3 4
162.G 170.0 162.0 17C.T. 162.C 170.0 162 .C 170.0
216.a
129.1
196.1
173.7
169.3
163.0
10 7.0
167.A
176.0
164.5
170.7
1U.0
171 .6
106.7*
112.1
233 . C
131 .6
£. L» 3 . C
161.2
161 .0
89.1
170.0
176.8
179.0
183.2
U2.6
149.C
*
96.7*
30.3*
135.8
96 .7
192. C
157.2
15 e. i?
13? .C
111.0
UCJ
2 4 ? . C
153.9
184.2
6 9.3
5 IP .1 *
151.6
175 .5
IbC.D
149.2
2 2 C . 9
144.7
19 4.3
14 7.3
12 3.0
174 .7
204 .0
199.3
160.6
114.0
2 C C . 5 *
1 1 6 . C
3 0 r . 4 *
196.0
12 2.3
1 £9 . 7
1 53.7
177.1
163. 5
124 .0
211 .5
174.C
145.9
13 2.3
104.0*
229 . C
116.5*
2 35 .9
253 .0
136 .5
2 2C . 5
15 0.9
174.C-
152.C
14 8.0
163.7
1 8 2 . C
156.9
137.3
13 3.0*
193.7
118.4*
212.3
176.0
1 37.9
129.?
79.4
132.n
144 .0
131 .0
1 77."
196.0
18* .2
110.5
111.0
149.?
85.4*
44.0
ne. 3
149.1
52.3
26 6 .7
17 2.0
135.0
137.0
187.3
210.0
163.2
1 3 0 . 4
2 u f . 0
156.6
7 6.4*
230. 7
-------
fy v.
1
2
3
4
5
6
7
8
9
1?
1 1
12
1 I
14
1 5
TABLE C-72
ENVIRONMENTAL MONITORING AND SUPPORT LADGRATQRY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA KETHOD 624 VALIDATION STUDY - PURGEAbLES **
RAW DATA FOP 1 , 1f2 , 2-TETRACHL0ROETHANE ANALYSIS bY WATER TYPE
NIGH YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATCR SURFACE WATER INDUSTRIAL EFFLUENT
56565656
630.3 612.C 650.0 612.3 680 .0 612.0 680.0 612.0
669.0
6 G 1 . C
553.9
741 .8
E06.6
72 3 .5
518.6
71 0 . G
659.0
57«
550.0
343 .0
464.0
584 .C
724.4
566.0
465 .0
634 .C
54 7 .4
564 .2
«8j.3
586 .C
414.0
44b.C
536.?
621 .C
437.2*
702 .4*
335.7
52 7 .2
A 96 .0
73C.G
592 .0
4 7 2.3
781 .A
83C.0
5G8 .2
5 2 3 .$
6 76 .0
677.0
'15.0
468 .0
5 ?2 .0
4 6 6 .0
531 .5
631.1
7 A 2 .0
4 7 5.0
6 57 .9
485.8
9 19.7
12 39.0*
315.0
5 4 3 .0
926.3*
pee.7*
442.C 362 .A
?56.6 644 .7
697. C 823 .0
562.5 703.6
ti3A.fi 73S.8
556.0 533.8
715 .0 634 .G
427.0 578.0
780 .0 554.0
532.4 637.3
438.0 442.0
471.? 463.1
632.C 577.0
"*71 .0* 3 51.0*
630.9 563.6
23vw. 5* 4 31.4*
840.3 460.7
730.0 425.C
630.4 690.*
753 .1 229.8
393.4 693.5
742.0 492.0
56'.0 557.C
5 35.0 5 3 8 . G
6 95 .1 574 . 5
416.0 555.0
574.8 453.9
697.0 568.0
4 3 3 . 0 29 A. C
579.0 516.4
315.3* 323.2*
165.9 878 .S
-------
1
2
3
4
5
6
7
6
9
10
1 1
12
13
14
15
TABLE C-73
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RFSEARCH AND DEVELOPfLNT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PIJRGEA&LES **
RAW DATA FOR 1 ,2-D I CHL0ROBENIENE/1 , 4-DICHL0 ANALYSIS BY WATER TyF
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATtR TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
1 2 1 2 1 2 1 2
16.0 16.3 16.0 16.3 16.0 16.3 16.0 16.3
21 .6
1C.6
19.A
19.5
19.4
21 .C
15.0
19.2
24.4
33.7*
IS.7
77.0*
22.9
12.6
19.4
17.7
17.4
13. ft
24.0
19.3
24.6
31.7
22.C
£7.4*
31 .1
6 .6*
17.f
19.?
20.*
*
10.6
2C .6
17.3
5 .4*
59.4*
16.9
2 2.6
7.3*
2C.C
17.0
1 8.2
*
13.2
28.7
25.5
23.2
0.6*
13.0
74.S*
21 .3
3.9
18.6
13.9
17.0
*
1 o. e *
24.9
21.2
23.7
45.2
35.2
89.9*
24.5
20.5
19.5
25.3
1 7.8
*
10.4*
19.4
16.2
25 .7
32.5
25.0
35.5*
2 P. .6
5.0
14.5
17.2
2C.4
*
12.C*
1< .4
17.0
16.3
3 T . 0
4 3.^
27.3
22.4
h .4
29.1
17.5
17.2
*
1 5.0*
13.4
U .2
2 0.?,
37.7
28. 5
1.9
-------
1
2
\
4
5
6
7
8
9
10
11
12
13
14
15
TABLE C-74
environmental monitoring and SUPPORT lahORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAaLES **
RAw DATA FOR 1 , 2-DICHL0ROBEN7EKE/1 , 4-DICHLO ANALYSIS BY WATER I VP
PEDIlir. YOUDFN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
34343434
20C.0 200.G 200 .0 2 0C .j 2C0.0 200.C 203.0 20C.G
254.1
53.3
193.7
210*1
226.0
«
84.5
215.4
203 .3
309.' j
160.2
168.?
315.5*
135.1
164.1
2 5 D . 5
217.6
186.8
122.4
212.4
197.5
306.0
*
92.6
22C.7*
14 5.8
37.7*
236 .8
193 .8
189.6
*
64 .6
266.7
3 1 j . C
163.0
166.7*
201 .E
3CI .3
220.0
171.8*
223.6
167.3
236. C
*
92.8
191.2
201.1
278 . D
3 4.1*
63.4
216. D
214.1
142.5
283 . 2
271 .2
225 .4
*
81.2*
297 .1
22C.0
265 .3
413.3
13.4
634.C*
113.1
128.C
233 .9
183.5
230.0
*
91.0*
181 .4
182.2
295 .0
176.3
164.5
272 .1 *
214.9
25.3
363. S
177.0
177.0
*
112.2*
2C4.7
231 .0
226 .:
232 .0
167.9
108.0
22 5. G
H1.6
275 .1
2u3.8
212.0
*
89.4*
175.5
212.0
46C.0*
193.7
31C.0
154.3
-------
1
2
3
4
5
6
7
8
9
1C
11
12
1 *
14
1 5
TABLE C-75
fchVIKON^i-MAL MOW I TORINO AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPPL NT
ENVIRONMENTAL PROTECTION AGENCY
*« EPA METHOD 624 VALIDATION STUDY - PURGEADLES **
RAW DATA FOR 1 , 2 - D I C H L 0 ROB E N Z EN E / 1 « 4~D I C H LO, A NA L Y S I S &v WATER fYF
HIGH YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
5 6 5 6 5 6 5 6
778,0 780.0 77-3.0 78C.0 77P.G 78C.0 77B.0 780.G
.1
972 .7
96? .6
553.7
918.0
4 06. 0
771.0
657.0
e 3 6. o
971.9
735.6
1 C 5 ? • 0 *
344.1
665 .7
75 5 .9
7GC.6
7iC • 0
448.G
572.0
973.0
965 . C
6 3 6 . t
614.2
110 9.9*
552 .0
519.8*
870.9
629.8
7 £ 2 • C
*
4 34 .0
951 .3
1335.0
7*3.0
313.?*
3 50 .6
522 .0
94 2 . C
o.:«
946.3
612.3
944.3
*
3 51.0
49e .1
668.0
138C.0
3 0 9.4*
65 3 .3
1 2 5 f . 6
743 .1
801.3
1031.5
723 .7
820.0
*
530.C*
774 .1
493 .C
926.0
934 .8
5 8 3.1
13 4 3.9*
3 8 3.1
356 .5
926.0
674 .7
e 3 6 . 0
*
444.0*
659 .9
686 .0
790.0
830.2
5 59.9
79C.3*
^ 5£ .9
SG5.2
610.7
495 .5
9 3 0.0
4
541 .0*
6C0.6
603 . C
697.0
1144.5
593 .2
4 09.?
793 .0
576.7
84 5.1
565 .4
614.0
*
4 2C.C*
563.5
925 .0
79 P . 0
734 .3
1G25 .8
61?.4
-------
AtfP
TRU
L AR
1
2
3
4
5
6
7
S
9
10
11
1 2
13
14
15
TABLE C-76
ENV1H0HMEMAL WON 1 *1 0 R I Ki G AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY * PURGE ABLE S **
RAW
DATA FOR
1.2
-OICHLORQETHANE
ANALYSIS BY
WATER TY
LOW
TOU DEN PAIR, UNITS - UG/L
DISTILLED
WATER
TAP
WATER
SURFACE
WATER
industrial
EFFLUENT
1
2
1
2
1
2
1
2
9.9
11.C
9.9
11. C
9.9
11.0
9.9
1 1.0
0.0*
7.4
6.9
2.8*
7.9
5.£
7.4
fc. 1
0.0*
17.1
c.o*
13.0
4 . &
0.0*
3.7
0.0*
10.0
11.6
9.9
11.5
10.6
11.3
10.3
16.4
11.7
10.7
10.4
1C.8
9.7
15.2
1 ?. 5
16.7
io.a
10.0
5.3*
10.7*
? .9*
4 . C *
9.2
10.9
10.1
12.8
9.2
14.3
9.1
11.2
9.2
9.4
11.2
7.1
6 . w
11.9
9.6
9.3
E .4
9.2
10.9
12.2
10.6
9.9
10.9
11.3
13.3
12.6
12.6
13.0
13.5
11.S
11.2
13.7
11.4
15.0
* • 6 *
10.4
9.9
1 C . 1
9.9
9.3
9.3
P.5
a .9
10.7
g .6
P.9
9.3
10.6
9.5
9.3
9.6
10.6
f .9
1C.4
9.5
1C.6
13.0
10.6
13.2
17.8
12.4
27.2*
19.1
16.2
O.P
10.9
10.9
11.0
37.3*
11.9
14.*
13.2
10.7
12.0
25.1*
27.4*
11 .7
13.9
23.1
12.3
5.9*
10.0*
-------
1
2
•7
4
5
6
7
a
9
10
11
12
13
14
15
TABLE C-77
INVIRONMENTAL PON1TORING AND SUPPORT LABORATORY
OFFICE CF RESEARCH AND DEVELOPMENT
ENVIRON CENTAL PROTECTION AGENCY
** EPA PETHOD 624 VALIDATION STUDY - PUKGEABLE S **
RAW DATA FOR 1,2-DICHL0RCETHANE ANALYSIS BY WATER TYPE
MEDIUM YOUDFN PAIR* UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
34343434
104.0 110.0 1G4.0 11C.: 1C4.0 11C.0 1G4.0 11C.0
H7.C
76.8
151.9
79.7
109.0
116.0
94.3
76 . 3
112.4
79.9
131.2
1GC.4
134.6
78.4
117.2
61.5
105.1
78.2
118.2
69.3
114.4
104.8
186.4*
par.7*
93.9
97.5
137.3
64.9
163.0
103.0
131 .2
124.7
12C.0
59.1
9 5.6*
45.6*
42.4*
83.8*
1G7.C
76.9
84.2
89.4
109.C
99.9
91 .8
70.9
99.5
6 0.4
82.G
122.0
86.1
102.C
1G1.0
94 .4
1 16 .C
96.9
113.3
81 .1
103.5
94.8
121.0
90. 3
112.1
132.9
124.C
13 2.2
i?2.r
140.0
1C9.C
137.0
141 .C
UP .0
128.7
114.2
11c.1
131.3
1C5.7
112.0
121 .0
112.2
123.2
1C5 .6
111.2
1G2.6
120. 1
111.9
87.1
112.8
141.3
93 .8
91.7
116.0
118.0
115.0
96 .4
137.G
124.5
*
338 .9*
1C5.2
1 6 C . 6
140.9
101.8
5 6.6
116.3
67.6
164 .0
73.3
125.9
116.9
119.1
77.5
139.1
159.5
151 .1
113.7
11.2*
111.5
94.2*
55.1*
-------
1
2
3
4
5
6
7
5
9
10
1 1
12
13
1 A
15
TABLE C-78
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTfcCTION AGENCY
** EPA KETHOD 624 VALIDATION STUDY - PUKGEAbLLS **
RAW DATA FOR 1,2-DICHLOROETHANE ANALYSIS BY WATER TYPE
HIGH YOUDEN PAIR, UMTS - UG/L
DISTILLTD WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
56565656
44C.G 396 .G 440.0 396.0 44C.0 396 .C 443 .G 396.0
456. 0
685 .2
456 .6
476.6
479 .0
475 .0
295 .0
427.4
438 .0
511.4
547.0
444 .0
246.9
556.1
539 .2
360.C
5 3 0.0
392 . b
413.6
306.0
41 7.C
380.0
401.4
4 78..C
43 5 .4
48 3.0
4 3 6 .0
313.5
440.5
326.1
4 53 .0
6 75.0*
445 .1
433 .7
409.C-
4 80.0
426.0
405 .4
471 .G
5 27.4
549 .0
523 .C
5C9.1
458 .2
3 90 .1
33 5 . j
540.2
43* .8
374.0
230.0*
584 .0
314.0
462.7
4G8..0
4 C 5. 3
51* .0
432.0
369.9
4 fe 2 . 4
481.4
41b.0
718.2*
46 7.2
323 .3
18 2.0*
367.0
474 .0
393. 1
4 4&.C
484 .6
521.0
449 .0
31 S . 7
334 .3
363 .fc
442 . C
5 3 7 . 0
436.2
289 .ft
390.0*
231.0
393 .C
431.5
371 .0
401.9
439 .C
4 1 9 . C
336 .5
554 .9
318.2
396 .0
754.3*
4 59 .9
497 .6
4 4 2 . n
322 .2
4 24 .0
497 .9
413.0
467 .2
514.0
528 .0
312.4
447.7
344.4*
365 .0
490 .3
1272.6*
56C.1
3 2 8.0
4 31.0
35C .0
454 .8
511.0
442 .3
428.0
469.0
2 6 6 .2
352.0
118.4*
-------
1
2
x
v«
A
5
6
7
8
9
ic
11
12
13
1 A
15
TABLE C-79
ENVIRONMENTAL MONITORING AND SUPPORT LAMORATORY
OFFICE or RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 62A VALIDATION STUDY - PURGEABLES **
RAW DATA FOR 1,2-DICHLOft0PR0PANI ANALYSIS PY WATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
12 12 12 12
13.5 15.0 13.5 15.0 13.5 15.0 13. 5 15.C
16.0
r.o*
17.A
18 .C
17.5
U.I
U • 7 *
17.2
2C.3
12.7
17.A
2 6.0*
19.1
17.6
22.7
18.2
32.3*
18.3
17.5
15.8
18. A
1 C . 5 *
20.9
2 7. A
17.5
19.1
92.0*
26. fi
2 0.1
24.9
17.2
C .0*
17.0
13.8
17.9
15.6
9 ~ A *
17.A
19.P
15.0
17.A
22 .0
19.6
69 .6 *
22 .A
19.0
15.5
18.9
21.3
17.5
18.6
16.2*
15.6
20.7
15.A
15.8
2 A. 0
15.6*
20.0
13.9
18.3
G. 0*
16.0
25.1
18.6
18. 3
13.5*
2C . 5
18.3
15.0
17.8
19.0
28.3
21.8
2C.0
20.C
C.C*
18.A
19.2
18.9
17.6
1 A .8*
u.a
19.9
1A .9
19.5
3 A . C *
23.*
22.3
2C .A
17.2
0.0*
13.A
31 .A*
6.9
15.0
11.7*
23.3
18.8
13.8
17.9
12.0
16.5
15 .A
17.A
17.1
C.O*
3 6.5*
19.2
1 A . t
17.5
1 A . 2 *
2 0.2
2 2.3
U.5
17.6
25.0
18.0
16.A
1 S.5
-------
MP
RU
AB
1
2
3
4
5
6
7
8
9
10
11
1?
13
14
15
TABLE C-80
ENVIRONMENTAL MONITORING AND SUPPORT LARCRATGRY
OFFICE Of RESEARCH AND D E VE LO PM E N T
ENVIRONMENTAL PROTECTION' AGENCY
** EPA f.FTHOD 624 VALIDATION STUDY - PURGEABLES **
RAW DATA FOR 1 , 2 - D 1 C H LO R 0 P R OP A N E ANALYSIS PY WATER TYPE
P E DI UP YOUDEN PAIR, UMTS - UC/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL E f FLUENT
3 4 3 4 3 4 3
<•
142.0 1 5 0 . C U2.C 1 5 u . 0 142 .0 150.0 1 42 .0 1 50.0
211.0
262 .1
177.6
255.9
2 28 . C
16 9,0
110.0*
192. 8
203 .0
181.7
2 C 0 . 1
24 5.0*
175 .6
195.7
36.2*
1 E C . 0
3 1 C . 1 *
1 fi 9 . 1
1*2.2
170.0
1 4 3 . C
1 5 0 . C; *
175.6
221 .0
166.7
199.5
266.0*
*
185.6
1 £ 6 . 2
223.4
129 .6
184.1
155.7
161 .C
154.0
126 .C *
14 5.9
191 .0
1 5 7 . C
191 .2
2 3 4 . C
4 ft6 .6*
27G.9
195.6
18 6.0
37C.4*
185.4
16?.3
157.0
167. j
1 4 0 . C *
192.8
22C.C
i e i .9
2C2.1
219.C
17c.C
175.8
185.9
203.0
3C7.1*
iac.2
219.2
167.3
145.4
130.0*
230.2
195 .C
145.6
18 6.8
2 09.0
225 .0
201 . 5
1 5G.0
222 .0
308.5*
185.8
243 .1
223 .C
1 8 1 . C
144.C*
173 .6
183.0
175.2
193 .1
250.0
216.0
218.3
169.5
181 .0
351 .1*
181.1
65.1*
168 .6
1 5F .0
147.C*
194 .7
?C1 .0
1 74 .6
140.3
2 58.0*
169.7
178.8
187. P
2 09 .0
346.6
191 . 3
312.5
22u.6
141.0
144.0*
213.2
22 5 .0
173.6
192.0
277.0
169.3
172.4
215.2
-------
1
2
3
4
5
6
7
8
9
10
11
12
1 3
1 4
15
TABLE C-81
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGtAULES **
RAW DATA FOR 1,2-D1CHL0ROPR0PANE ANALYSIS H Y WATER TYPE
HIGH YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
56565656
600.0 54C.3 630.C 54C.0 600. 0 540.C 600.C 540 .C
822.0
1574.5*
650.3
5 5 5 .9
808 .0
679.0
2 6 9 • G *
65 5 .9
576 .0
74 5.6
866.0
764 .0*
375 .7
706.0
604 .3
579.0
15 7 6.0*
5 £ 2 . 3
528.7
551.0
414.0
349.0*
635 .2
692.0
574 .2
749.0
596.0*
445.5
457.9
319.9
719.C
1140.5*
£42.3
582 .3
656 .0
5 4 2 .0
343.C*
534 .1
575 .C
631.3
837.C*
604 .0
£75.0
605 .2
569 .0
612.0
1415.1*
612.6
5 6 £ . 6
6 6 0*0
5 42 .0
333.j*
635.6
596.0
568.7
76 9.3
683.0
560.4
530.2
58 8.8
779.C
1903.2*
626. 5
614.6
678.0
4 73 .0
462.0*
672 .9
5 2 5 .0
613.7
781 .0
557.0
482.9
399 .8
573 .8
659.0
1645.4*
593 .8
349.4
797.0
5 40.3
362.0*
739.5
5 OC-.O
5 5 5 .0
6 81.0
624 .0
4 76 .0
682 .4
699.2
731 .0
1 772 .0*
605 . 0
587.5
908 .6
5 2 7 . 1
368.0*
667.1
5 5 7.0
623 .2
782 .0
107.0*
544 .9
580.8
6 05 .C
713.0
12a5.7*
65 2 .3
777.2
491.6
524 .0
3 51.0*
728.4
6 3 5 .0
559.9
675 .0
560.0
43 0 .2
429.0
781 .3
-------
1
2
3
4
5
6
7
8
9
10
1 1
1?
13
14
15
TABLE C-82
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPvEM
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGEABLES **
RAW DATA FOR 1t3-DICHLOR00EN7ENE ANALYSIS BY JATER TYPE
LOW YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
12 12 12 12
8.0 7*2 6.0 7.? 8.0 7.2 8.0 7,2
10.ft
9.6
9.9
10.0
7.9*
*
9.8*
9.7
9.6
10.0
0.0*
10.3
3 7.3*
1 C • 5
17.3*
7.8
7.7
9.2
*
5.2*
10.6
9.7
8.1
12.5
9.7
30.2*
H .6
4.9
8.4
9.4
9.4
*
4 .0*
1P.0
9.0
11.9
4.9*
33.5*
12.1
9.5
17.6
8.5
7.9
7.2
*
6.6*
29.1
1C.3
7.4
5.3*
3.3
24.3
10.7
5.3
9.4
6.6
8.6
*
5.3*
27.4*
10.4
6.8
14.0
19.G
38.7*
11.3
11.9
8.0
1C.3
7.7
*
4.7*
12.0
7.2
9.0
6.5
13.9
14.1
14 .0
11.3
6.8
7.8
7.4
*
3.1*
10.0
P .9
6.3
13.0
21 .6
17.9
1C.6
6.4
11.9
8 . C
6.6
*
6.1*
7.5
7.9
7.1
4.2
12.£
5.9
-------
MP
RU
AB
1
2
3
4
5
6
7
6
9
10
11
12
13
14
15
TABLE C-83
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL PROTECTION AGENCY
** EPA METHOD 624 VALIDATION STUDY - PURGlAbLES **
RAW DATA FOR 1 , 3 - D 1 C H L0 R OB E N 2 E N E ANALYSIS BY UATEK TYPE
MEDIUM YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUlNT
3 4 3 4 3 4 3 A
120.0 114.C 120.C 114.0 12C.0 114.0 120.C 114.0
15 5.1
135.6
120.2
112.2
118.0
*
46.3*
134.3
115.0
18 5.0*
129.5
126.2
205.7*
13 5.1
15C.C
131.3
124.5
103.0
*
50.C*
130.8
114.0
163.0
*
64.2
125.3*
90.3
128.0
139.0
121 .0
110.0
*
4 3.3*
117.3
174.0
fi8.fi
115.7*
163.0
161 .5
123.0
157.3
124.7
93.1
126.D
•
55.2*
113.8
114.0
156.C
39.3*
42.1
167.5
131.7
156.7
1 36.6
159.5
128.2
«
54.4*
166.2
12 8.0
14 7.0
174 .1
123.0
145.7
134.7
139.7
138.6
106.1
113.0
*
45.3*
113.5
1C4.0
156.0
120.8
115.2
161 .5
127.4
145.3
198.1*
12?.8
1 16.C
*
60 .6*
94 .0
135.0
128 .0
131 .0
127.C
114.5
131.0
158.5
1^8.1
10F.4
1 j 6 . 0
*
4 3.8*
125.3
112.0
258.0*
1*5.1
230 .8*
134.9
-------
1
2
3
4
5
6
7
8
9
10
11
12
13
14
IS
TABLE C-84
ENVIRONMENTAL MONITORING AND SUPPORT LAf'ORATOKY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL- PROTECTION AGFNCY
** EPA METHOD 624 VALIDATION STUDY - PURGEAtfLE S **
RAW DATA FOR 1 ,3-DICHLOROBENZENl ANALYSIS BY ^'ATLft TYPt
HIGH YOUDEN PAIR, UNITS - UG/L
DISTILLED WATER TAP WATER SURFACE WATER INDUSTRIAL EFFLUENT
5 6 5 6 5 6 5 6
A 2 2 • 0 480.C 432 .0 48C.C 432 , 0 480.0 432 . 0 4BC.0
4 55 .1
684 .0
5 38.8
296.7
4 49.0
*
1 OF .0*
387.5
3 58.0
427.0
793.5
521 .4
5 7 5.2*
493.1
695.1
481.1
4 70 . 4
456 .C
*
259 . O
441 .7
610.0
5 6 5 . Z
516.4
5 31.?
7 5 4.5*
313. C
43?.3
468 .0
311 .6
419.0
*
211 • C *
399 .8
720. C*
4 2G.C
202.4*
2 59 .2
420.0
610.0
682.3
563.2
370.4
579. 3
*
2 5 5.0*
415.0
414.0
759.1
257.5-
51C.0
699.6
421 . 7
688.2
549.7
402.C
463 .C
*
319. O
476.8
274 .j
4 92 .C
331.3
454 .0
747 .8
575 .7
698 .0*
575 .6
447.3
469.C
*
323.0*
498 .6
418 .C
468 .0
5 1 8 . 2
475 .8
473 .1
5 03 .4
655 .5 *
337 .1
350.2
473 .0
*
167.0*
393.1
327 .0
378 .0
457.2
4 23 .9
405 .5
50h . Q
7C1 .5
465 .7
326 .0
377.C
*
230 . u*
447.1
5 5 5 .C
47 7 .C
475 .9
826.7
535 .9
-------
TABLE O 85- BLANK VALUES FOR VALIDATION ANALYSES - TAP WATER
CO MP 01^ D
LABORATORY
7 8 S
10
11
12
13
1 4
1*5
N>
h-»
BENZENE
BROHODICFLCROMEThANE
BROMOFOHM
BROMOMETHAKE
CARBON TETRACHLORIDE
CHLOFOBENZEKE
CHLQROETMnE
CHLOROFORM
ChLQROMETHm
CIS-I |3-DI (iHOROPRoPENE
DIBROMOCHLOROMETHAME
ETHYL BENZENE
METHYLENE cflcride
TETRACHLORCETHENL
TOLUENE
TRANS-] ,2-DICHLOROETHENE
TRANS- 1, 3-C KHLOROPROPENE
.2
23.3*
0
1.3*
0
0
0
0
24,1
26 .? •
C
0
12*4
1 4.3*
0
0.6
1*5*
0
l.l«
0
0*1*
0
0
c
0
0
c
3.9
0
c
0
0
0
0
0
0
0
c
O.R 0
0.9*
0
1 .2
6.8 18.3
0 0
0.1 24.0 63*7
0« 7 3.4
0 0
5*7 2*.a
5.6*
0.3 0
0.6*
0.4 2.6
0.2*
0 0
3*6
0
0
0
0
0
1.4
0
0
0
0
0
31.4
0
0
0
0
0
0
5.8
0
0
0
Q
Q
0
0
0
0
3*0
0
0
1*2 38.8 27.0
Q 3.6 0
20.6 43.4 13.9
0 Q 0
0
0
0
0
1.3
0
0
0
0
17.0 47.7 24.9
0
0
31 .7
0
0
0
0
0
0
0
0
0
0
1 .6
0
0
0
0
0 4.7 0
1.6*
0 66.3 11.4
1.7*
0 0 0
2.2*
0 0 0
0 0 0
1.1*
0 1.6' 0
3.3*
0.5 0 0
0 *
0 49.2 \2f
1 .5*
0 0 0
0.5 0 0
0 •
0 29.7 1.2
1.6*
0 0 0
3.5*
151 0.5 2 0.6
2 0.5*
0 2.0 0
2.9*
0 0 0
2.7*
0 0 0
1.3*
0 0 0
1.4*
-------
TABLE C-85. (Continued)
laboratory
COHPOUfcD
1
2
3
4
5
6
7
6
9
10
11
12
13
14
TR1C hLOR OE ThENF
0
C
0
0
0
0
0
0
0
0
a
0
0
0
2.3*
trjchloroflucropethane
0
0
0
0.6
0
0
0
0
Q
0
0
0
0
0
1 .9*
1,1-DICHLOPOETHANE
0
0
0.1
0
0
0
0
0
0
0
a
0
0.5
0
1.2*
] ,1-niCHLOROETHENE
0
c
0
0
0
0
0
0
0
0
0
0
0
0
1 .5 •
ltlil-TRICHCROElhANE
0
0
0
0
0
0
0
0
0
0
0
0
0
1 O A
0
Itl,2-TRICHLCR0ETHANE
0
0
0
0
0
0
•
0
0
0
0
0
I • o +
O.b
0
2.7*
1*1i2»2-T£TRACHL0R0fTHANE
0
0
0
0
0
0
a
0
0
0
0
0
0
0
1»2-0!CHL0RC8ENZENE/I*4-DICHL0
0
c
0
0
0
0
0
0
0
0
0
0
0
0
1 i2-DICHLORCETHANE
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1 ,3*
1»2-0ICHL0RCPR0PANL
0
a
0
0
0
0
0
0
D
0
0
0
1.4
0
2.2*
1»3-0ICHL0R0BEN?EKE
0
0
0
Q
0
0
0
0
0
0
0
0
0
3.2
2-CHLORETHYLVINYL ETHER
0
0
6*6
0
0
0
0
0
2.
3 0
0
0
0
0
1.1*
6.0*
• LABS 1 A f D 13 VALUES ARE FOP
APPULES
1« 4 ANO 6>.
LAB
3
valles
ARE
FOR
ampules
2.
3 ANO
5.
15
0
0
0
0
0
0
0
0
0
0
0
0
-------
TABLE C-86. BLANK VALUES FOR VALIDATION ANALYSES - SURFACE WATER
LABORATORY
COMPOUWO
J
2
3
4
5
6
7
e
5
10
11
1 2
13
14
1 5
BENZENE
0
0
1 .1
0
1.0
1.7
C
0
0
0
0
0
0.2
0
3.?.
1.1*
0 -
BROMOOICHLOROHETHANE
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
BR010F OR M
Q
0
0
0
0
0
0
3
Q
0
0
0
0*1
A *
0
0
bromomlihake
0
c
0
0
0
0
0
0
0
0
0
0
u •
0
0
0
CARBON TFT RACHLORIDE
0
0
0.1
0
0
0
0
0
0
0
0
0
0
0
0
0.1 •
CMLOROBENZEAE
0
0
0
0
0
0
0.3
0
0
0
0
0
0.3
n a
0
0.7
CHLOROET HAKE
0
0
0
0
0
3.4
0
0
0
0
0
0
u •
0.3
n *
0
0
CHLOROFORM
1.0
0
0
2.7
1.3
0.2
4.3
0
0
1.2
0
0
u •
0
0
17.8
0.1«
/
CHLOROMETl-.m
0
0
0
0
0
0
0
0
0
0
0
0
0.4
0
0
0.3*
CIS- 1 »3-OICFlOROPROPENE
0
0
D
0
0
0
0
0
0
0
0
0
0
0
0
OIBROMOCH OROHETHANE
Q
0
0
0
0
0
0
0
0
0
0
0
0
0
0
ETHYL BEN^EKt
0
0
0
0
0
0
1.1
0
0
0
0
0
0.6
A *
0
0.6
METHYLENE CHOP IOE
2 .1
10.7
1.9
60.7
11.1
11.4
(.4
0
12.0
58.1
0
112
U •
15.2
355
294 1
5.2*
26.3*
TETRACHLORCETHENE
0
0
0.2
0
0
0
1.4
l]
0
0
0
0
0.3
0
0
0.5 *
0 *
TOLUENE
0
0
0.?
2.4
0
0.9
3.3
0
0
0
0
0
0
0
1 .?
0.3*
0.7*
TRANS-1» 2-CICHLOROETHENE
0
0
0
0
0
0
0
0
0
0
0
~
0
0
0
TRANS-1iJ-OICHLCRCPROPENE
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
TRICHLORCETFENE
0
0
0
0
0
0.5
0
0
0
0
0
0
0.1
A M
0
2.6
TRICHLOROFLLCROPETHANE
0
0
0
0
Q
0
0
0
0
0
0
0
u *
0.1
0
0
o *
-------
TABLE C-86. (Continued)
LABORATORY
COHPOUhD
1
2
3
4
5
6
7
B
9
10
11
12
13
14
1!
l»l-OrCHLORCETHANC
0
0
0.2
0
0
0
0
0
0
0
0
0
0
0
0
0.1*
1#1 — DICHLORCETHENE
0
0
0
0
0
0
0
0
0
0
0
0
0.1
n *
0
0
UWI-TRIOLCROEUANE
0
0
0
1.1
0
0
0
0
0
0
0
Q
0
0
0
1« 1 • 2 - TR ICHOROETHAMr
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
It 1 t2, 2-tethachloroethane
0
c
0
0
0
0
0
0
0
0
0
0
0
0
0
1»2-DICHLOHCBEN2ENE f\#4-OICHLO
1.9
0
0
0
0
0
0
0
0
0
0
0
2.3
ft A
0
0
1 »2-DICHLORCETHANE
0
0
0
0
0
0
0
0
0
0
0
G
u •
0
0
0
1i2-DIChLOROFROPANE
0
0
0
0
0
Q
0
0
0
0
0
0
0.1
A M.
0
0
1»3-DJCHL0RCBENZENE
0.2
0
0
0
0
0
0
0
0
0
0
0
U •
1 .4
ft ~
0
0
2-CHLORETHtlVlMfL ETHER
0
0
7,7
0
0
0
0
0
2.7
0
0
0
u *
0
0
0
* LAB 3 VALUES ARE FOR AMPUL IS 2, 3 AKC 5« LAB 13 VALUES ARE FOR AHRULES 1« 3 AND 6«
-------
TABLE C-87. BLANK VALUES FOR VALIDATION ANALYSES - INDUSTRIAL EFFLUENT
LABORATORY
COUP OUK'D
1
2
3
4
5
6
7
8
5
10
11
12
13
14
15
BENZENE
1.7
0
1.1
0.6
2b.2
1 .2
0
0
0
0
0
0
0
0
0.2
0 « 3*
3.2*
BROMOO ICHLOROHETHANE
0
0
0
4. 1
0
0
0
0
0
0
0
0
0
3.1
3.0
0.3*
BROHOFOR M
0
0
0
D
0
0
0
0
0
0
0
0
0
0
0
RROHOMETHAKE
0
c
0
0
0
0
0
0
0
0
0
0
0
0
0
CARBCN TETRACHLCRlOf
0
c
0
0
0
0
0
0
0
0
0
0
0
0
0
3.8 *
CHLOROBENZENE
0
0
0
0
0
0
0
0
0
0
0
0
0
0
o.s
CHL OROET HA^ E
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.0*
CHLOROFORM
1.4
1 .2
0
7.7
28.4
20.4
0
0
0
7.0
0
0
0
1 2 .4
46.5
1.3*
2.4*
CHL OR 0 ME T h 4KE
0
0
0
0
0
0
0
0
0
0
0
Q
0
0
0
C1S-1i3-OICHLOROPROPFNF
0
0
0
0
0
0
0
0
0
0
0
0
Q
0
0
DIBROHOCHLOROHETHANE
0
0
0
0 . R
0
0
0
0
0
0
0
0
0
0.5
> 0
ETHYL BENZEKE
q .;
c
0
0
43.4
0
0
0
0
0
0
0
0
0
1.2
0 •
0 .1 *
METHYLENE CHOP TOE
If .1
s:.3
0
84.7
2120
5.1
2.5
10.1
13.5
55.fi
0
53.6
1 *1
29.?
i 10.1
10.0*
9*8*
TETRACHLORCETHENE
0.6
1.9
0
1 7 A
0
116
0
0
2.1
0
3.2
0
0
0
0.3
¦ 3.6
TOLUENE
o.e
c
If ' •
0.1
2.4
to
.
ro
0.6
1.0
0
0.9
0
0
0
0
0.5
O.P
0.4*
6*1*
TRANS-l,2-niCHL0R0ETHENE
0
0
0
23.0
Q
0
0
0
0
0
0
a
a
0
0.**
TRANS - 1 »3-C KHLOROPROPENE
0
(
0
0
Q
0
0
0
0
0
0
0
0
0
0
TR ICHLOROETHENE
0
0
0
41.7
23.fi
0
0
0
0
0
0
0
0
0
9.e
0.2*
TRICHLOROFlUOROMETHANE
0*1
n *
fl.O
0
0
0
0
0
0
0
0
0
0
0
0
0
191-DICHL0RCETHANL
U •
Q
0
0.1
0
0
0
0
0
0
0
0
0
0
0
4.2
-------
TABLE C-87. (Continued)
LABORATORY
COKPnukD 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
ro
t\>
ro
1,1-01chlorcethenl
l,l»l-TRlCHCfiCmANE
l#li2-TRIChL0R0ET^ANE
1*1t2»2-TE7RACHLOKOETHANC
1»2-0ICHL0RCBENZENE/1«4-DICHL0
1«2-01CHLORCETHANE
1»2-DICHLORCPROPANt
1.3-DICHLOROBENZENE
2-CHLORETNUVINYL ETHER
0
0
0
0
0
0
0
3
0
0
0
0
0
0
0
0
4.4
1.7
0
82.6
0
0.7
2.0
0
0
0
0
0
0
30*9
16.8*
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
c
0
0
0
0
0
0
0
0
0
0
0
0
2.1
0
c
0
0
0
0
0
e.o
0
0
0
0
0
0
10.0
2. 1*
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
e.4
0
0
0
D
0
0
0
0
n
0
0
0
0
0
0
0
0
3.6
0
0
0
0
0
0
1.7
0.6*
0
c
8.2
0
0
0
0
0
4.1
0
0
0
0
0
0
6 • 9 •
It 3
AfcD
5. LAB
3 VALUES
ARE
FOR
AMPULES It
4
AND 5.
-------
APPENDIX D
EPA METHOD 624 - PURGEABLES
223
-------
United States
Environmental Protection
Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
Research and Development
SEPA Test Method
Purgeables —
Method 624
1. Scope and Application
1.1 This method covers the determi-
nation of a number of purgeable
organics. The following parameters
may be determined by this method:
Parameter
Benzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethylvinyl ether
Chloroform
Chloromethane
Dibromochloromethane
1.2-Dichlorobenzene
1.3-Dichlorobenzene
1,4*Dichlorobenzene
1,1 -Dichloroethane
1,2-Dichloroethane
1.1 -Dichloroethene
trans-1,2-Dichloroethene
1,2-Dichloropropane
cis-1,3-Dichloropropene
trans-1. 3-Dichloropropene
Ethyl benzene
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1 -Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride
1.2 The method may be extended to
screen samples for acrolein (STORET
No- 34210, CAS No. 107-02-8) and
acrylonitrile {STORET 3421 5, CAS No.
107-1 3-1), however, the preferred
STORET No.
CAS No.
34030
71-43-2
32101
75-27-4
32104
75-25-2
34413
74-83-9
32102
56-23-5
34301
108-90-7
34311
75-00-3
34576
110-75-8
32106
67-66-3
34418
74-87-3
32105
124-48-1
34536
95-50-1
34566
541-73-1
34571
106-46-7
34496
75-34-3
34531
107-06-2
34501
75-35-4
34546
156-60-5
34541
78-87-5
34704
10061-01-5
34699
10061-02-6
34371
100-41-4
34423
75-09-2
34516
79-34-5
34475
127-18-4
34010
108-88-3
34506
71-55-6
34511
79-00-5
39180
79-01-6
34488
75-69-4
39175
75-01-4
method for these two compounds is
method 603.
1.3 This is a purge and trap gas
chromatographic/mass spectrometer
624 ?
July 1962
224
-------
IGC/MS) method applicable to the
determination of the compounds listed
above in municipal and industrial
discnarges as provided under 40 CFR
136.1.
1.4 The method detection limit (MDL,
defined in Section 1 4.1 )(11 for each
parameter is listed in Table 1. The MDL
for a specific wastewater differ from
those listed, depending upon the
nature of interferences in the sample
matrix.
1.5 Until the U.S. Environmental Pro-
tection Agency establishes perfor-
mance criteria based upon the results
of interiaboratory testing, any
alternative GC/MS method which
meets the performance criteria
described in Section 8.2 will be
permitted. Performance must be
verified for such ijiodification by
analyzing wastewater as described in
Section 8.2.2. In addition, the
laboratory must successfully partici-
pate in the applicable performance
evaluation studies.
1.6 This method is restricted to use
by or under the supervision of analysts
experienced in the use of purge and
trap systems and gas chromatography
mass spectrometers and skilled in the
interpretation of mass spectra. Each
analyst must demonstrate the ability to
generate acceptable results with this
method using the procedure described
in Section 8.2.
2. Summary of Method
2.1 An inert gas is bubbled through a
5-mL sample contained in a specially*
designed purging chamber at ambient
temperature. The purgeables are
efficiently transferred from the
aqueous phase to the vapor phase. The
vapor is swept through a sorbent
column where the purgeables are
trapped. After purging is completed,
the sorbent column is heated and
backflushed with the inert gas to
desorb the purgeables onto a gas
chromatographic column. The gas
chromatograph is temperature
programmed to separate the
purgeables which are then detected
with a mass spectrometer^.3).
3. Interferences
3.1 Impurities in the purge gas,
organic compounds out-gassing from
the plumbing ahead of the trap and
solvent vapors in the laboratory
account for the majority of contamina-
tion problems. The analytical system
must be demonstrated to be free from
contamination under the conditions of
the analysis by running laboratory
reagent blanks as described in Section
8.5. The use of non-TFE plastic tubing,
non-TFE thread sealants, or flow
controllers with rubber components in
the purging device should be avoided.
3.2 Samples can be contaminated by
diffusion of volatile organics (particu-
larly fluorocarbons and methylene
chloride) through the septum seal into
the sample during shipment and
storage. A field reagent blank prepared
from reagent water and carried through
the sampling and handling protocol can
serve as a check on such
contamination.
3.3 Contamination by carry over can
occur whenever high level and low
level samples are sequentially
analyzed. To reduce carry over, the
purging device and sample syringe
must be rinsed with reagent water
between sample analyses. Whenever
an unusually concentrated sample is
encountered, it should be followed by
an analysis of reagent water to check
for cross contamination. For samples
containing large amounts of water-
soluble materials, suspended solids,
high boiling compounds or high purge-
able levels, it may be necessary to
wash out the purging device with a
detergent solution, rinse it with distilled
water, and then dry it in a 105 °C oven
between analyses. The trap and other
parts of the system are aiso subject to
contamination; therefore, frequent
bakeout and purging of the entire
system may be required.
4. Safety
4.1 The toxicity or carcinogenicity of
each reagent used in this method has
not been precisely defined; however,
each chemical compound should be
treated as a potential health hazard.
From this viewpoint, exposure to these
chemicals must be reduced to the
lowest possible level by whatever
means available. The laboratory is
responsible for maintaining a current
awareness file of OSHA regulations
regarding the safe handling of the
chemicals specified in this method. A
reference file of material data handling
sheets should also be made available to
all personnel involved in the chemical
analysis. Additional references to
laboratory safety are available and
have been identified^5 71 for the
information of the analyst.
4.2 The following parameters
covered by this method have been
tentatively classified as known or
suspected, human or mammalian
carcinogens: benzene, carbon
624-2 July 1982
tetrachloride, chloroform,
1,4-dichlorobenzene. and vinyl
chloride. Primary standards of these
toxic compounds should be prepared in
a hood. A NIOSH/MESA approved
toxic gas respirator should be worn
when the analyst handles high
concentrations of these toxic
compounds.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete
sampling.
5. 7.1 Vial — 25-mL capacity or larger,
equipped with a screw cap with hole in
center (Pierce #1 3075 or equivalent).
Detergent wash, rinse with tap and
distilled water, and dry at 105 °C
before use.
5.1.2 Septum—Teflon-faced silicone
(Pierce 01 2722 or equivalent).
Detergent wash, rinse with tap and
distilled weter, and dry at 1 05 °C for
one hour before use.
5.2 Purge and trap device—The
purge and trap device consists of three
separate pieces of equipment: the
sample purger, trap, and the desorber.
Several complete devices are now-
commercially available.
5.2.1 The sample purger must be
designed to accept 5-mL samples with
a water column at least 3 cm deep.
The gaseous head space between the
water column and the trap must have a
total volume of less than 1 5-mL. The
purge gas must pass through the water
column as finely divided bubbles with a
diameter of less than 3 mm at the
ohgin. The purge gas must be intro-
duced no more than 5 mm from the
base of the water column. The sample
purger, illustrated in Figure 1, meets
these design criteria.
5.2.2 The trap must be at least 25
cm long and have an inside diameter of
at least 0.105 inch. The trap must be
packed to contain the following mini-
mum lengths of adsorbents: 1.0 cm of
methyl silicone coated packing (Sec-
tion 6.3.2), 1 5 cm of 2,6-diphenylene
oxide polymer (Section 6.3.1), and 8
cm of silica gel, (Section 6.3.3). The
minimum specifications for the trap are
illustrated in Figure 2.
5.2.3 The desorber should be
capable of rapidly heating the trap to
1 80 °C. The polymer section of the
trap should not be heeted higher than
180 °C and the remaining sections
should not exceed 220 °C. The
desorber design, illustrated in Figure 2,
meets these criteria.
225
-------
5.2.4 The purge and trap device may
be assembled as a separate unit'or be
coupled to a gas chromatograph as
illustrated in Figures 3 and 4.
5.3 GC/MS system.
5.3.1 Gas chromatograph —An ana-
lytical system complete with a temper-
ature programmable gas chromato-
graph suitable for on-column injection
and all required accessories including
syringes, analytical columns, and
gases.
5.3.2 Column —6 ft long x 0.1 in ID
stainless steel or glass, packed with
1 % SP-1000 on Carbopack B (60/80
mesh) or equivalent. This column was
used to develop the method perfor-
mance statements in Section 14.
Guidelines for the use of alternate
column packings are provided in
Section 11.1.
5.3.3 Mass spectrometer—Capable
of scanning from 20 to 260 amu every
seven seconds or less, utilizing 70
volts (nominal) electron energy in the
electron impact ionization mode and
producing a mass spectrum which
meets all the criteria in Table 2 when
50 ng of 4-bromofluorobenzene (BFB)
is injected through the gas chromato-
graph inlet.
5.3.4 GC/MS interface —Any gas
chromatograph to mass spectrometer
interface that gives acceptable
calibration points at 50 ng or less per
injection for each of the parameters of
interest and achieves all acceptable
performance criteria (see Section 10)
may be used. Gas chromatograph to
mass spectrometer interfaces con-
structed of ail-glass or glass-lined
materials are recommended. Glass can
be deactivated by silanizing with
dichloro-dimethylsilane.
5.3.5 Data system —A computer
system must be interfaced to the mass
spectrometer that allows the
continuous acquisition and storage on
machine readable media of all mass
spectra obtained throughout the
duration of the chromatographic
program. The computer must have
software that allows searching any
GC/MS data file for ions of a specified
mass and plotting such ion abundances
versus time or scan number. This type
of plot is defined as an Extracted Ion
Current Profile (EICP). Software must
also be available that allows integrating
the abundance in any EICP between
specified time or scan number limits.
5.4 Syringes— 5-ml glass hypoder-
mic with Luerlok tip (two each), if
applicable to the purging device.
5.5 Micro syringes— 25-ml, 0.006
Inch ID needle.
5.6 Syringe valve —two-way, with
luer ends (three each), if applicable to
the purging oevice.
5.7 Syringe— 5-ml, gas-tight with
shut-off valve.
5.B Bottle— 1 5-ml, screw-cap, with
Teflon cap liner.
5.9 Balance —Analytical, capable of
accurately weighing 0.0001 g.
6. Reagents
6.1 Reagent water—Reagent water is
defined as a water in which an inter-
feres is not observed at the MDl of
the parameters of interest.
6.1.1 Reagent water may be gener-
ated by passing tap water through a
carbon filter bed containing about 453
g of activated carbon (Calgon Corp.,
Filtrasorb-300 or equivalent).
6.1.2 A water purification system
(Millipore Super-Q or equivalent) may
be used to generate reagent water.
6.1.3 Reagent water may also be
prepared by boiling water for 1 5
minutes. Subsequently, while maintain-
ing the temperature at 90 °C, bubble a
contaminant-free inert gas through the
water for one hour. While still hot,
transfer the water to a narrow-mouth
screw-cap bottle and seal with a
Teflon-lined septum and cap.
6.2 Sodium thiosulfate —(ACS)
Granular.
6.3 Trap materials
6.3.1 2,6-Diphenylene oxide
polymer — Tenax (60/80 mesh),
chromatographic grade or equivalent.
6.3.2 Methyl silicone packing— 3%
OV-1 on Chromosorb-W (60/80 mesh)
or equivalent.
6.3.3 Silica gel Davison Chemical,
(35/60 mesh), grade-1 5 or equivalent.
6.4 Methanol —Pesticide quality or
equivalent.
6.5 Stock standard solutions —Stock
standard solutions may be prepared
from pure standard materials or
purchased as certified solutions.
Prepare stock standard solutions in
methanol using assayed liquids or
gases as appropriate. Because of the
toxicity of some of the organohalides,
primary dilutions of these materials
should be prepared in a hood. A
NIOSH/MESA approved toxic gas
respirator should be used when the
analyst handles high concentrations of
such materials.
6.5.1 Place about 9 .8 ml of
methanol into a 10-ml ground glass
stoppered volumetric flask. Allow the
fiask to stand, unstoppered. for about
1 0 minutes or until all alcohol wetted
surfaces have dried. Weigh the flask to
the nearest 0.1 mg.
6.5.2 Add the assayed reference
material as described below:
6.5.2.1 Liquids —Using a 100-pl
syringe, immediately add two or more
drops of assayed reference material to
the flask, then reweigh. The liquid
must fall directly into the alcohol
without contacting the neck of the
flask.
6.5.2.2 Gases—To prepare standards
for any of the four haiocarbons that
boil below 30 °C (bromomethane.
chloroethane, chloromethane, and vinyl
chloride), fill a 5-ml valved gas-tight
syringe with the reference standard to
the 5.0-ml mark, lower the needle to
5 mm above the methanol meniscus.
Slowly introduce the reference stan-
dard above the surface of the liquid.
The heavy gas rapidly dissolves in the
methanol.
6.5.3 Reweigh, dilute to volume,
stopper, then mix by inverting the flask
several times. Calculate the concentra-
tion in micrograms per microliter from
the net gain in weight. When
compound purity is assayed to be 96%
or greater, the weight may be used
without correction to calculate the
concentration of the stock standard.
Commercially prepared stock standards
may be used at any concentration if
they are certified by the manufacturer
or by an independent source.
6.5.4 Transfer the stock standard
solution into a Teflon-sealed screw-cap
bottle. Store, with minimal headspace,
at - 10 ° to - 20 °C and protect from
light.
6.5.5 Prepare fresh standards weekly
for the four gases and 2-chloroethyl-
vinyl ether. All other standards must be
replaced after one month, or sooner if
comparison with check standards indi-
cate a problem.
6.6 Secondary dilution standards-
Using stock standard solutions, prepare
secondary dilution standards in
methanol that contain the compounds
of interest, either singly or mixed
together. The secondary dilution
standards should be prepared at
concentrations such that the aqueous
calibration standards prepared in
Section 7.3.1 or 7.4.1 will bracket the
624-3
226 July 1982
-------
working range of the analytical system.
Seconaary dilution standards should be
stored with minimal headspace and
should be checked frequently for signs
of degradation or evaporation, espe-
cially just prior to preparing calibration
standards from them. Quality control
cneck standards that can used to
determine the accuracy of calibration
standards, will be available from the
U.S. Environmental Protection Agency,
Environmental Monitoring and Support
Laboratory. Cincinnati, Ohio 45268.
6.7 Surrogate standard spiking
solution—Select a minimum of three
surrogate compounds from Table 3.
Prepare stock standard solutions for
each surrogate standard in methanol as
described in Section 6.5. Prepare a
surrogate standard spiking solution
from these stock standards at a con-
centration of 1 50 yg/10 ml in water.
Store the spiking solution at 4 °C in
Teflon sealed glass containers with a,
minimum of headspace. The solutions
should checked frequently for stability.
They should be replaced after six
months. The addition of 10 of this
solution to 5 ml of sample or standard
is equivalent to a concentration of 30
jjg/L of each surrogate standard.
Surrogate standard soiking solutions,
appropriate for use with this method,
will be available from the U.S.
Environmental Protection Agency,
Environmental Monitoring and Support
Laboratory. Cincinnati. Ohio 45268.
6.B BFB Standard —Prepare a 25
Mg/*iL solution of BFB in methanol.
7. Calibration
7.1 Assemble a purge and trap
device that meets the specifications in
Section 5.2. Condition the trap over-
night at 180 °C by back flushing with
an inert gas flow of at least 20
mL/min. Prior to use, daily condition
traps 10 minutes while backflushing at
180 °C.
7.2 Connect the purge and trap
device to a gas chromatograph. The
gas chromatograph must be operated
using temperature and flow rate
parameters equivalent to those in Table
1. Calibrate the purge and trap-GC/MS
system using either the external stan-
dard technique (Section 7.3) or the
internal standard technique (Section
7.4).
7.3 External standard calibration
procedure:
7.3.1 Prepare calibration standards
at a minimum of three concentration
levels for each parameter by carefully
adding 20.0 mL of one or more secon-
dary dilution standards to 50. 250. or
500 ml of reagent water. A 25-wL
syringe with a 0.006 inch ID needle
should be used for this operation. One
of the external standards should be at a
concentration near, but aoove, the
MDL (See Table 1J and the other
concentrations should correspond to
the expected range of concentrations
found in real samples or should define
the working range of the GC/MS
system. Aqueous standards may be
stored up to 24 hours, if held in sealed
vials with zero headspace as described
in Section 9.2. If not so stored, they
must be discarded after one hour.
7.3.2 Analyze each calibration
standard according to Section 11, and
tabulate the area response of the
primary characteristic ion (See Table 4)
against the concentration in the
standard. The results can be used to
prepare a calibration curve for each
compound. Alternatively, if the ratio of
response to concentration {calibration
factor) is a constant over the working
range (<10% relative standard devia-
tion, RSD). linearity through the origin
can be assumed and the average ratio
or calibration factor can be used in
place of a calibration curve.
7.3.3 The working calibration curve
or calibration factor must be verified on
each working day by the measurement
of one or more calibration standards. If
the response for any parameter varies
from the predicted response by more
than ± 10%. the test must be repeated
using a fresh calibration standard.
Alternatively, a new calibration curve
or calibration factor must be prepared
for that parameter.
7.4 Internal standard calibration
procedure. To use this approach, the
analyst must select one or more
internal standards that are similar in
analytical behavior to the compounds
of interest. The analyst must further
demonstrate that the measurement of
the internal standard is not affected by
method or matrix interferences.
Because of these limitations, no
internal standard can be suggested that
is applicable to all samples. Due to their
generally unique retention times,
bromochloromethane. 2-bromo-1-
chloropropane, and 1,4-dichlorobutane
have been used successfully as internal
standards.
7.4.1 Prepare calibration standards
at a minimum of three concentration
levels for each parameter of interest as
described in Section 7.3.1.
7.4.2 Prepare a spiking solution
containing each of the internal
624-4 July 7982
standards using the procedures
described in Sections 6.5 and 6.6. It is
recommended that the secondary dilu-
tion standard be prepared at a concen-
tration of 1 5 M9'ml of each internal
standard compound. The addition of
1 0 uL of this standard to 5.0 ml of
sample or calibration standard would
be equivalent to 30 m?/L.
7.4.3 Analyze each calibration
standard, according to Section 11,
adding 10 mL of internal standard
spiking solution directly to the syringe
(Section 1 1.4). Tabulate the area
response of the characteristic ions
against concentration for each
compound and internal standard and
calculate response factors (RF) for
each compound using equation 1.
Eq. 1 RF a (A#C1#)/(AiaCs)
where:
A9 = Area of the characteristic ion
for the parameter to be
measured.
AIS * Area of the characteristic ion
for the internal standard.
Cl9 ¦ Concentration of the internal
standard.
C, » Concentration of the
parameter to be measured.
If the RF value over the working range
is a constant (<10% RSD), the RF can
be assumed to be invariant and the
average RF can be used for
calculations. Alternatively, the results
can be used to plot a calibration curve
or response ratios. A,/Ai#, vs. RF.
7.4.4 The working calibration curve
or RF must be verified on each working
day by the measurement of one or
more calibration standards. If the
response for any parameter varies from
the predicted response by more than
± 10%, the test must be repeated
using a fresh calibration standard.
Alternatively, a new calibration curve
must be prepared for that compound.
8. Quality Control
8.1 Each laboratory that uses this
method is required to operate a formal
quality control program. The minimum
requirements of this program consist of
an initial demonstration of laboratory
capability and the analysis of spiked
samples as a continuing check on
performance. The laboratory is required
to maintain performance records to
define the quality of data that is
generated. Ongoing performance
checks must be compared with
established performance criteria to
determine if the results of analyses are
within accuracy and precision limits
expected of the method.
227
-------
8. 7. 7 Before performing any
analyses, the analyst must
demonstrate the ability to generate
acceptable accuracy and precision with
this method. This ability is estaolished
as described in Section 8.2.
8. 7.2 In recognition of the rapid
advances that are occurring in chroma-
tography, the analyst is permitted to
certain options to improve the separa-
tions or lower the cost of measure-
ments. Each time such modifications
are made to the method, the analyst is
required to repeat the procedure in
Section 8.2.
8. 7.3 The laboratory must spike all
samples with surrogate standards to
monitor continuing laboratory
performance. This procedure is
described in Section 8.4.
8.2 To establish the ability to
generate acceptable accuracy and
precision, the analyst must perform the
following operations.
8.2. 7 Select a representative spike
concentration for each parameter to be
measured. Using stock standards,
prepare a quality control check sample
concentrate in methanol 500 times
more concentrated than the selected
concentrations. Quality control check
sample concentrates, appropriate for
use with this method, will be available
from the U.S. Environmental Protection
Agency. Environmental Monitoring and
Support Laboratory, Cincinnati, Ohio
45268.
8.2.2 Using a syringe, add 10 jiL of
the check sample concentrate and 10
mL of the surrogate standard dosing
solution (Section 6.7) to each of a
minimum of four 5-mL aliquots of
reagent water. A representative
wastewater may be used in place of
the reagent water, but one or more
additional aliquots must be analyzed to
determine background levels, and the
spike level must exceed twice the
background level for the test to be
valid. Analyze the aliquots according to
the method beginning in Section 11.
8.2.3 Calculate the average percent
recovery, (R), and the standard devia-
tion of the percent recovery (s), for all
parameters and surrogate standards.
Wastewater background corrections
must be made before R and s calcu-
lations are performed.
8.2.4 Using Table 5, note the
average recovery (X) and standard
deviation (p) expected for each method
parameter. Compare these to the
calculated values for R and s. If s > p or
X - Rl > p. review potential problem
areas and repeat the test.
8.2.5 The U.S. Environmental Pro-
tection Agency plans to estaolish
performance criteria for R and s based
upon the results of interlaboratory
testing. When they become available,
these criteria must be met before any
samples may be analyzed.
8.3 The analyst must calculate
method performance criteria for each
of the surrogate standards.
8.3.7 Calculate upper and lower
control limits for method performance
for each surrogate standard, using the
values for R and s calculated in Section
8.2.3:
Upper Control Limit (UCL) = R + 3s
Lower Control Limit ILCL) = R - 3s
The UCL and LCL can be used to
construct control charts10' that are
useful in observing trends in
performance. The control limits above
must be replaced by method perfor-
mance criteria as they become avail-
able from the U.S. Environmental
Protection Agency.
8.3.2 For each surrogate standard,
the laboratory must develop and main-
tain separate accuracy statements of
laboratory performance for wastewater
samples. An accuracy statement for
the method is defined as R ± s. The
accuracy statement should be
developed by the analysis of four
aliquots of wastewater as described in
Section 8 2.2, followed by the calcu-
lation of R and s. Alternately, the
analyst may use four wastewater data
points gathered through the require-
ment for continuing quality control in
Section 8.4. The accuracy statements
should be updated regularly(8>.
8.4 The laboratory is required to
spike all of their samples with the
surrogate standard spiking solution to
monitor spike recoveries. If the
recovery for any surrogate standard
does not fall within the control limits
for method performance, the results
reported for that sample must be
qualified as described in Section 13.3.
The laboratory should monitor the
frequency of data so qualified to
ensure that it remains at or below 5%.
6.5 Each day, the analyst must
demonstrate, through the analysis of
reagent water, that interferences from
the analytical system are under control.
8.6 It is recommended that the
laboratory adopt additional quality
assurance practices for use with this
method. The specific practices that are
most productive oepend upon the
needs of the laboratory and the nature
of the samples. Field duplicates may be
analyzed to monitor the precision of
the sampling technique. Whenever
possible, the iaooratory should perform
analvsis of standard reference
materials and participate in relevant
performance evaluation studies.
9. Sample Collection,
Preservation, and Handling
9.1 All samples must be iced or
refrigerated from the time of collection
until extraction. If the sample contains
residual chlorine, add sodium
thiosulfate preservative (10 mg/40 mL
is sufficient for up to 5 ppm CI2) to the
empty sample bottles just prior to
shipping to the sampling site. U.S.
Environmental Protection Agency
methods 330.4 and 330.5 may be
used for measurement of residual
chlorine'9'. Field test kits are available
for this purpose.
9.2 Grab samples must be collected
in glass containers having a total
volume of at least 25 mL. Fill the
sample bottle just to overflowing in
such a manner that no air bubbles pass
through the sample as the bottle is
being filled. Seal the bottle so that no
air bubbles are entrapped in it. If
preservative has been added, shake
vigorously for one minute. Maintain the
hermetic seal on the sample bottle until
time of analysis.
9.3 Experimental evidence indicates
that some aromatic compounds,
notably benzene, toluene, and ethyl
benzene are susceptible to rapid
biological degradation under certain
environmental conditions'31.
Refrigeration along may not be
adequate to preserve these compounds
in wastewaters for more than seven
days. For this reason, a separate
sample should be collected, acidified,
and analyzed when these aromatics are
to be determined. Collect about 500
mL of sample in a clean container.
Adjust the pH of the sample to about 2
by adding HCI (1 -*• 1) while stirring.
Check pH with narrow range (1.4 to
2.8) pH paper. Fill a sample container
as described in Section 9.2. If chlorine
residual is present, add sodium thio-
sulfate to another sample container
and fill as in Section 9.2 and mix
thoroughly.
9.4 All samples must be analyze
within 14 days of collection.
10. Jaily GC/MS Performance
Tests
10.1 At the beginning of each day
that analyses are to be performed, the
624 5
228 July 1982
-------
GC/MS system must be checked to see
if acceptable performance criteria are
achievea for BFB'101. The performance
test must be passed before any
samples, blanks, or standards are
analyzed, unless the instrument has
met the DFTPP test described in
method 6.26 earlier in the day.
10.2 These performance tests
require the following instrumental
parameters.
Electron Energy: 70 Volts (nominal)
Mass Range: 20 to 260
Scan Time: to give at least 5
scans per peak but
not to exceed 7
seconds per scan.
10.3 At the beginning of each day,
inject 2 mL of 8FB solution directly on
column. Alternately, add 2 jiL of BFB
solution to 5.0 ml of reagent water or
standard solution and analyze
according to Section 11. Obtain a
background corrected mass spectrum
of BFB and check that all the key ion
criteria in Table 2 are achieved. If all
the criteria are not achieved, the
analyst must retune the mass
spectrometer and repeat the test until
all criteria are achieved.
11. Sample Extraction and
Gas Chromatography
11.1 Table 1 summarizes the
recommended operating conditions for
the gas chromatograph. This table
includes retention times and method
detection limits that were achieved
under these conditions. An example of
the parameter separations achieved by
Column 1 is shown in Figure 5. Other
packed columns or chromatographic
conditions may be used if the
requirements of Section 8.2 are met.
11.2 After achieving the key ion
abundance criteria in Section 10.
calibrate the system daily as described
in Section 7.
11.3 Adjust the purge gas (helium)
flow rate to 40 ± 3 mL/min. Attach
the trap inlet to the purging device, and
set the device to purge. Open the
syringe valve located on the purging
device sample introduction needle.
11.4 Remove the plunger from a
5-mi syringe and attach a closed
syringe valve. Open the sample or
standard bottle which has been
allowed to come to ambient
temperature, and carefully pour the
sample into the syringe barrel to just
short of overflowing. Replace the
syringe plunger and compress the
sample. Open the syringe valve and
vent any residual air while adjusting the
sample volume'to 5.0 ml. Since this
process of taking an aliquot destroys
the validity of the sample for future
analysis, the analyst should fill a
second syringe at this time to protect
against possible loss of data. Add 10.0
mL of the surrogate spiking solution
(Section 6.7) and. if applicable, 10.0
lil of the internal standard spiking
solution (Section 7.4.2) through the
valve bore, then close the valve. The
surrogate and internal standards may
be mixed and added as a single spiking
solution.
11.5 Attach the syringe-syringe
valve assembly to the syringe valve on
the purging device. Open the syringe
valves and inject the sample into the
purging chamber.
11.6 Close both valves and purge the
sample for 11.0 ±0.1 minutes at
ambient temperature.
11.7 At the conclusion of the purge
time, attach the trap to the
chromatograph, adjust the device to
the desorb mode, and begin the gas
chromatographic temperature program.
Concurrently, introduce the trapped
materials to the gas chromatographic
column by rapidly heating the trap to
1 80 °C while backflushing the trap
with an inert gas between 20 and 60
mL/min for four minutes. If this rapid
heating requirement cannot be met, the
gas chromatographic column must be
used as a secondary trap by cooling it
to 30 °C (or subambient. if problems
persist) instead of the recommended
Initial temperature of 45 °C.
11.8 While the trap is being desorbed
into the gas chromatograph, empty the
purging chamber using the sample
introduction syringe. Wash the
chamber with two 5-mL flushes of
reagent water.
11.9 After desorbing the sample for
four minutes, recondition the trap by
returning the purge and trap device to
the purge mode. Wait 1 5 seconds then
close the syringe valve on the purging
device to begin gas flow through the
trap. The trap temperature should be
maintained at 1 80 °C. Trap
temperatures up to 230 °C may be
employed, however, the higher
temperature will shorten the useful life
of the trap. After approximately seven
minutes turn off the trap heater and
open the syringe valve to stop the gas
flow through the trap. When cool, the
trap is ready for the next sample.
11.10 If the response for any ion
exceeds the working range of the
system, dilute the sample aliquot in the
second syringe with reagent water and
reanalyze.
12. Qualitative Identification
12.1 Obtain EICPs for the primary ion
(Table 4) and at least two secondary
ions for each parameter of interest. The
following criteria must be met to make
a quantitative identification.
12.1.1 The characteristic ions of
each parameter of interest must
maximize in the same or within one
scan of each other.
12.1.2 The retention time must fall
within ± 30 seconds of the retention
time of the authentic compound.
12.1.3 The relative peak heights of
the three characteristic ions in the
EICPs must fall within ± 20% of the
relative intensities of these ions in a
reference mass spectrum. The
reference mass spectrum can be
obtained from a standard analyzed in
the GC/MS system or from a reference
library.
12.2 Structural isomers that have
very similar mass spectra and less than
30 seconds difference in retention
time, can be explicitly identified only if
the resolution between authentic
isomers in a standard mix is
acceptable. Acceptable resolution is
achieved if the baseline to valley height
between the isomers is less than 25%
of the sum of the two peak heights.
Otherwise, structural isomers are
identified as isomeric pairs.
13. Calculations
13.1 When a parameter has been
identified, the quantitation of that
parameter should be based on the
integrated abundance from the EICP of
the first listed characteristic ion given
in Table 4. If the sample produces an
interference for the primary ion. use a
secondary characteristic ion to
quantitate. Quantitation may be
performed using the external or internal
standard techniques.
13.1.1 If the external standard
calibration procedure is used, calculate
the concentration of the parameter
being measured from the area of the
characteristic ion using the calibration
curve or calibration factor in Section
7.3.2.
13.1.2 If the internal standard
calibration procedure was used,
calculate the concentration in the
sample using the response factor (RF)
determined in Section 7.4.3 and
equation 2.
Eq. 2.
Concentration ^g/l »
-------
As = Area of tne characteristic ion
for the parameter or surrogate
standard to be measurec.
A,s = Area of tne characteristic ion
for the internal standard.
CIS = Concentration of the internal
standard.
13.2 Report results in micrograms
per liter. The results for cis- and
trans-1.3 aichiorooropene should be
reported as total 1.3-dichloropropene
(STORET No. 3456 1, CAS No.
542-75-6}. When duplicate and spiked
samples are analyzed, report all data
obtained with the sample results.
13.3 If any of the surrogate standard
recoveries fall outside the control limns
which were established as directed in
Section 8.4, data for ail parameters
determined by this method in that
sample must be labeled as suspect.
14. Method Performance
14.1 The method detection limit
(MDL) is defined as the minimum
concentrationx>f a substance that can
be measured and reported with 99%
confidence that the value is above
zero,1). The MDL concentrations listed
in Table 1 were obtained using reagent
water<12i. Similar results were
achieved using representative
wastewaters.
14.2 The average recoveries and the
average standard deviations of the
percent recoveries, presented in Table
5. were the result of a study of the
accuracy and precision of this method
by several laboratories. The values
listed represent the results from 2 to 4
laboratories'131.
14.3 The U.S. Environmental Protec-
tion Agency is in the process of
conducting an interlaboratory method
study to fully define the performance
of this method.
References
1. See Appendix A.
2. Bellar, T.A., and J.J. lichtenberg,
Journal American Water Works
Association, 66, p. 739, (1 974).
3. Bellar, T.A., and J.J. Lichtenberg,
"Semi-Automated Headspace Analysis
Qf Drinking Waters and Industrial
Waters for Purgeable Volatile Organic
Compounds," Measurement of Organic
Pollutants in Water and Wastewater,
C.E. Van Hall, editor, American Society
for Testing and Materials. Philadelphia,
PA. Special Technical Publication 686,
1978.
4. "Sampling and Analysis Procedures
for Screening of Industrial Effluents for
Priority Pollutants." U.S.
Environmental Protection Agency,
Environmental Monitoring and Support
Laooratory, Cincinnati, OH 45268,
March 1977, Revised April 1977.
Effluent Guidelines Division,
Washington, DC 10460.
5. "Carcinogens —Working with
Carcinogens," Department of Health,
Education, and Welfare, Public Health
Service, Center for Disease Control,
National Institute for Occupational
Safety and Health, Publication No.
77-206, Aug. 1977.
6. "OSHA Safety and Health
Standards. General Industry,"
(29CFR1 9 1 0), Occupational Safety
and Health Administration. OSHA
2206, (Revised, January 1976).
7. "Safety in Academic Chemistry
Laboratories." American Chemical
Society Publication. Committee on
Chemical Safety. 3rd Edition, 1979.
8. "Handbook of Analytical Quality
Control in Water and Wastewater
Laboratories," EPA-600/4-79-01 9,
U.S. Environmental Protection Agency,
Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45260,
March 1979.
9. "Methods 330.4 (Titrimetric, DPD-
FAS) and 330.5 (Spectrophotometric,
DPDI for Chlorine, Total Residual,"
Methods for Chemical Analysis of
Water and Wastes, EPA
600/4-79-020, U.S. Environmental
Protection Agency, Environmental
Monitoring and Support Laboratory,
Cincinnati, Ohio 45268, March 1 979.
10. Budde, W.L. and Eichelberger,
J.W., "Performance Tests for the
Evaluation of Computerized Gas
Chromatography/Mass Spectrometry
Equipment and Laboratories,"
EPA-600/4-80-025, U.S.
Environmental Protection Agency,
Environmental Monitoring and Support
Laboratory, Cincinnati, OH 45268, p.
16, April 1 980.
1 1. Eichelberg, J.W. Harris, L.E., and
Budde, W.L., "Reference Compound to
Calibrate Ion Abundance Measurement
in Gas Chromatography —Mass
Spectrometry Systems.", Analytical
Chemistry, 47, 995-1000 (1979).
1 2. "Method Detection Limit for
Methods 624 and 625," Olynyk, P.,
Budde, W.L. Eichelberger, J.W.,
unpublished report. October 1980.
1 3. Kleopfer, R.D., "POTW Toxic
Study, Analytical Quality Assurance
Final Report." U.S. Environmental
Protection Agency, Region VII, Kansas
City, Kansas 661 1 5, 1981.
624-7
July 1982
230
-------
Table 1. Chromatographic Conditions and Method Detection Limits
Retention Time
Method
fminJ
Detection
Parameter
Column 1
Umit (vg/L)
Chloromethane
2.3
nd
Bromomethane
3.1
nd
Vinyl chloride
3.8
nd
Chloroethane
4.6
nd
Methylene chloride
6.4
2.8
Trichlorofluoromethene
a. 3
nd
1,1 -Dichloroethene
9.0
2.8
1,1 -Dichloroethane
10.1
4.7
trans- /, 2-Dichloroethene
10.8
1.6
Chloroform
11.4
1.6
1.2-Dichloroethane
12. 1
2.8
1,1,1- Tnchloroe thane
13.4
3.8
Carbon tetrachlonde
13.7
2.8
Bromodichloromethane
14.3
2.2
1,2 -Dichloropropane
15.7
6.0
trans-1,3-D/chioropropene
15.9
5.0
Trichloroethene
16.5
1.9
Benzene
17.0
4.4
Dibromochiorome thane
17.1
3.1
1,1,2'Trichloroethane
17.2
5.0
ciS' 1,3'Dichloropropene
17.2
nd
2'Chloroethylvinyl ether
18.6
nd
Bromoform
19.8
4.7
1,1,2.2-Tetrachloroethane
22.1
6.9
Tetra chloroeth ene
22.2
4.1
Toluene
23.5
6.0
Chlorobenzene
24.6
6.0
Ethyl benzene
26.4
7.2
1,3-Oichlorobenzene
33.9
nd
1,2 -D/chlorobenzene
35.0
nd
1.4-Oichlorobenzene
35.4
nd
nd » not determined
Column conditions: CarbopakB I60/Q0 mesh) coated with 1 % SP- 1000packed in a
6 ft by 2 mm ID glass column with helium carrier gas at a flow rate of 30 mUmin.
Column temperature is isothermal at 45 °C for 3 min, then programmed at 8°C per
minute to 220°C and held for 15 min.
Table 2. BFB Key Ion Abundance Criteria
Mass
Ion Abundance Criteria
50
15 to 40% of mass 95
75
30 to 60% of mass 95
95
Base Peak, 100% Relative Abundance
96
5 to 9% of mass 95
173
<2% of mass 1 74
174
>50% of mass 95
175
5 to 9% of mass 1 74
176
>95 % but < 101% of mass 1 74
177
5 to 9% of mass 1 76
624-8
July J 982
231
-------
Table 3. Suggested Surrogate and Internal Standards
Retention Time
Primary
Secondary
Compound
(minj*
Ion
Ions
Surrogate Standards
Benzene d-6
17.0
84
—
4-Bromofiuorobenzene
28.3
95
174, 176
1,2-Dich/oroethane d-4
12, 1
102
—
1,4-Difluorobenzene
79.6
1 14
63, 88
Ethylbenzene d-5
26.4
1 11
—
Ethylbenzene d• 10
26.4
98
—
Fluorobenzene
18.4
96
70
Pentafluorobenzene
23.5
168
-
Internal Standards
Bromochloromethane
9.3
128
49, 130f 51
2-Bromo• 1 •chloropropane
19.2
77
79, 156
1,4 •Dich/orobu tane
25.8
55
90, 92
*For chromatographic conditions, see Table 1.
Table 4. Characteristic Ions for Purgeabie Organics
Primary
Parameter Ion Secondary Ions
Chloromethane
50
52
Bromomethane
94
96
Vinyl chloride
62
64
Chloroethane
64
66
Methylene chloride
84
49.
51, 86
Trichlorofluoromethane
101
103
1,1 -Dichloroethene
96
61.
98
1,1 -Dichloroethane
63
65.
83. 85, 98, 100
trans¦ 1,2-Dich/oroethene
96
61.
98
Chloroform
83
85
1,2-Dich/oroethane
98
62.
64, 100
1,1,1-Trichioroethane
97
99,
117, 119
Carbon tetrachloride
117
119,
121
Bromodichloromethane
127
83,
85, 129
1,2'Dichloropropane
112
63,
65, 114
trans-1,3-Dichloropropene
75
77
Trichloroethene
130
95,
97, 132
Benzene
78
Dibromochloromethane
127
129.
208, 206
1.1,2-Trichforoethane
97
83,
85, 99, 132, 134
cis-1,3-Dichr/oropropene
75
77
2-Chloroethylviny/ ether
106
63,
65
Bromoform
173
17 7,
175, 250, 252, 254, 256
1,1,2,2-Tetrachloroethane
168
83,
85, 131, 133. 166
Tetrachloroethene
164
129,
131, 166
Toluene
92
91
Chiorobenzene
112
1 14
Ethyl benzene
106
91
1,3'Dichlorobenzene
146
148,
113
1,2'Oichlorobenzene
146
148,
113
1,4'Oichiorobenzene
146
148,
113
624-9
232 My r982
-------
Table 5. Accuracy and Precision for Purgeable Organics
Reagent Water
Wastewater
A verage
Standard
A verage
Standard
Percent
Deviation
Percent
Deviation
Parameter
Recovery
(%)
Recovery
(%)
Benzene
99
9
98
10
8romodichloromethane
102
12
103
10
Qromoform
104
14
105
16
Bromomethane
100
20
88
23
Carbon tetrachloride
102
16
104
15
Chlorobenzene
100
7
102
9
Chloroethene
97
22
103
31
2-Chloroethylvinyl ether
101
13
95
17
Chloroform
101
to
101
12
Chloromethane
99
19
99
24
Oibromochlorome thane
103
11
104
14
1,1 -Oichloroethane
101
10
104
15
1,2-Oichloroethane
100
a
102
10
1,1 -Oichloroethene
102
17
99
15
trans• 1,2-Dichloroe thene
99
12
101
10
1,2-Oichloropropane
102
8
103
12
ciS' 1,3-Oichloropropene
105
15
102
19
trans• 1,3-Oichloropropene
104
11
100
18
Ethyl benzene
100
8
103
10
Methylene chloride
96
16
89
28
1,1,2.2-Tetrachloroethane
102
9
104
14
Tetrachforoethene
101
9
100
11
Toluene
101
9
98
14
1,1,7 - Tnchloroethane
101
11
102
16
1,1,2-Trichtoroethane
101
10
104
15
Trichloroethene
101
9
100
12
Trichforofluoromethane
103
11
107
19
Vinyl chloride
100
13
98
25
Samples were spiked between 10 and 1000
Optional
Foam
Trap
^_Exit '/4 in.
OD.
14mm
I nJ 00¦
Inlet V4 in.
b'""~ 0.0.
V4 in.
0.0 exit
^ Sample iniat
2-way Syringe valve
17cm 20 gauge syringe needle
^6mm 0.0. Rubber Septum
, ^ 10mm 0.0.
Inlet
'/4 in. 0.0.
in. O.D.
\\yStainless Steel
13X molecular
sieve purge
10mm glass frit
medium porosity
gas filter
Purge gas
flow control
624^10
233
Figure 1. Purging device
July 1982
-------
Packing procedure
Gloss
woof
Grade 15
Silica gel
5mm
8cm\
Tenax 15cm
3% OV-1 1cm
Glass 5mm
woot
Construction
Compression fitting
•nut and ferrules
14ft TVfoot resistance
wire wrapped solid
Thermocouple/controller
sensor
Electronic
temperature
control
and
pyrometer
Tubing 25 cm.
0.105 in. l.D.
0.125 m. 0.0.
stainless steel
Trap inlet
Figure 2. Trap packings and construct/on to include desorb capability
Carrier gas flow control
Pressure regulator
Liquid injection ports
/. i Column oven
K h j> T I! I! n—- Confirmatory
J \ To detector
column
Purge gas
flow control \\
13X molecular
sieve fitter
6-port
valve
Analytical column
\ optional 4-port column
selection valve
Trap inlet
Resistance wire
^Heater control
Note:
AH lines between
trap and GC
should be heated
to 80°C
Purging
device
Figure 3. Schemetic of purge and trap device — purge mode
624-11
July 1982
234
-------
Carrier gas flow control
Pressure regulator
Purge gas
How control v
13X molecular
sieve fitter
1
Lm,d in,ecvon portsJCo,umn
oven
jg^-l v
^ | ~ - — — - i_
'f 1 • - i- | Analytical column
" "* L v— Confirmatory column
rJ"« I / To detector
optional 4-port column
selection valve
6-port Trap inlet
valve Resistance wire
Heater control
Trap\u_ Trap
1low< 170°C
Purging
device
{ On
Note:
All lines between
trep end GC
should be heated
to 95° C
Figure 4. Schematic of purge and trap device — desorb mode
Column: 1% SP-1000 on Supelcoport
Program: 45°C 3 mm.. 8° per min. to 220°C.
Detector: Mass spectrometer
*§
Is
«C «
-
^ £
S 5
« -c
.1^
• , 8.
^ 3
to 12 14- 16 18 20
Retention time, minutes
22 24 26 28
Figure 5. Gas chromatogram of volatile organics by purge and trap.
624 12
July 1982
235
------- |