-------
-------
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DISCLAIMER
The information in this document has been funded wholly or in
part by the United States Environmental Protection Agency under
contract No. 68-03-2856 to Monsanto Company. It has been subject
to the Agency's peer and administrative 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..
11
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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 (E^SL)-Cincinnati
research responsibilities are to:
• Develop and evaluate techniques to measure the presence and
concentration of physical, chemical, and radiological pollut-
ants in water, wastewater, bottom sediments, and solid waste.
/'
• Investigate methods for the concentration, recovery, and
identification of viruses, bacteria, and other microorganisms
in water.
• Conduct studies to determine the responses of aquatic organ-
isms to water quality.
• Conduct an Agency-wide quality assurance program to assure
standardization and quality control of systems for rionitoring
water and wastewater.
This publication reports the results of EPA's interlaboratory
method study for the following compounds:
benzene 1,4-dichlorobenzene
chlorobenzene ethylbenzene
1,2-dichlorobenzene toluene
1,3-dichlorobenzene
iii
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Federal agencies, states, municipalities, universities, private
laboratories, and industry should find this inLerlaboratory study
useful in monitoring and controlling pollution in the environment.
Robert L. Booth, Acting Director
Environmental Monitoring and Support Laboratory
iv
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ABSTRACT
Described herein are the experimental design and the results of an
interlaboratory study of an analytical method for detecting purge-
able aromatics in water. The method, EPA Method 602, Purgeable
Aromatics, employs a purge-and-trap chromatographic technique for
determining seven aromatic hydrocarbon ar.alytes in water matrices.
Three Youden pairs of spiking solutions were used and contained
benzene, chlorob«;nzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene,
1,4-
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This report was submitted in fulfillment of Contract 68-03-2856
by Monsanto Company under the sponsorship of the U.S. Environmen-
tal Protection Agency and covers a period from September 1979 to
December 1982.
VI
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CONTENTS
Foreword iii
Abstract v
Tables viii
Acknowledgements xi
1. Introduction 1
2. Conclusions 4
3. Recommendations 8
4. Description of Study 9
Selection of participating laboratories 9
Phase I - Analysis of prestudy conference samples 10
Phase II - Prestudy conference 17
Phase III - Interlaboratory method study 18
5. Statistical Treatment of Data 21
Rejection of outliers 21
Statistical summaries 27
Comparison of accuracy and precision
across water types 39
6. Results and Discussion 46
Accuracy 46
Precision 50
Effects of water types 64
Responses to questionnaire 66
Other Monsanto Company findings during
preliminary studies 70
References 72
Appendices
A. Purgeable aromatics Method 602 73
B. Additional notes on Method 602 84
C. Preliminary investigation of Method 602 92
D. Analyses of standard spiking solutions employed
in Method 602 96
E. Raw Data 100
F. Revised data from Laboratory 12 125
G. Effects of water type on precision and accuracy. . . . 131
VII
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TABLES
Number Page
1 Regression Equations for Accuracy and Precision. . 5
2 Laboratories Participating ir EPA Method 602
Interlaboratory Study 11
3 Procedure for Preparation of Stock Solutions ... 12
4 Procedure for Preparation of Aqueous
Calibration standards 13
5 Procedure for Spiking Water 14
6 Results of Method 602 Frestudy Analyses:
Purgeable Aromatics 16
7 Concentrations of Aromatics in Spiked Solutions. . 19
8 Youden Laboratory Ranking Procedure for
Benzene Data in Water 3 24
9 Critical Values for t (Onesided Test) When
Standard Deviation is Calculated from
the Same Samples 26
10 Results of Test for Individual Outliers by the
t-Test (Benzene in Water 3) 26
11 Statistical Summary for Benzene Analyses by
Water Type 30
12 Statistical Summary for Chlorobenzene Analyses
by Water Type 31
13 Statistical Summary for 1,2-Dichlorobenzene
Analyses by Water Type 32
14 Statistical Summary for 1,3-Dichlorobenzene
Analyses by Water Type 33
15 Statistical Summary for 1,4-Dichlorobenzene
Analyses by Water Type 34
viii
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TABLES (continued)
Number Page
16 Statistical Summary for Ethylbenzene
Analyses by Water Type 35
17 Statistical Summary for Toluene Analyses by
Water Type 36
18 Method 602 Accuracy 47
19 Method 602 Precision (% RSD) 51
20 Method 602 Precision (% RSD-SA) 53
21 Summary of Precision (% RSD) by Analyte, Water
Type, and Concentration Level 56
22 Summary of Precision (% RSD-SA) by Analyte,
Water Type, and Concentration Level 58
23 Relative Magnitude of Intercepts in the Linear
Regression Equations 60
24 Comparison of Single Operator Accuracy and
Precision 64
25 Summary of the Tests for Difference Across
Water Types 65
26 Laboratory Analytical Conditions 67
27 Automated (5830/40) Gas Chromatographs 89
28 Initial Set Points 89
29 Summary of Method 602 Detection Limit Data .... 95
30 Chromatographic Conditions 98
31 Stability Data 99
32 Raw Data for Benzene Analysis by Water Type. . . . 101
33 Raw Data for Chlorobenzene Analysis by Water Type. 104
34 Raw Data for 1,2-Dichlorobenzene Analysis by
Water Type 107
ix
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TABLES (continued)
Number
Page
35 Raw Data for 1,3-Dichlorobenzene Analysis by
Water Type 110
36 Raw Data for 1,4-Dichlorobenzene Analysis by
Water Type 113
37 Raw Data for Ethylbenzene Analysis by Water Type . 116
38 Raw Data for Toluene Analysis by Water Type. . . . 119
39 Blank Values in Distilled Water 122
40 Blank Values in Tap Water 123
41 Blank Values in Surface Water 124
42 Blank Values in Wastewater 1 125
43 Blank Values in Wastewater 2 126
44 Blank Values in Wastewater 3 127
45 Revised Data from Laboratory 12 129
46 Effect of Water Type on Benzene Analysis 137
47 Effc:t of Water Type on Chlorobenzene Analysis . . 133
48 Effect of Wat^r Type on 1,2-Dichlorobe:izene
Analysis 134
49 Effect of Water Type on 1,3-Dichlorobenzene
Analysis 135
50 Effect of Water Type on 1,4-Dichlorobenzene
Analysis 136
51 Effect of Water Type on Ethylbenzene Analysis. . . 137
52 Effect of Water Type on Toluene Analysis 138
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ACKNOWLEDGEMENTS
The authors gratefully acknowledge the hard work and cooperation
of the staff of the Quality Assurance Branch, EMSL, who assisted
in the study. They especially acknov;ledge the excellent techni-
cal assistance, guidance, and understanding of Raymond Wesselman
of EMSL. Also acknowledged is the work of Dr. Thomas Bishop at
Battelle Columbus Laboratories, Columbus, Ohio, for statistical
analysis of the data under contract 68-03-2624.
XI
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SECTION 1
INTRODUCTION
The various analytical laboratories of the U.S. Environmental
Protection Agency (EPA) gather water quality data to provide in-
formation on water resources, to assist research activities, and
to evaluate pollution abatement activities. The success of the
Agency's pollution control activities, particularly when legal
action is involved, dapends upon the reliability of the data pro-
vided by the laboratories.
Under provisions of the Clean Water Act, th« EPA is required to
promulgate guidelines establishing test procedures for the
analysis of pollutants. The Clean Water Act Amendments of 1977
emphasize the control of toxic pollutants and declare the 65
"priority" pollutants and classes of pollutants to be toxic under
Section 307(a) of the Act. This report is one of a series that
investigates the analytical behavior of selected priority pollu-
tants and suggests a suitable test procedure for their measurement.
The priority pollutants to be analyzed by Method 602 covered by
this report are the following purgeable aromatics:
benzene
chlorobenzene
1,2-dichlorobenzene
1,3-dichlorobenzene
1,4-dichlorobenzene
ethylbenzene
toluene
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The Environmental Monitoring and Support Laboratory-Cincinnati
(EMSL-Ci) of the EPA develops analytical methods and conducts a
quality assurance program for the water laboratories. This program
is designed to maximize the reliability and legal defensibility of
all water quality information collected by E:A laboratories. The
responsibility for these activities is assigned to the Quality
Assurance Branch (QAB). One of these activities is to conduct
interlaboratory tests of the methods. This report presents the
results of interlaboratory study 25 on Method 602 for purgeable
aromatics.
The study consisted of three distinct phases. Phase I involved the
analysis of the prestudy samples by 20 participating laboratories.
Two samples were analyzed for each of the seven purgeable aromatics;
a medium concentration sample to be analyzed in drinking water
supplied by the participating laboratories and a low level sample to
be analyzed in a wastewater sample supplied by Monsanto Company.
The objective of Phase I was to become familiar with the methodology
employed and to identify any potential problems associated with the
analytical methodology. Accuracy was not as important as being
familiar with the methodology. A short report, including the data
obtained and any potential problems encountered, was received by
Monsanto Company at the completion of Phase I from each subcon-
tracting laboratory.
Phase II consisted of a prestudy conference held at U.S. Environ-
mental Protection Agency (EPA) in Cincinnati, Ohio, after the data
from the Phase I samples had been evaluated. The purpose of the
prestudy conference was to discuss the results of the Phase I sample
analyses and any problems encountered in the methodology. Each
subcontracting laboratory sent at least one analyst to this meeting.
-------
Phase III consisted of the formal interlaboratory study. Each
of the seven arcmatic purgeables were analyzed at six concentra-
tions (three Youden pairs) in six different water matrices. The
participating laboratories each supplied its own distilled water,
drinking water and surface water. Monsanto Company supplied the
three industrial wastewaters. In addition, the participating
laboratories performed analyses of all water blanks with no
spiked compounds. Each participating laboratory then issued a
report to Monsanto Company containing all data obtained, copies
of all chromatograms, and any comments.
The final step in the study was to conduct a statistical analysis
of -ill data obtained. This analysis was conducted by Battelle
Columbus Laboratories, Columbus, Ohio, under contract 68-03-2624
employing a system of computer programs known as the Interlabora-
tory Method Validation Study (IMVS) system. _•.
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SECTION 2
CONCLUSIONS
The object of this study was to characterize the performance of
Method 602 in terms of accuracy, overall precision, sinyle-analyst
precision and the effect of water types on accuracy and precision.
Through statistical analyses of 5,040 analytical values, estimates
of accuracy and precision were made and expressed as regression
equations, which are shown in Table 1.
The accuracy of the method is obtained by comparing the mean recovery
to the true values of the concentration. Expressed as percent
recovery it ranges from 86% to 97% in distilled, tap, and surface
water. Excluding the values where large interferences entered into
play, the accuracy in wastewaters ranges from 84% to 100%. Large
interferences (background) existed in wastewater 5 for chlorobenzene
and toluene. At the lowest concentration levels, recoveries
exceeding 500% were reported. At the middle and high levels, average
recoveries were 94% and 86%, respectively, for chlorobenzene and
toluene.
The overall standard deviation indicates the precision associated
with measurements generated by a group of laboratories. The percent
relative standard deviation (%RSD) for all waters, ranges from 9.9%
to 39.8% for the middle and high Youden pairs. The low Youden pair
ranges from 20.9% to 55% in distilled, tap, and surface water. The
range in wastewater is 30.5% to 63.7% excluding chlorohenzene and
toluene. In all cases, the highest %RSD (poorest precision) was at
the lowest Youden pair.
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TABLE 1. REGRESSION EQUATIONS FOR ACCURACY AND PRECISION
UATEK TYPE
APPLICABLE CONC. MANGE
UlSTILLEU UATEK
SINGLE-ANALYST PKECISION
OVEKALL PKECISIUN
ACCUKACY
TAP UATEK
SINGLE-ANALYST PKECISION
OVEKALL PKECISION
ACCUKACY
SUKFACE UATEK
SINGLE-ANALYST PKECISION
OVEKALL "KECISION
ACCUKACY
UAbTE UATEK 1
SINGLE -ANALYST PKECISION
OVEKALL PKECISION
ACCUKACY
WASTE UATEK 2
SINGLE-ANALYST PKECISION
OVEKALL PKECISIUN
ACCUKACY
UASTE UATEK j
SINGLE-ANALYST PKECISIUN
UVEKALL PKtCISlUN
ACCUKACV
BENZENE
(2.20 - bbO
SH « 0.09X
S •= C.21X *
X = 0.92C »
SK =• U.11X
S « 0.22X *
X « 0.97C *
SK * O.OUX
S • 0.19X *
X » 0.93C »
SK ' 0.1 3X
S = 0.26X »
X - 0.91C *
SK * O.U9X
S • 0.2bX *
X > U.87C »
SK * 0.10X
S = U.2bX *
X « 0.93C »
CHLOKOBLMENE
.00)
» O.b9
O.b6
O.b7
- U.U6
1.11
0.8b
«• 0.17
O.J8
0.37
» O.b6
O.b'J
O.Ub
» 0.89
0.97
0.36
«• 0.43
O.b8
U.bO
(2
SK
S
X
SK
S
X
SK
S
X
SK
S
X
SK
S
X
SK
S
X
.20 - bbl
= 0.09X
* 0.1 7X +
= 0.9bC »
= 0.1UX
= O.lbX »
= 0.9'C »
= U.OHX
= 0.19X +
=• o.'..r -
= O.GltX
- (I.21X »
= 0.93C »
= 0.09X
' U.3IX *
= 0.63C »
= O.HIX
= O.lbX »
= 0.92C »
.00)
t 0.23
0.10
0.02
* 0.12
0.36
0.12
» 0.14
0.20
0.14
» 3.02
2.33
l.Hb
»14.83
11.81
19.77
» 0.43
0.8b
U.lb
I.
(2
SK
S
X
SH
S
X
SK
S
X
SK
S
X
SK
S
X
SK
S
X
2-UICHLOKOriENlENE
.20 - 600
= U.17X
= U.22X *
= U.93C +
= 0.10X
= O.I8X »
= 0.91C »
= 0.10X
= 0.18X »
= 0.89C »
= U.I1X
= 0.2bX »
= 0.90C +
* 0.10X
« 0.17X »
• 0.9bC *
=• O.lbX
- 0.181 »
' 0.88C -
.00)
- 0.04
U.b3
U.52
* 0.42
0.28
0.44
» 0.04
0.12
0.21
* 0.93
0.37
0.38
+ 0.90
1.12
0.69
» U.14
U.bl
0.39
1.
(2
SK
S
X
SK
S
X
SK
S
X
SK
S
X
SK
S
X
SK
S
X
3-UICHLUKI>BEN2ENE
.20 - bbO
= O.lbX
« 0.19X +
= 0.96C -
= 0.08X
= O.lbX »
= 0.93C »
= 0.10X
= 0.18X +
' 0.93C t
= O.lbX
= 0.36X »
= l.OOC ;
= 0.10X
•= 0.19X »
* 0.92C »
' 0.12X
' O.lbX »
» 0.94C »
.00)
- 0.10
0.09
O.Ob
» 0.33
0.33
0.21
» 0.01
O.HO
0.40
» 0.4b
0.«3
3.36
» O.b2
0.79
O.bO
» 0.29
U.-J3
0.16
X ' NEAN KLtUVLrfY
C - TKUE VALUt HJK I ML CONCENTKAT ION
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TABLE 1 (continued)
WATCH TYPE
APPLICABLE CONC. RANI i
I.
(2
4-UlCHLUKOUEWENE
EIHVLHEN/INL
.2U - bbO.UU) (2
.2U - bbl
.00)
TOLUENL
(2
.10 - -,:bO.OO)
DISTILLED WATEK
SINGLE -ANALYST
PRECISION
UVEKALL PKECISlUN
ACCURACY
TAP WATEK
SINGLE -ANALYST
PKECISlUN
UVEKALL PRECIS1UN
ACCURACY
SURFACE WATER
SINGLE-ANALYST
PKECISlUN
UVEKALL PKECISlUN
ACCURACY
WASTE WATER 1
SINGLE-ANALYST
PRECISIUN
UVEKALL PRECISIUN
ACCURACY
WASTE WATER 2
SINGLF. -ANALYST
PRECISION
SK
S
X
SK
S
X
SK
S
X
SK
S
X
SK
UVERALL PRECISIUN S
ACCURACY
WASTE WATEK 3
SINGLE-ANALYST
PRECISIUN
UVEKALL PKS.CISIOR
ACCURACY
X
SK
S
X
-- U.lbX
« U.2UX
* (t.')X.
* U.U9X
« U.lbX
= U.91C
* U.12X
- U.l/X
* U.88C
- U.O/X
= 0.1UX
• U.89C
» U.10X
• U.I9X
- u.9bC
» U.U9X
* U.lbX
• 0.91C
» 0.2«
» 0.41
- 0.09
» 0.39
» 0.39
» 0.26
- U.Ob
» 0.8b
» U.2/
* 0.8b
» O.b9
» O.b4
* O.bb
» U.49
» U.3J
• U.34
» U.33
» U.il
SK
S
X
SK
S
X
SK
S
X
SK
S
A
SK
S
X
SR
S
X
- 0.1/X
= U.2bX v
= U.94C »
= o.lux
= 0.20X »
= o.y/c *
- O.UHX
= J.21X *
= U.^JC »
= o.ux
= 0.21X «
= 'J.W4C »
- U.I1X
= O.ZbX »
= O.HbC »
= O.I3X
= U.i'lIX t
- U.8% «
» U
0.
U.
» 0
0.
0.
.4b
23
31
.IH
b8
41
» 0.33
0.
0.
» 0
0.
0.
3b
20
.38
40
3H
> 0.4b
0.
0.
* U
0.
0.
bJ
14
'.b2
78
73
SR
S
X
SK
S
X
SK
S
X
SK
S
X
SK
S
X
SH
S
X
= 0. '»X
= O.I8X
» 0.44C
= 0.101
= O.;MX
= 0.94C
= 0 08X
= 0.i?bX
* 0.4JC
= 0. MX
= D.24X
- (l.-'/C
• 0.1«.',
= O.L'HX
= 0.71C
- 0.1UX
» 0.21X
• 0.4IC
» 0.48
« 0.71
» O.bb
+ 0.18
• O.lh
» 0.17
» 0.18
• 0.33
» 0.02
* I.Ob
* O.b7
» o.m
• 3.47
» 4.3b
» 8.»>3
* 1.20
» l.bb
• 1.01
X ' MEAN KECOVLKY
C * TKUE VALUL tUrt (HE CONCENTKATION
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The single-analyst standar'd deviation indicates the precision
associated within a single laboratory. The percent relative
standard deviation for a single analyst (%3SD-SA) for all waters,
ranges from 6.1% to 31.8% for the middle and high Youden pair. Th<>
low Youden pair ranges front 9.0% to 33.7% for distilled, tap, and
surface water. The range in wastewaters is 20.9% to 43.5%,
excluding chlorobenzene and toluene. In all cases, the highest
%RSD-SA (poorest precision) was at the lowest Youden pair.
A statistical comparison of the effec': of water type was perforned
indicating a a tatistically significant difference for six of the
analyte/water matrix combinations. Of these six cases, a practical
significant difference was established in only two cases;
chlorobenzene and toluene in water 5.
-------
SECTION 3
RECOMMENDATIONS
Method 602 is recommended for the analysis of purceable aromatics
in municipal and industrial wastewaters. The accuracy and pre-
cision are acceptable, while the matrix effects are significant
only at low concentration levels.
tiecouse deposition of high-boiling compounds and column bleed onto
the photoJonization detector (PID) lamp window causes a continual
less of detector response, frequent cleaning of the lamp window is
recommended. This may be aleviated by not exceeding the column
temperature 9C°C recommended in Method. 602. Venting of the
column at higher temperature (e.g., 150°C) through the detector
can lead to fouling of the detector window.
Potential carry-over problems from contaminated water can be
lessened or eliminated by analyzing a blank sample prior to the
next water sample.
Care must be taken in vhe preparation of laboratory pure water.
Contamination from solvents in the atmosphere is common.
Teflon is not recommended for gas lines. Methylene chloride per-
meates the Teflon, and naphthalene, which is used as a lubricant
in the drawing of the Teflon, responds to the PID. Copper or
stainless steel gas lines are recommended.
6
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SECTION 4
DESCRIPTION OF STUDY
SELECTION OF PARTICIPATING LABORATORIES
In June .1980, as prime contractor, Monsanto Company sent requests
for quotation (RFQ) to approximately 150 laboratories which had
been identified as potential subcontractors for this interlabora-
tory study. The RFQ contained a Scope of Work, the fixed price
allowed for the effort, a description of the projected timing of
the required analyses, and a copy of the analytical method. The
detailed writeup for Method 602 as published by EPA on 15 May
1979 is presented in Appendix A of this report. Interested labo-
ratories wers asked to respond to the RFQ by providing the
following .information:
• Facilities available at the laboratory, including all
instrumentation to be urad for the study.
• Previous experience in carrying out the types of analyses
specified in the Scope of Work for the compounds of
interest.
• Handling procedures for working with hazardous and poten-
tially hazardous chemicals.
• The organization and managerial structure of the laboratory,
identifying those personnel involved in managing this study.
-------
• The analyst involved in the analyses to be per-
formed, including his/her experience.
• Quality control/qua]ity assurance procedures and good
laboratory practices followed by the laboratory.
Approximately 25 proposals were received in response to the RFQ.
The proposals received were ranked, and the 20 most qualified
laboratories were selected for participation. Table 2 lists the
participating laboratories for the EPA Method 602 interlaboratory
study. Throughout this report, data provided by these laborator-
ies will be identified only by an anonymous code number.
Phase I - Analysis of Prestudy Conference Samples
In November 1980, MRC forwarded to each of the 20 participating
laboratories two sealed glass ampuls containing mixod concen-
trates of the seven aromatic compounds in methanol, and a sample
of an industrial wastewater. Also forwarded were procedures for
the preparation of stock solutions, procedures for the preparation
of aqueous calibration standards, and procedures for spiking the
drinking water and wastewater with the prestudy samples contained
iii the ampuls. The recommended procedures are presented in
Tables 3, 4, and 5.
At this same time, applicable notes on Method 602 were sent to
each participating laboratory. The notes on Method 602 for the
analysis of preconference samples are included in Appendix B of
this report and referenced by paragraph/section number of the
test method as presented in Appendix A. The notes on Method 602
included recommended procedures to minimize cross contamination
from sample to sample, recommended procedures for cleaning the
purge path and analytical column of high-boiling compounds,
appropriate purge/trap samplers and purging vessel design avid
capacities, recommended contents of the sorbent trap, methods to
10
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TABLE 2. LABORATORIES PARTICIPATING IN EPA
METHOD 602 INTERLABORATORY STUDY
Acurex Corporation
285 Clyde Avenue
Mountain View, CA 94042
Analytics
Division of CBL
Subsidiary of Rohm & Haas Co.
1415 Rhoadmiller
Richmond, VA 23260
Clayton Environmental Consultants, Inc.
25711 Southfield Road
Southfield, MI
Engineering Science, Inc.
Research and Development Laboratory
600 Bancroft Way
Berkeley, CA 94710
Environmental Research Group, Inc.
117 North First
Ann Arbor, MI 48104
ERCO/Energy Research Co., Inc.
165 Alewife Brook Parkway
Cambridge, MA 0213B
Global Geochemistry Corp.
6919 Eton Avenue
Canoga Park, CA 91303
Jacobs Laboratories (formerly PJB
Laboratories)
373 South Fail- Oaks Avenue
Pasadena, CA 91105
Normandeau Associates. Inc. (formerly
Texas Instruments, Inc.)
1710 Firman Drive
Richardson, TX 75081
Northrop Services, Inc.
Environmental Services
P.O. Box 437
Little Rock AR 72203
Orlando Laboratories, Inc.
P.O. Box 8008
90 West Jersey Street
Orland, FL 32i'0&
PLOCo Environmental, Inc.
11499 Chester I'.oad
Cincinnati, OH 45246
SERCO Laboratories
Sanitary Engineering Laboratories, Inc.
1931 West County Road, C2
Roseville. MN 55113
State of N#w York
Department of Health
Tower Building
The Governor Nelson A. Rockeller
Empire State Plaza
Albany, NY 12201
Technical Services, Inc.
103-7 Stockton Street
P.O. Box 52329
Jacksonville. FL 32201
UBTL, Division of University of Utah
Research Institute
520 Wakara Way
Salt Lake City, UT 84108
Versar, Inc.
6621 Electronic Drive
Springfield, VA 22151
Weston Designers Consultants
Weston Way
West Chester, PA 19380
Wilson Laboratories
Analytical & Research Chemists and
Biologists
528 North Ninth
Salina, KS 67401
O'Brien & Cere Engrs.,
Box 4873
1304 Buckley Road
Syracuse, NY 13221
Inc.
11
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TABLE 3. PROCEDURE FOR PREPARATION OF STOCK SOLUTIONS
1. Place about 9.8 mL of methyl alcohol into a ground glass
stoppered 10-mL volumetric flask.
2. Allow the flask to stand unstoppered about 10 minutes or
until all alcohol wetted surfaces have dried.
3. Weigh the flask to the nearest 0.1 mg.
4. Using a 100-pL syringe, immediately add 2 drops of the
reference standard to the flask, then reweigh. Be sure
that the 2 drops fall directly into the alcohol without
contacting the neck of the flask.
5. Dilute to volume, stopper, then mix by inverting the
flask several times.
6. Transfer the solution to a dated and labeled 15-mL screw-
cap bottle with a Teflon cap liner.
7. Calculate the concentration in micrograms per microliter
from the net gain in weight.
8. Store the solution at 4°C.
All standard solutions prepared in methyl alcohol
are stable up to four weeks when stored under these
conditions. They should be discarded after that
time has elapsed.
Because of the toxicity of the purgeables, it is
necessary to prepare primary dilutions in a hood.
It is further recommended that a NIOSH/MESA-
approved toxic gas respirator be used when the
analyst handles high concentrations of such
materials.
1.2
-------
TABLE 4. PROCEDURE FOR PREPARATION OF AQUEOUS
CALIBRATION STANDARDS
To prepare accurate standard solutions, the following precau-
tions must be observed:
• Do not inject less than 20 pL of c'.lconolic standards into
100 mL of reagent water.
• Use a 25-pL Hamilton 702N microsyringe or equivalent.
(Variations in needle geometry will adversely affect the
ability to deliver reproducible volumes of methanolic
standard into water.)
• Rapidly inject the alcoholic standard into the expanded
area of the filled volumetric fia&k. Remove the needle
as fast as possible after injection.
• Mix aqueous standards by inverting the flask three times
only.
• Never use pipets to dilute or transfer samples or aqueous
standards.
• Aqueous standards wher stored with a headspace are not
stable and should be discarded after one hour.
13
_.*.. ^ ...... .lJU. J
J
-------
TABLE 5. PROCEDURE FOR SPIKING WAT2R
If duplicate analyses are to be performed on one ampul,
concurrently perform all of the following steps below
in duplicate:
• Fill a 100-mL volumetric flask to volume with reagent
water.
• Stablize the ampuls to 20°C.
• Use a 25-pL Hamilton 702N microsyringe or equivalent.
(Variations in needle geometry will adversely affect
the ability to deliver reproducible volumes of
methanolic standard into water.)
• Open the ampuls by breaking off the top at the break
area on the neck and immediately fill the syringe.
• Rapidly inject 20 uL of the ampul concentrate into the
expanded area of the fill&d volumetric flask. Remove
the needle as fast as possible after injection.
• Mix the sample by inverting the flask three times only.
• Never use pipets to dilute or transfer samples
or aqueous standards.
• Aqueous solutions when stored with a headspace are not
stable and should be discarded after one hour.
14
-------
control loss in the PID (especially in the analyses of wastewater
matrices), recommended purge, desorb and vent cycles, recommended
use of organic-free water to prevent contamination from laboratory
air. and recommended quality assurance practices.
The notes on Method 602 were developed after agreement was reached
by EPA and MRC concerning which method steps were to be rigidly
fixed and which conditions could be optimized by the individual
laboratory. Some latitude was permitted in (1) selection of
purge/trap samples (Hewlett-Packard as well as Tekmar); (2) trap
material (potential omission of 3% OV-l); (3) chromatographic
column material either 5% SP-1200 or 5% SP-2100. The majority
of the Method 602 procedural steps were to te rigidly observed
in this interlaboratory study.
Notes on Method 602 largely resulting from the experience gained
by MRC uralysts in the preliminary studies of the method are pre-
sented in Appendix C.
The two ampuls sent to the participating laboratories for the pre-
study conference analyses contained concentrated mixtures of the
seven aromatic compounds such that, when they were spiked into the
two waters, the resulting concentrations of the individual
aromatics would be:
Concentration
50 to 63 pg/L
2.5 to 3.2 ug/L
The analysis of the higher concentration sample in drinking water
assured that, the method could be properly implemented by the
laboratories with a minimum of difficulty. Analysis of the lower
concentration in the wastewater was intended to evaluate any
method or detection limit problems that could arise under more
adverse conditions. The results of these analyses are presented
in Table 6.
15
-------
TABLE 6. RESULTS OF METHOD 602 PRESTUDY ANALYSES:
(M9/L)
PURGEABLE AROMAT1CS
C Oil-pound
Laboratory
01
02
03
04
05
06
07
08
09
10
11
12
13
14
IS
16
17
18
19
20
True value
Hean*
Standard
deviation
Range
Benzene
44
S2.6
49
34.66
42
4.46
50.5
58
49
61
3.8
NO
87.2
40
50
41
24
MD-B7.2
MD
1.1
2.3
0.48
0.5
0.05
0.«54
1
2.8
ND
0.5
ND
ND
ND
2.5
0.7
0.9
HD-2.8
Chlorobenzene
38
42.3
64
43.63
38
4.57
40.7
38
53
45
2.1
32
54.3
9.5
63
36
19
2.1-64
ND
1.0
11
0.64
6
0.14
1.68
4
1.6
7.1
0.6
6.3
HD
55.2
3.2
6.8
14
ND-55.2
1,2-Dichloro-
benzene
44
55.6
59
34.56
46
5.00
48.9
64
67
26
ND
48
68.5
45.0
50
44
21
ND-68.S
ND
1.1
2.1
0.42
2.2
c.a
1.573
5
0.8
1.5
ND
2.9
ND
3.3
2.5
1.5
1.5
ND-5
1,3-Dichloro-
benzene
44
53.7
61
34.33
51
5.52
51.8
56
63
54
2.3
47
&:.i
40.2
50
45
19
2.3-63
ND
1.0
1.5
0.64
1.6
0.08
0.14
4
2.1
1.2
2.0
2.5
ND
3.0
2.5
1.4
1.2
ND-4
1,4-Dichloro-
benzene
44
57.2
56
36.88
40
6.13
52.9
66
63
55
1.6
45
59.7
43.5
51
4b
19
1.6-66
ND
0.1
0.3
ND
ND
0.01
0.192
<1
0.3
0.4
1.8
1.3
ND
1.0
2.6
0.5
0.6
ND-1.8
Ethylbenzene
44
54
57
41.77
49
6.67
48.5
44
78
59
2.6
46
62.5
11.3
50
43
22
2.6-78
ND
1.2
1.4
1.07
1.4
0.08
1.094
<1
1.2
1.1
0.2
2.6
ND
12.5
2.5
1.8
3.2
Hii-12.5
Toluene
42
53.4
46
40.00
45
5.71
51.1
48
67
60
2.6
45
88.0
44
50
46
22
2.6-88
ND
ND
120
70.89
128
1.79
ND
120
12
115
9.9
126
ND
100.1
2.5
57
58
ND-128
"Data reported as "Not Detected" was calculated as 0. Data reported as
-------
The Jata shown in Table 6 include correction for the blank values
of the aromatics in the various laboratories' drinking water and
in the wastewater. If the value for a compound in the blank was
greater than or equal to the value in the sample, ND (not de-
tected) was reported. N-l statistics were used to calculate the
standard deviation; ND was calculated as "0",
-------
the HNU high temperature Model PI-51 detector is stable for
extended periods of time, i.e., 6 weeks. If the low temper-
ature model detector is substituted or if the column is
heated abovs 90°C and purged through the detector, detector
window fouling and subsequent instability can result.]
• A quenching effect of the PID is observed whenever water
or methanol is eluting from the column.
• Poor separation of the given compounds may be due to the
column. A poorly packed column, packing degradation,
and improper packing material can cause poor resolution.
Phase III - Interlaboratory Method Study
The method study samples were sent to the participating labora-
tories in March 1981. The design of the interlaboratory method
study was based on Youden's original plan for collaborative eval-
uation of precision and accuracy for analytical methods [1].
According to Youden's design, instead of duplicate analyses,
samples are analyzed in pairs, and each sample of a pair has
slightly different concentrations of the constituents. The anal-
yst is directed to perform a single analysis and report one value
for each sample.
Six spiking solutions were made such that three different concen-
tration ranges were each represented by two different solutions
(a Youden pair). The spiking solutions, which were sent in sealed
ampuls, were at such a concentration that after dilution in water,
solutions 1 and 2 would have aromatic concentrations at a low
level of about 2 pg/L, solutions 3 and 4 would have concentrations
at about 50 pg/L, and solutions 5 and 6 would yield concentrations
about 10 times the intermediate level. Table 7 shows the indivi-
dual aromatic compound concentrations that should result from each
spiked water sample.
18
-------
TABLE 7. CONCENTRATIONS OF AROMAT1CS IN SPIKED SOLUTIONS
(M9/L)
Solution concentration
Compound
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Toluene
1
2.2
2.2
2.2
2.2
2.2
2.2
2.1
2
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3
46
46
46
46
46
46
46
4
54
54
54
54
54
54
54
5
450
450
449
450
450
452
450
6
550
551
600
550
550
D51
550
The concentrated spiking solutions shipped to the participating
laboratories were sealed in glass ampuls employing a Cozzoli Model
HS1 ampul sealer. Analyses of the concentrations of the aromatic
compounds in the ampuls shipped to the participating laboratories
were conducted by MRC employing direct injection chromatographic
procedures. These data are reported in Appendix D.
The participating laboratories again received instructions for
the analysis of the aromatic compounds in the six water samples
including the procedures for preparation of stock solutions.
calibration standards, and quality control samples. In addition,
each laboratory received a questionnaire and notes from the pre-
study conference.
The results from the 20 participating laboratories employing EPA
Method 602 for analysis of the seven aromatic compounds in the
six water samples are presented in Appendix E. All values shown
are corrected for blank values. Corrected values less than zero
are shown as zero.
19
-------
When informed that there might be some consistent srror in their
data, Laboratory 12 responded with a new set of data stating that
data was originally quantitated using peak heights, and that a
change in integrator attenuation was inadvertantly omitted from
the earliex calculations. At that time, Monsanto Company could
not substantiate this change in data values, and it was decided
that the earlier da*~a should be subjected to statistical analysis.
The revised data from Laboratory 12 are presented in Appendix F
of this report.
20
-------
SECTION 5
STATISTICAL TREATMENT OF DATA
Data os ,i:-ied from the interlaboratory study were subjected to
statist..^;.! j-.nalyses by the Battelle Columbus Laboratories,
Columbus, Ohio, under EPA Contract 68-03-2624. The analyses were
performed employing the Interlabrratory Method Validation Study
(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 system
included tests for the rejection of outliers (both whole labora-
tories for a water type and individual data points), estimation
of mean recovery (accuracy), estimation of single-analyst and
overall precision, and tests for the effects of water type on
accuracy and precision.
REJECTION OF OUTLIERS
An outlying observation, or "outlier," is a data point that
appears to deviate markedly from other members of the sample in
which it occurs. Outlying data points are very commonly encount-
ered 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 nethod.
These outlying points cannot be removed indiscriminantl^J, however,
because they may represent an extreme manifestation of the random
variability inherent in the method.
21
-------
ASTM procedure E178-80, "Standard Practice for Dealing with
Outlying Observations" (4], and ASTM procedure D2777-77 [3]
present explicit statistical rules and methods for identifi-
cation of outliers.
Data from outlying laboratories for a particular water type were
rejected employing Youden's laboratory ranking test procedure [3,
5] at the 5% level of significance. Data remaining after the
laboratory ranking procedure were subjected to individual outlier
tests. After all zero, missing, "less chan" and "noncfetect" data
were rejected as outliers, the average and standard deviation for
all remaining data were examined using cne sided Student's t-test
outlier rejection test constructed by Thompson [6]. All data
rejected as outliers for this study are identified by an asterisk
in the tables of raw data shown in Appendix E.
Youden's Laboratory Ranking Procedure
Using the data for each water type, Youden's laboratory ranking
test [3, 5] was performed at the 5% level of significance. The
Youden laboratory ranking procedure requires a complete set of
data from each laboratory within each water type. Missing data
from laboratory "i" for water type "j" were replaced by the
following procedure. Letting X.... denote the reported measurement
1JK
from laboratory "i1
it is assumed that
from laboratory "i" for water type "j" and concentration level C. ,
Xijk ' Pj ' S ' Li '
where p. and y. are fixed parameters which determine the effect of
water type "j;" L. is the systematic error due to laboratory "i," and
e... is the random intralaboratory error.
22
-------
Taking natural logarithms, it follows that
fin XijR = *n p . * Yj £n CR + in L. +
-------
TABLE 8. YOUDEN LABOPATORY RANKING PROCEDURE
FOR BENZENE DATA IN WATER 3
Labor-
atory
number
1
2
3
4
5
6
t
/
8
9
10
11
12
13
14
15
16
17
18
19
20
Ampul 1
B
4
15
9
13
7
10
18
3
12
16
20
19
6
1
17
2
5
14
11
Ampul 2
16
5
18
11
15
13.5
10
19
4
13.5
7
9
2
6
1
20
3
12
17
8
Ranking
Ampul 3
17
11
20
9
16
15
12
8
5
7
10
1
3
13
2
19
4
6
18
14
values
Ampul 4
18
12
20
8
16
13
11
15
7
4
17
1
2
10
3
19
6
5
9
14
Ampul 5
18
6
3
8
11
16
9
5
20
12.5
14.5
1
4
7
2
19
17
12.5
10
14.5
Ampul 6
18
5
3
7
9
16
11
10
20
6
15
1
4
8
7
12
19
13
14
17
Cumulative
score
95
43
79
52
80
70.5
63
75
59
55
79.5
33a
34
5°w
h
11°
b
106
51
53.5
82
78.5
Laboratory 12 rejected since ampul 1 value was a "nondetected" skewing rating
to exceed lower (22) limit.
Laboratories rejected versus upper and lower criteria of 104 and 22.
test based on calculation of the average value, X, for each ampul
and the standard deviation of the remaining values.
The criterion for rejection of individual outliers is based on
calculation of Thompson's T-value [3,6].
In these calculations the mean recovery, X, is given by
n
i£
(3)
24
-------
and! Lhc» standard deviation, s, is given by
(x.. -x)2 (4)
where X. = individual analyses
n = number of retained analyses
values in the ampul set
The Thompson's T-test is defined as
X -x
T. ~ — (5)
is * '
where X is the retained X. value farthest away from the mean (X)
of the set of retained data. The data point maybe rejected if the
value of T calculated exceeds critical values for T (two-sided
test 25% significance level) as presented in Table 9. If the
extreme value is rejected as an outlier, the test is repeated for
th2 next most extreme value among the remaining data until the
value being tested passes the test. Table 10 summarizes calcula-
tions to examine suspect data points for benzene in water 3 by
the T-test for outliers.
As shown in Table 10, e:.x additional data points are identified as
outliers by the Thompson T-test for the illustrative example of
the analyte benzene in water 3. In summary, of the original 120
data points for benzene in water 3 (20 laboratories s: 6 ampuls),
all data points for laboratories 12, 15, and 16 were rejected on
the basis of Youden's laboratory ranking procedure (total of 18
points), and seven additional data points were found to be out-
liers based on Thompson's T-test (for a total of the 25 data
points). These same outlier tests were applied for all seven
analytes in the six water matrices. All outlier data points are
marked with an asterisk in Appendix E.
25
-------
TABLE 9. CRITICAL VALUES FOR THOMPSON'S T (FWO-SIDED TEST) WHEN
STANDARD DEVIATION IS CALCULATED FROM '•'HE SAME PAMPLSS
Number of
observations,
n
5%
significance
level
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
.15
.48
.71
.89
.02
.13
.21
.29
.3t-
.41
.46
.51
.ZS
.58
.62
.65
.68
.71
TABLE 10. RESULTS OF TEST FOR INDIVIDUAL
OUTLIERS (BENZENE IN WATER 3)
Extreme
Ampul Laboratory Valre Mean
Calculated Critical
deviation T T Decision
2
1
2
3
4
3
4
13
17
17
3
3
13
13
14
7
8
19
20
127
124
.70
.19
.27
.10
.70
.00
.00
4.05
2.79
3.38"
43. 9S
48. 58
45.8
50.6
3
1
1
9
9
24
23
.12
.38
.54
.05
.42
.6
.3
3
3
3
2
2
3
3
.41
.22
.18
.74
.95
.30
.15
2
2
?
2
2
2
2
.62
.62
.58
.58
.58
.62
.62
Reject
Reject
Reject
Reject
Reject
Reject
Reject
Rejected afttr higher value from same ampul was rejected.
26
-------
STATISTICAL SUMMARIES
After the outlier rejection tests were performed, the following
summary statistics were calculated employing the remaining data
I
for each ampul (single analyte, single concentration, single water I
matrix): L
• Number of retained data points, n
• Mean recovery of retained data, X
• Accuracy as a percent of relative error, % RE
• Overall absolute standard deviation, S
• Percent relative overall standard deviation, % RSD
• Absolute single-analyst standard deviation, SR
• Percent relative single-analyst standard deviation,
% RSD-SA
All of these statistics, except the single-analyst, absolute and
relative standard deviations, were calculated using the retained
data for each ampul. The basic statistical formulas used for
these calculations are given below, where Xj , X2 , . . . , X denote
the values for the n retained data points xbr a given ampul.
Mean Recovery (X):
X = X. (3)
Accuracy as a % Relative Error:
27
-------
Overall Standard Deviation:
s =W:TT Z- (x. - x)2 (4)
and
Percent Relative Overall Standard Deviation:
% RSD = | x 100 (7)
The overall standard deviation, S, indicates the precision
associated with measurements generated by a group of laboratories.
This represents the broad variation in the data collected in a
collaborative study. A measure of how well an individual analyst
can expect to perform in his own laboratory is another important
measure of precision. This single-analyst precision, denoted by
SR, is measured by
m
SR =V~,r , v Z(D.-D)2 (8)
where m = number of retained Youden-paired observations
D. = difference between observations in the i pair
D = average of D. values
The Youden-pair design employed in this study permits the calcula-
tion 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.
28
-------
The percent relative standard deviation for the single-analyst
precision is calculated by
% RSD-SA = — x 100 " (9)
X*
where X* is the average of the two mean recoveries corresponding
to the two ampuls defining the particular Youden pair. These sum-
mary statistics are presented in Tables 11 through 17 for each of
the seven purgeable aromatic compounds in the six water matrices.
It is often the case that a systematic relationship exists between
the mean recovery (X) and the true concentration level (C) of the
analyte in the sample. In addition, there are often systematic
relationships between the precision statistics (S and SR) and the
mean recovery (X). Usually these systematic relationships can be
adequately approximated by a linear relationship (i.e., by a
straight line). Once these straight lines are established, they
can be used to conveniently summarize the behavior of the method
within a water type, and they can aid in comparing the behavior
of the method across water types. In addition they can be used
to obtain estimates of the accuracy and precision at any concen-
tration level within the applicable range studied. They can
also be used to predict the behavior of the method when used
under similar conditions. These important relationships are
discussed below.
Statements of Method Accuracy
The accuracy of the method is characterized by the relationship of
the mean recovery (X) to the true concentration (C) of the analyte
in the water sample. In order to obtain a mathematical expression
29
-------
TABLE 11. STATISTICAL SUMMARY FOR BENZENE ANALYSES BY WATER TYPE
UATfK 1
WATEK 2
WATEK 3
WATEK 4
WATEK b
WATEK b
W
O
LOW YOUUEN PA IX
NUMBER OF DATA POltTS
TKUE CONC (Cl UU/l
HI AN RECOVERY (X)
ACCUKACY(lHti. EkROK)
OVERALL STU ULV (S)
OVEKALL KEL SID UEV. i
SINGLE STU UEV, (SK)
ANALYST KEL UEV. I
MEUILM YOUUEN PAIR
NUMBER OF DATA POINTS
TKUE CONC (C) UU/L
MtAN RECOVEKY (X)
ACCURACY (tREL ERROR)
OVEKALL STU OEV (S)
OVEKALL KEL STO UEV. I
SINGLE STU UEV. (SK)
ANALYST KEL UEV. X
HIGH YOUUEN HAIR
NUMHEK OF DATA POINTS
TKUE CONC (C) Uli/L
HE AN KECOVEKY (X)
ACCURACY(IKEL EKKOK)
OVEKALL STU ULV (S)
OVEKALL KEL SID UEV. I
SINGLE STU UEV. (SK)
ANALYST KEL UEV. 1
1
16
2,20
2.43
10. b4
0.81
33.46
0
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3
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4b.UU
44.01
-4.33
b.6l
ib.02
3
7
b
It)
4bU.OO
422.83
-6.04
10b.23
24.89
bb
12
2
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3.00
3.63
20.90
1.H9
W.Ob
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4
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48.23
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8.18
16.96
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487. bl
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111.42
22. 8b
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2.20
3.11
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2.08
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46.00
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16. H2
b
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4bU.OO
433.44
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120.32
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3.48
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l.bl
43.43
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8.16
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4i-0.b9
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107.82
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3.06
1.96
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27. b7
0.40
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487. Ob
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1
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2.33
b./l
1.37
b8.89
1
43
3
16
46.00
42.97
-6.b9
b.83
13.69
4
11
b
18
4bO.UO
400.11
-11.09
117. b3
29.40
44
10
2
14
3.00
2.87
-4.21
1.97
68.42
.14
.82
4
18
b4.00
42.90
-20. b6
11. bb
26.93
.73
.02
6
18
bbO.OO
4HJ.67
-12.06
1MI.60
31.14
.21
.00
1
lb
2.20
2.b2
14.70
1.09
43. Ob
0.
24.
3
17
46.00
44.04
-4.26
11.99
27.22
b.
11.
b
17
4bO.OO
43b.41
-3.24
99. Bb
22.93
41.
8.
2
14
3.00
3.37
12.48
l.bl
47.79
71
09
4
17
b4.CO
48.69
-9.U3
12. ib
?b.78
22
26
b
17
bbO.OO
b09./l
-7.33
119.82
23. bl
83
8b
WATEK LEGEND
1 - OISTILLEU WATEK
2 - TAP WATEK
3 - SURFACE WATEK
4 - WASTE WATER 1
b - WASTE WATER 2
6 - WASTE WATER 3
-------
TABLE 12. STATISTICAL SUMMARY FOR CHLOROBENZENE ANALYSES BY WATER TYPE
WATEK 1
WAfEK 2
HATEK 3
UAH.K 4
UATEK
WAUK 6
U
LOU YOUUEN PA IK
NUHBEK UK UATA POINTS
TKUt CUNC (C) UG/L
ML AM KECUVEKY (X)
ACCUKACY(JREL EKKUK)
UVEKALL SFU 1>EV (b)
UVEKALL 1 Jl STO UEV, I
SINGLE STU UEV. (SH)
ANALYST HEL UEV, %
MEU1UM YOUUEN PAIR
NUMBEK OF UATA POINTS
TKUE CUNC (C) UG/L
MEAN KECOVEKY (X)
ACCUKACY(48£L EKKOK)
UVEKALL STU UEV (S)
UVEKALL KEL STU UEV. I
SINGLE STU UEV. (SK)
ANALYST KEL UEV. *
HIGH YOUUEN PAIK
NUMBEK OF UATA PUINlS
TKUE COHC (C) UG/L
HtAN KECOVEKY (X)
ACUJKACY(iKEI EKKUK)
OVEKALL STU UEV (S)
UVEKALL KEL STO UEV. t
SINGLE STU OEV, (SK)
ANALYST KEL OEV. t
WATtK LEGENU
1
18
2.2U
2.2U
U.1U
0.4JJ
21.81
0
18
3
17
46.00
44. bl
-3.24
7.47
16.77
4
8
5
17
4bO.OO
'436.29
-3.0!>
b7.27
13.13
45
y
2
17
3.UU
2.72
-9.31
0.54
19.96
,4b
.34
4
19
b4.00
52. b4
-2.70
11.04
21.02
.23
.71
6
19
bbl.OU
bOb.84
-8.20
88. 60
17. b2
.78
.12
1
i;
2.20
2.3U
4.63
U.8b
3h.72
3
16
46. UU
47.24
2.69
9.13
19.33
b
16
4bO.OO
411.44
-H.b7
6b.6U
lb.96
2
16
3.00
2.74
-8.b8
0.64
23.28
0.37
14.69
4
16
b4.00
b3.02
-1.H2
7.67
14.47
6.66
13.28
6
17
bbl.OO
487. b3
-11. b2
87.49
17. 9b
31.92
7.10
I
17
2.20
1.94
-11.84
O.bO
2b.71
0.
14.
3
18
46. 00
4b.43
-1.24
9.78
21.b:i
3.
7.
b
18
4bO.OO
394.89
-12. 2b
71.72
18.16
36.
H.
2
17
3.UO
2.48
-17.37
0.80
32. 2b
32
44
4
18
b4.0U
bO.J7
-6.73
1U.73
21. 3U
72
n
6
19
bbl.UO
48b.0b
-11.97
8U.91
16.68
b2
30
1
12
2.20
2.68
21.63
2.76
103.00
'\.
70.
3
18
46.00
42.72
-7.14
11.92
27.91
b.
13.
b
16
4bU.OO
413.38
-8.14
6b.l3
lb.76
46.
10.
?
9
J.OO
6.97
132.30
4.64
tji.bi
41
n
4
18
b4.00
4S.54
-lb.66
11. bb
2b.b9
7b
OA
6
17
bbl.OO
bUO./l
-9.13
H7.76
17. b3
62
m
I
b
2.20
23.40
963.64
21.62
92.38
17
83
3
18
46.00
b4.90
19.48
36.38
66.18
16
32
b
17
4'jO.OO
400.29
-U.Ob
108.48
27.10
68
Ib
2
6
3.00
17. bO
483.33
14.92
8S.28
.04
.34
4
18
b4.00
4b.bl
-lb.73
2b.97
57.08
.32
.48
6
18
bbl.OO
470.83
-14. bb
122.01
2b.9l
.01
.01
1
17
2.20
2.3b
6.8/
l.JH
b8.Hl
3
18
46.00
44.!>2
-3.01
9.32
20. 8H
b
17
4bO.OI)
410. 4/
-H.7H
bl.4/
12. b4
2
Ib
3.UO
2.b2
-lb.84
l.Ub
42.08
U.6H
28.116
4
18
b4.0U
bO.07
-1.il
10.04
20. Ib
b.69
12.03
6
1H
bbl.UO
492.17
-10.68
/2.20
14.67
44.67
9.90
1 - UlsriLLEU UATEK
2 - TAP UATEK
J - SUKtACE gATEK
4 - WASH WAItK 1
b - UASIE WAII.K 2
6 - HASH UAUK 3
-------
TABLE 13. STATISTICAL SUMMARY FOR 1,2-DICHLOROBENZENE ANALYSES BY WATER TYPE
WATEK 1
HAfEH 2
WAFER 3
WAltR 4
WAItK b
WATE* b
W
ro
LOU YOUOEN PA!K
NUNBEK OF DATA POINTS
TKUE CUtt (C) Uli/L
WAN RECOVERY (X)
ACCURACY (WEL ERROR)
OVERALL STO UEV (S)
OVERALL REL STU UEV. I
SINGLE STU UEV. (SK)
ANALYST KEL UEV, I
MEDIUM YOUOEN PAIR
NUMBEK ;iF UATA POINTS
TKUE CONC (C) UU/L
MEAN KECUVEKY (X)
ACCURACY (WEL ERROR)
OVEMALL STU UEV (S)
OVEKALL KEL STO UEV. *
SINGLE STD DEV. (SK)
ANALYST KEL UEV. I
HIGH YOUUEN PAIR
NUMBER UF DATA POINTS
TKUE CONC (C) UU/L
ML AN KECOVEKV (X)
ACCURACY (1KEL EKKOK)
OVEKALL SlU UEV (S)
UVEHALL KEL STU UEV. t
SINGLE STU UEV. (SK)
ANALYST KEL UEV. I
HATER LEGEND
1 - OISTILLEU UAIEK
2 - TAP WATtV
3 . SUKfACE WAIEK
4 - HAb'L WAIIK 1
b - yASlt UAII K t
C - WASH WAIEK J
1
16
2.20
2.79
26.68
1.42
b0.8b
0
Ib
3
la
46. OU
48.13
4.64
11.46
23. Hi
9
IS
b
18
449.00
44.'. 17
-0.41
dU.27
17. 95
74
Ib
2
14
3.00
2.92
-2. HI
0.84
28. 98
.4S
.6b
4
18
&4.00
49. 6b
-U.Ub
10.64
?1.43
.10
.62
6
18
610.00
bU0.17
-1S.64
124.63
2'>./2
.18
.66
1
16
2.20
2.b9
I/. 93
U.H9
34.28
0.
2b.
3
17
46.00
4b.41
• 1.28
6.06
13.3b
4.
8.
b
18
449. 00
427. 06
-4.89
91.39
21.40
•bb.
12.
2
16
3.00
2.88
-3.96
0.63
21.88
70
b7
4
18
b4.00
51. 3b
-4.91
7.72
lb.03
24
77
6
18
6UU.OO
488.11
-lH.6b
111.21
22.78
06
03
1
12
2.20
2.09
-b.04
0.33
16.03
0.
11.
3
17
46.00
4b.SU
-0.22
7.37
16. Ob
4.
8.
b
17
449.00
394.24
-12.20
89.13
22.61
47.
10.
2
14
3.00
2.99
-0.24
1.02
33.99
29
22
4
16
b4.00
49.18
-8.92
6.06
12.31
10
63
6
16
600. OU
466.38
-22.27
88. 3b
18.94
Ib
96
1
13
2.20
2.07
-b.94
0.68
32.87
1
43
3
17
46.00
43.81
-4.76
7.74
17.67
b
11
'3
18
449.00
404. 2H
-8...
li.-4.17
JO.J4
b4
12
2
16
3.00
3.b8
19.40
1.9b
b4.42
.23
.47
4
17
b4.UO
48.46
-10.26
8.43
17.40
.12
.09
6
18
fr'jO.OU
477. bO
-2U.42
132.22
2/.69
.3b
.26
1
14
2.20
2.78
26. b6
1.88
67. b7
1.
38.
3
17
46.00
48.44
S.29
7.70
lb.89
b.
11.
b
17
449.00
444.94
-0.90
9'l.b8
21.26
bl.
10.
2
13
3.00
3.bb
18.28
1.28
3t.9S
23
72
4
17
b4.00
49.92
-7.b6
10.18
20.40
82
83
6
17
bUO.IJO
b.'H.71
-11.88
9^.06
;s.?4
16
bl
1
13
2.20
1.63
-26.12
0.71
43.40
0
2
Ib
3.00
2.11
-2".o7
I.Ob
49.66
.41
21.76
3
16
46.00
42.46
-7.70
b.12
12. Ob
7
17
b
16
449.00
'.20.09
-6.31
80. bO
19.14
b3
11
4
16
b4.UO
48.22
-10.7)
11.62
24. 09
.96
.bb
6
16
600.00
467.13
-22. Ib
80. Ml)
17.30
.13
.97
-------
TABLE 14. STATISTICAL SUMMAKY FOR 1,3-DICHLOROBENZENE ANALYSES BY WATER TYPE
WAUK
WAIIk I
UA1LK 3
WAUK 4
UAtLX b
UAIEM b
U)
LOW YOUOEN PAIK
NUMBER OF DATA POINTS
TKUL CONC (C) Uli/L
ML AN KECUVEKY (X)
ACCURACY (WtL EKKOK)
OVtKALL STO UtV (S)
OVtKALL MEL STU UtV. 1
SINGLE STU UtV. (SH)
ANALYST Kit UtV. 1
MEDIUM YOUOEN PAlK
NUMUEK Of UATA POINTS
TKUE CONC (C) UG/L
HI AN HECUVEKY (X)
ACCUKACY(1KEL EKKOM)
OVtKALL STO UtV (S>
UVEKAU KtL STU UtV. 1
SINGLE STO OtV. (SM)
ANALYST KfL UtV. 1
HIGH YUUUEN PA IK
NOMaEK OF UATA POINTS
TKOE CONC (C) OG/L
ML AM KtlUVtKY (X)
ACCOM AC Y( IKE L EKKOK)
OVLKALL SIU OtV (S)
OVtKALL MEL StO UtV. I
SINGLE STO OtV. (SK)
ANALYST KEL UtV. I
UATEK LEUENO
1 - UISTILLEU WATLH
t . TAP WAftK
3 - SUHFAU WAttK
4 - WASH WAII.K I
b • WA^It WAll K t
b - WAj(L WAlLK }
1
lb
?.20
Z.07
-b.7J
U.4b
i?8
11.13
23. 3b
9
18
b
IB
4bU.OO
443.89
-1.3b
bH.bH
lb.4b
b4
il
i!
lb
3.00
2. 78
-7.2.J
O.b7
23.93
.26
.86
4
If
b«.oo
bl./4
-4.1U
y.68
18.71
.13
.37
b
18
bSO.OO
473. Ob
-13.99
87. b9
18. b2
.70
.93
1
lb
2. A)
2.36
7.12
O.H4
3b.49
0.
20.
3
17
4b.OO
4b.9H
-O.Ob
b.34
13.79
4.
8.
b
16
4b(I.UO
399. bO
-11.22
bl.bb
lb.41
36.
8.
2
lb
3.00
2.82
-6.13
O.b3
18.94
b4
9b
4
17
b4.00
b4.b2
0.97
7.36
13. bl
30
bb
b
17
bbO.OU
4/8.94
-12.92
94.42
19.71
47
30
1
Irt
2.20
- 2.60
18.11
1.47
bb.73
0.
10.
3
1H
46. UU
46. lb
0.33
7.12
lb.43
4.
9.
b
18
4bO.UO
412.44
-8.3b
99. lib
24.21
49.
10.
2
17
3.00
2.89
-3.b7
1.07
36.91
30
94
4
18
b4.00
b2.44
-2.88
B.71
Ib.bl
8b
83
b
18
bbU.OO
4H7.ll
-11.43
97.72
20.06
1)1
9.1
I
/
2.20
3.40
S4.bb
1.8U
b2.90
1
20
3
17
46.00
42. 8b
-b.8b
Ib.b!
38. b2
9
19
S
1U
4bO.OO
413. 8b
-8.03
12b.2b
30. bl
b2
11
2
9
3.00
10.39
246.44
7.05
67.80
.44
.91
4
18
b4.00
b3.88
-0.23
1'2.16
41.12
.31
.24
6
17
bbD.OO
b01.82
-8.76
lib. 09
22.93
.98
.b7
1
13
2.20
2.8b
29. bb
1.42
49.75
0
21
3
18
46. UO
43.86
-4.6b
6.31
14.40
1
7
b
18
4hU 00
4J3.7H
-3.bO
9rt.84
22.79
60
12
2
11
3.00
2.b2
-12.82
1.20
4b.74
.79
.82
4
17
b4.00
49.14
-9.01
9.49
19.31
.b3
.04
b
18
bbO.OO
MV.bO
-H.b4
lOb.lb
20.93
.60
.94
1
lb
2.20
2.18
-1.00
0.79
36. bO
0
22
3
17
46.00
43.94
-4.49
b.4b
12.39
6
12
b
17
4bU.OO
421.82
-b.2b
82. bl
19. b8
bO
11
2
lb
3.00
3.02
0.71
0.89
29.43
.b9
.79
4
17
b4.00
b2.81
-2.20
9.^2
1U.21
.23
.88
b
I/
b^O.OU
482.06
-12. 3b
77.83
16. lb
.93
.27
-------
TABLE 15. STATISTICAL SUMMARY FOR 1,4-DICHLOROBENZENE ANALYSES BY WATER TYPE
UAItK 1
WAUK 2
WMLK 3
WAItK 4
WAItK b
MARK 6
LUM YOUUtN PA IK
NUMtEK Of OAtA POINIS
TMUE CUNC (C) Uli/L
HtAN HLCUVEMY (X)
ACCURACY (WtL EKXO«)
OVtKALL STU Uf« (SJ
OVERALL KU STO UtV. 1
SINULE STl! UtV, (SK)
ANALYST MEL UEV. 1
HEOIUH VOUUEN HA IK
NUHBEH Of DATA POINTS
TKUt CUNL (C) UG/L
WAN KECUVtKY .' M
ACCURACY) MEL EKKOK)
UVEKALL STU OtV (S)
OVEKALL MEL STU UEV, 1
SINGLE STU OtV. (SK)
ANALYST MEL DEV. 1
HIUH YOUULN PAIM
NUMtftK OK UAIA PU1NTS
TKUt CUNC (C) Uli/L
KIAN HECUVIKY (I)
ACCtWACY(lKtL EKKUK)
OVEMALL SIU UtV (S)
UVEMALL MtL SIU UEV, 1
SlNtiLE STU UtV. (SK)
ANALYST MEL utv. i
UA;E!) LEU.NU
i
16
z.;.-u
l'.U4
-;.4i
u.su
44.21
J
27
3
14
46. 00
46.46
Z.U4
I/. 63
26. B4
H
1M
b
14
4bU.Ut)
421. bU
-b.29
67. bU
16. UJ
to
H
2
16
3.UU
2.b7
•14.48
0.82
31.83
.63
.28
4
14
b4.00
bU.3U
-6.85
4.07
1«.02
.76
.00
6
14
bbO.UO
474.63
-13. 7U
112.18
23.63
.22
.44
1
Ib
2.20
2.32
b.bB
U.H7
37.46
0
23
3
16
46.00
44.16
-4.01
4.74
10.73
4
4
b
17
4bO.OO
34b.82
-12.04
70.12
17.71
J4
4
2
16
3.00
2.m
-b.40
O.bO
21.12
.62
.4b
4
17
b4.00
b2.b4
-2.60
6.41
13.13
.63
.b/
b
17
bbU.OO
464. H8
-lb.48
41.16
14.01
. JH
.Ib
1
Irt
2..'0
2.i2
U.Bb
1.2U
b7.82
3
Irt
4b.OO
44.77
-2.68
6.18
13.81
b
18
4bU.OO
3/7.17
-16.14
Ml.bl
21.51
2
IK
3.00
2.H4
-b.4H
1.24
43. b7
U.24
4.36
4
18
!>4.00
4:t.b4
-4.84
b.4b
14.^8
b.b4
11. 4b
b
Irt
bbO.OO
446.33
-18. 8b
44. 4b
21.16
4b.Hb
11.14
1
10
2.20
2.42
4.«b
i.Ol
41.44
3
17
46.00
42. bl
-7.b8
7.22
16.49
b
18
4bO.OO
344.83
-12.26
8b.81
21.73
2
11
3.00
3.3b
11.07
1.22
3b.34
1.07
37.21
4
It)
b4.CO
48.11
-10.42
8.67
17.81
2.78
6.14
6
17
bbU.UO
478.00
-13.04
88.21
18. 4b
4b.0b
lU.bb
I
11
2.20
2.01
-B.bl
0.70
34.64
1
38
3
17
46.00
4b.8b
-0.33
b.3l
11. b7
b
11
b
18
4bO.UO
417.00
-7.33
H7.b7
21.00
SO
11
2
Ib
3.00
3.4b
31.62
1.43
48.41
.Ib
,b2
4
18
b4.00
bl.Ol
-b.b3
4.28
18.19
.37
.09
6
18
bbO.OO
441.89
-!0.b7
87.78
17.84
.12
.03
1
14
2.20
2.06
-6.b3
0.46
22.39
0
22
3
17
46.00
42.10
-8.48
4.48
10.63
4
9
b
17
4bO.OO
403. 3b
-10.37
'•>.9b
18.83
42
9
2
16
3.00
2.43
-2.42
1.13
38. b7
.b7
.72
4
17
b4.00
bl.42
-4.77
7.12
13. 8b
.47
.bb
6
17
bbO.OO
47b.88
-U.24
bb.87
14.02
.b4
.b7
1 - UlSllLLLU UAFtK
2 - TAP UAItM
3 - SUHfACt UAU w
4 - WAML MAI; K I
b - UASII WAIIM t
b - UAblL WAIIX J
-------
TABLE 16. STATISTICAL SUMMARY FOR ETHYLBENZENE ANALYSES BY WATER TYPE
MARK 1
UAIIK
MAI IK J
WATCH 4
HATLK b
WAItK 6
OJ
in
LOW YOUUtN PA IK
NlMBEK JF UAIA POINTS
Ixut CUNC (C) OG/L
NIAH KtCOVEKY (1)
ACCOHACY(U
-------
TABLE 17. STATISTICAL SUMMARY FOR TOLUENE ANALYSES BY WATER TYPE
WAFEK 1
UAHK 2
UATtK 3
WATLK 4
WAFtH b
WATtM b
LOU YOUDEK PA IX
NUMBEK 'If DATA POINTS
TKUE CONC (C) UU/L
Hi AN KECUVEKY (X)
fiCCUKACY(lKSL EKKOK)
UVLKALL STU 01 V (S)
UVEKALL KEL STD UtV. 1
SINGLE STU UEV. (SH)
ANALYST MEL UEV. i
HEUIUH YUUUEN PAIK
N10WEK OF DATA HUlNTS
TKUt CUNC (C) UU/L
MEAN RECUVf.KY (X)
ACCUKACY(W£L tKROR)
UVEKALL STU UEV (S)
UVEKALL KEL STU UEV, i
SINGLE STU UEV, (SK)
ANALYST KEL UlV, 1
HIGH YOUUEN HAlK
NUHtfEK OF UATA POINTS
TKUE CONC (C) Ub/L
ML AN RECUVEKV (X)
A'JCUKACYftHEL tKHOK)
OVEKALL STL) UtV (b)
UVEKALL MtL SIU ULV. 1
SINGLE STU UEV. (SH)
ANALYST KEL UEV, S
UATEK LEliENU
1
19
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2.81
33.81
i.bb
!>8.84
U.
2b.
3
16
46. OU
44.31
-3.67
6.64
Ib.UU
4.
8.
b
1?
SbU.OO
444. by
-l.i'O
U1.63
18.36
b2.
10.
2
16
3.0U
3.08
2.62
U.70
22.87
7b
'.7
4
17
64.00
bU.72
-6.08
9. 62
18.46
Ib
73
6
18
bbO.UO
bib. 00
-6.36
114.73
22.28
11
86
1
16
2.10
2.14
2.14
0.66
30.94
3
16
46.00
44.82
-2.bb
8.73
19.47
b
17
4bU.UO
417.29
-7.27
102.411
i4.b4
2
17
3.110
2.%
-1.47
0.67
22. 7b
u.4;«
16.97
4
P
b4.UO
b3.24
-1.41
10.19
19.14
6.16
12.bt>
6
17
bbO.OO
4H3.1'9
-12.13
!'.!/. 7«
22. 3U
3b.b7
8.12
1
16
2.10
1.91
-9.20
U.bO
26.27
0.
Ib.
3
18
46. OU
43.76
-4.87
!U.i7
23. 2b
3.
;.
b
Irt
4MKUU
4 18. lib
-1.1(1
94.38
23.77
42.
9.
2
18
3.0U
2.91
-2.17
1.76
6U.02
38
91)
4
lei
b4.UO
49.49
-8.34
11.44
23.12
61
7b
6
18
bbO.UU
49!>./8
-9.86
106. IV
21.42
12
22
I
14
2.10
2.86
36.12
1.12
39.29
1
44
3
!9
46.00
41.12
-10.62
7.8*
19.13
b
13
b
19
4bU.UO
4U7.M
-'J.42
1U9.98
26.98
bl
11
2
17
3.00
3.48
lb.94
1.90
b4.71
.40
.33
4
19
b4.UO
46.44
-14. Ul
11. H2
2b.4b
.79
.23
6
19
bbO.UU
47U.H9
-14.38
127.12
27. UO
.12
.64
1
b
2.10
12.47
494. Ub
11.28
90.39
b
b4
3
17
46.00
b2.53
14.19
22.87
43.54
Ib
31
b
17
4bO.UO
34H..8?
-11.37
106.88
26. 80
60
13
2
9
3.00
b.96
98. b9
b.40
90.61
.03
.b3
4
14
b4.00
42.72
-2U.89
7.01
ib.40
.16
.82
6
17
bbtl.OO
499.6b
-9. ib
149.77
29.. 18
.17
.39
|
Ib
2.10
2.99
42.60
1.77
b9.09
1
46
3
18
46.00
42.66
-7.26
11.13
26. U9
6
14
b
H
4jU.OU
4
-------
for this relationship, a regression line of the form
X = a -f b • C (10)
was fitted to the data by regression techniques.
It is often the case that the true concentration values vary
over a wide range. In such cases;, the mean recovery statistics
associated wit>. the laiger concentration values tend to dominate
the fitted regression line producing relatively larger errors
in the estimates of mean recovery at the lower concentration
values. In order to eliminate this problem, a weighted least
squares technique was used to fit the mean recovery data to the
true concentration values. The weighted least squares technique
was performed by dividing both sides of Equation (10) by C
resulting in Equation (11).
§ a ' § * b (11)
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 concentration
levels.
Statements of Method Precision
The precision of the method is characterized by the relationships
between precision statistics (S and SR) and mean recovery (X). In
order to obtain a mathematical expression for these relationships,
regression lines of the form
37
-------
S = d + e • X (12)
and
SR = f + g • X* (13)
were fitted to the data.
As discussed previously with respect to accuracy, the values of X
and X* often vary over a wide range. In such cases the standard
deviation statistics associated with the larger mean recovery
values will dominate the regression lines. This will produce
relatively larger errors in the estimates of S and SR at the
lower mean recovery values. Therefore, a weighted least squares
technique was also used to establish the values of the parameters
d, e, f, and g in Equations (12) and (13). The weighted least
squares technique was performed by dividing both sides of
Equation (12) by X resulting in Equation (14)
S = d • J + e (14)
and by dividing both sides of Equation (13) by X* resulting in
Equation (15)
If the intercepts, e and g, are negligible, then the slopes, d
and f, are good approximations to the overall and single-analyst
percent relative standard deviations, respectively. These, in
turn, are measures of the method precision.
38
-------
COMPARISON OF ACCURACY AND PRECISION ACROSS WATER TYPES
It is possible that the accuracy and precision of Method 602 depend
on the water type analyzed. The summary statistics X, S, and SR
are calculated separately for each concentration level within each
water type. They can be compared across water types in order to
obtain information about the effects of water type on accuracy and
precision. However, the use of these summary statistics in this
manner has several disadvantages. First, it is cumbersome because
there are 36 mean recovery statistics (X) (six ampuls x six
waters), 36 overall precision statistics (S), and 18 single-
analyst precision statistics (SR) 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
SR, comparisons based on these statistics can lead to inconsistent
conclusions about the effect of water type. For example, dis-
tilled water may appear to produce a significantly lower value
than drinking water for the precision statistic S at a high con-
centration, but a significantly higher value for S at a low
concentration.
An altrrnat.ive approach [21, has been developed to test for the
effects of water type. This alternative 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 level. If significant differences are estab-
lished by this alternative technique, then the summary statistics
can be used xor further local analysis.
The test for the effect of water type is calculated using the
following statistical model. If X... denotes the measurement
1 j K
reported by laboratory "i." for water type "j," and ampul "k,"
then
39
-------
C. -1 • L. • r, . .. ( 1 )
k i IJK
where i = 1,2,..., n
j = 1.2
k = 1,2,..., 6
Model components B. and y are fixed parameters that determine
the effect of Writer type j on the behavior of the observed
measurements (X... ). The parameter C. is the true concentration
2. J f\ K.
level associated with ampul "k." The model component L. is a
random factor which accounts for the systematic error associated
with laboratory "i." The model component, c. .. is the random factcr
1 J K
that accounts for the intralaboratory 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 (X. .. ) and the true concentration
1J K
level (C.) through the use of the exponent Y- on C. • This makes
K. j "
the model more flexible in comparison to straight-line models.
Second, as will be noted below, an inherent increasing relation-
ship exists between the variability in the data and the concen-
tration level C. in this model. This property is important
because it is typical 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.-v). The expected value for the
1J K
data modeled by Equation 1 is
E = Pj ' Ck ' E
-------
Precision is related to the variability in the measurements (X. .,
The variance of the data modeled b^ Equation 1 is
2
Var(Xijk) =|p, • C,, J| Var(L, • £.,„). (17)
which is an increasing function of C. . (See Reference 2 for a
complete discussion of this model.)
The accuracy and precision of Method 602 depend upon water type
through Equations 16 and 17 and the parameters p. and Y'« If P-
and Y vary with j vi.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 1 represents the basic
model. However, taking natural logarithms of both sides of Equa-
tion 1, the following straight line regression model is obtained.
Pj + Yj *n Cu + in L. + £n e,^ (2)
The parameter £n p . is the intercept, and y is the slope of the
regression line associated with water type "j." It is assumed that
in L. is normally distributed with mean O and variance or2, that
i LI
£n e... is normally distributed with mean O and variance o.2, and
X J Ix tf
that the S.n L. and in c . .. terms are independent.
Based on Equation 2, the comparison of water types reduces to the
comparison of straight lines. Distilled water is viewed as a
control, and each of the remaining lines is compared directly to
the line for distilled water.
41
. i .a»
-------
Using the data on the log-log scale and regression techniques, the
parameter £n B. (and hence B ) and y. can be estimated. These
estimates are then used to test the null hypothesis that there is
no effect due to water type. The formal null and alternative
hypothesis, H_ and H., respectively are given by:
HQ: £n B. - £n ^ = 0 and y. - 1± = 0 for j = 2 (18)
H : £n B. - £11 B i- 0 and/or y. - y. / 0 for some j = 2 (19)
A J J. ] 1
The null hypothesis (HQ) is tested against the alternative hypoth-
esis (H.) using an F-statistic. The probability of obtaining the
value of an F-statistic as large as the value which was actually
observed, Prob(F > F OBS), is calculated under the assumption that
HO is true. HQ is rejected in favor of H if Prob(F > F OBS) is
less than 0.05.
If HQ is not rejected, then there is no evidence in the data that
the B. vary with "j" or that the y. vary with "j." Therefore,
there 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 (£n B. - £n B) and (Y. - Y,) is
statistically different from zero. However this does not guarantee
there will be a statistically significant direct effect attribut-
able 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 water type is judged to be statis-
tically significant only if one of the differences, (£n B. - £n B,)
and/or (y- - y-^), is statistically different 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 95% confidence. If zero is contained within the
confidence interval, then there is no evidence that the correspond-
ing difference is significantly different from zero.
42
-------
If at least one of the confidence intervals for the differences
(£n p. - JLn p.) or (y . - YI) fails to include zero, then the stat-
istical significance of the effect due to water type has been
established. However, establishment of a statistically signifi-
cant effect due to water type does not necessarily mean that the
effect is of practical importance. Practical importance is
related to the size and interpretation of the differences.
The interpretation of the differences involves comparing the mean
recovery and standard deviation for each water type to the mean
recovery and standard deviation obtained for distilled water.
These comparisons are made on a relative basis. The mean recovery
for water type "j," given by Equation 16, is compared to that for
distilled water (j = 1) on a relative basis by
E _ Pj Ck E
(The ratio of the standard deviations would be equivalent to
Equation 20; therefore, the interpretation of the effect on
precision is the same as that for the effect on mean recovery.)
The ratio in Equation 20 is a measure of the relative difference
in mean recovery between water type "j" and distilled water. It is
composed of two parts (a) p ./P-i / which is independent of the true
3 -1- ( Y - Y )
concentration level (i.e., the constant bias), and (b) C. j 1 ,
which depends on the true concentration level (i.e., the concen-
tration dependent bias). If (y • - Y-.) is zero, then the relative
difference in mean recovery is p./p,, which is independent of con-
centration level C. . Then the mean recovery of water type "j" is
p./Pi x 100 percent of the mean recovery for distilled water. If
43
-------
(Y- - Y-i) is not zero, then the mean recovery of water type "j" is
IY• - Y ]
( [Pj/Pjl'Cj^3 * ) x 100% of that for distilled water, and
therefore depends on the true concentration level C. .
To illustrate these points, consider the following example. Sup-
pose that a significant F-value has been obtained, and the confid-
ence intervals for all of the differences contain zero except for
water type 5. For water type 5, the point estimate for (i'n P5 -
£n p.) is -0.38, and the confidence interval for (£n p - in p, ) is
(-0.69, -0.07). The point estimate for (YS - Yi) is -0.07, and the
confidence interval for (YS ~ Yi ) is (-0.04, 0.18). In this case,
a statistically significant effect due to water type has been es-
tablished that involves only water type 5. The practical signific-
ance of this effect is judged by considering Equation 20. The
ratio of mean recoveries for water type 5 and distilled water is
given by
E(Xi5k> !§<*5 ' *1>
E " ^k ( '
and the ratio of the standard deviations is given by
/Var(Xi. ) p^ (YS - YI)
' J = -^C (22)
VarfX ^ B^k l**/
vax\A.. .. 7 p. n.
j. J.JC X
Because the confidence interval for (YC - Yi) contains zero, this
difference is assumed to be insignificant and is set to zero.
Therefore, Equations 21 and 22 reduce to Pc/Pi• The point estimate
for (£n p_ - in p..) was -0.38. Therefore, the point estimate for
Pc/P^ is 0.68, and the mean recovery for water type 5 is estimated
to be 68% of the mean recovery for distilled water. Similarly,
the standard deviation for the data for water type 5 is estimated
to be 68% of the standard deviation for distilled water. Since
44
-------
the 95% confidence interval for (£n (?5 - In p,) was (-0.69, -0.07),
any value in the interval (0.50, 0.93) is a reasonable estimate for
3s/Pj, and the mean recovery (standard deviation) foj. water type 5
can be claimed to be from 50% to 93% of the mean recovery (standard
deviation) for distilled water. The practical significance of the
effect due to water type 5 would depend on the importance of a mean
recovery (standard deviation) that is between 50% and 93% of the
mean recovery (standard deviation) observed for distilled water.
The comparison of accuracy and precision across water types just
discussed, is based on the assumption that Equation (1) 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 identifies 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
precision and accuracy.
Results of the accuracy and precision comparison among the waters
in the study are presented in Appendix G.
45
-------
SECTION 6
RESULTS AND DISCUSSION
The objective of this study was to characterize the performance of
Method 602 in terms of accuracy, overall precision, single-analyst
precision, and the effect of water type on accuracy and precision.
One measure of the performance of the method is that 17% of the
5040 analytical values were rejected as outliers, which is equiva-
lent to rejecting data fror.i about three of the twenty laboratories.
The 17% level of data rejection is normal for this type of study
and is acceptable. Of the 17% outliers, 10% were rejected through
application of Youden's laboratory ranking procedure and 7%
were rejected employing the Thompson T-test.
ACCURACY
The accuracy of Method 602 is obtained by comparing the mean
recovery, x, to the true values of concentration in pg/L. In
Tables 11 through 17, individual values of accuracy as percent
relative error are listed for each analyte, in each water matrix,
end at each of the six concentration levels in that water matrix
(three Youden pairs). This results in 252 separate values for
accuracy. The linear regression of mean recovery, x, vernus true
concentration level, c, provides values representing the percent
recovery over all of. the concentration levels. This reduces the
separate values for accuracy to 42, one value for each of seven
analytes in each of six waters. Table 18 presents the percent re-
covery for each compound in water types as measured by the slopes
of the linear equations for recovery presented earlier in Table 1.
46
-------
TABLE 18. METHOD 602 ACCURACY
Compound
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichlorobenzene
Ethylbenzene
Toluene
Average- analyte
Water
_ . a
Regression
slope
92
95
93
96
93
94
94
94
1
Average
recovery
100
97
96
95
93
98
103
97
Water
Regression
slope
97
94
91
93
91
97
94
94
2
Average
recovery
109
96
96
96
94
103
97
99
Water 3
Regression
slope
93
92
89
93
88
93
93
92
Average
recovery
98
90
92
99
91
95
93
94
(continued)
-------
TABLE 18 (continued)
CD
Compound
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichlorobenzene
Ethylbenzene
Toluene
Average analyte
Water
Regression
slope
91
93C
90
iooc
89
94
87
92
4
Average
recovery
91
119C
95
146°
96
99
101
107
Water
Regression
slope
87
63C
95
92
95
86
71C
84
S
Average
recovery
92
337C
105
99
100
88
194C
145
Water
Regression
slope
93
92
88
94
91
89
91
91
6
Average
recovery
100
94
83
96
92
99
105
96
Average all
Regression
slope
92
88
91
95
91
92
88
waters
Average
recovery
98
138
95
105
94
97
116
Slope of regression equation for X in Table 36.
b
Average of mean recoveries calculated from Tables 29 through 35.
Differences in accuracy values >±15%.
-------
This is a simplified approach because the intercept portion of the
regression equation is assumed to be insignificant. The values
are compared to percent recoveries calculated from the average of
the quotients x:c presented in Tables 11 through 17.
Table 18 shows that the percent recoveries (accuracies) calcu-
lated by the two methods are in substantial agreement. Minor
discrepancies of approximately 10% can be traced to the lowest
Youden-pair concentrations. These slightly higher percent re-
coveries are due to small amounts of interferences added to small
amounts of spiked compound. This shows the need and value of the
weighted regression equation concept. Simple averaging places too
much emphasis on the .lowest Youden pair. Major discrepancies do
occur in water 5 for chlorobenzene and toluene. These discrepan-
cies can be traced to the extremely high average recoveries of
these analytes in the low Youden-pair ampuls for water 5 as pre-
sented in Tables 12 and 17 (percent recoveries of 1064 and 583
for chlorobenzene, and 594 and 199 for toluene at the low concen-
trations). This is attributed to high background or blank values
of chlorobenzene and toluene in water 5 (average of 226 ».ig/L for
ch.1 orobenzene and 1.27 pg/L for toluene over the 20 laboratories).
The mean recovery fur chlorobenzene and toluene for the middle and
high Youden-pair concentration are 94.5% and 86.4%, respectively.
Large discrepancies are also noted for chlorobenzene and 1,3-
dichlorobenzene in water 4 where the average blank values of these
analytes were 28.9 pg/L and 42.8 pg/L, respectively. While these
background concentrations are lower than those for chlorobenzene
and toluene in water 5 they are sufficiently high to cause
unnaturally high recoveries in the low Youden pair concentrations
(see Tables 12 and 14). In addition the intercepts of the lineal-
regression equations for chlorobenzene and 1,3-dichlorobenzene
in water 4 and chlorobenzene and toluene in water 5 cannot be
considered negligible since they represent a significant percent-
age of the average values for accuracy as calculated from the data
49
-------
in Tables 12, 14, and 17 (this is presented later in Table 23).
Of all possible combinations of analyte and water these four cases
are the only ones where the intercept value exceeds one percent
of the average value of accuracy.
PRECISION
The overall and single-analyst precisions of Method 602 were
determined as percent relative standard deviations for each
analyte, water type, and concentration level. As presented in
Tables 1.1 through 17, 252 individual values of overall percent
relative standard deviation and 126 individual values of single-
analyst percent relative standard deviation result. The linear
regression of standard deviation, s, versus mean recovery, x, pro-
vides values of percent relative standard deviation over all the
concentration ranges. This reduces the separate measures of pre-
cision to 42, one valua for each of seven analytes in each of six
water-types. Tables 19 and 20 present the percent relative stand-
ard deviations as measured by the slopes of the linear regression
equations presented earlier in Table 1 for the overall and the
single-analyst precision, respectively. These values are compared
to the averages of the percent relative standard deviatons pre-
sented in Tables 11 through 17.
In 'jeneral, the linear regression slope yields higher precision
val xes (lower percent relative standard deviation). The major
discrepencies in the precision values (% RSD and % RSD-SA) occur
for chlorobenzene in waters 4 and 5 and for toluene in waters 5
and 6. These differences can be traced to the low precision of
measurements for toluene and chlorobenzene in the low Youden-pair
analyses (see Tables 12 and 17). These poor precision values also
can be attributed to the high background concentrations for chloro-
benzene in water 5 and toluene in waters 5 and 6 (see Appendix E)
and subsequent variability in the values corrected for background
(blank value).
50
-------
TABLE 19. METHOD 602 PRECISION (% RPD)
Compound
Benzene
Chlorobenzene
1 , 2-Dichloi obenzene
1 . 3-Dichlorobenzene
1 ,4-Dichlor obenzene
Ethylbenzene
Toluene
Average analyte
Water
Regression
slope
21
17
22
19
20
26
18
20
1
Average
% RSD
28
18
28
20
27
29
26
25
Water
Regression
slope
22
16
18
15
15
20
21
18
2
Average
% RSD
34
21
21
19
20
29
23
24
Water 3
Regression
slope
19
19
18
18
17
21
25
20
Average
% RSD
24
23
20
28
29
26
30
26
(continued)
-------
TABLE 19 (continued)
Compound
Benzene
Chlorobenzene
1 ,2-Dichlorobenzene
1 , 3-Dichlorobenzene
in 1 ,4-Dichiorobenzene
(0
Ethylbenzen-
Toluene
Average analyte
Water
Regression
slope
26
21C
25
36
18
21
24
24
4
Average
% RSD
36
43C
30
42
26
27
32
34
Water
Regression
slope
25
31C
17
19
19
25
23C
23
5
Average
% RSD
38
59°
30
29
25
33
50°
38
Water
Regression
slope
25
16
18
16
15
20
21C
19
6
Average
% RSD
32
26
28
22
20
30
38C
28
Average all
Regression
slope
23
20
20
21
17
22
23
waters
Average
% RSD
32
32
26
27
25
29
33
Slope of regression equation for S in Table 36.
Average of % RSD values in Tables 29 through 35.
Differences in prevision values exceed 15 units.
-------
TABLE 20. METHOD 602 PRECISION {% RSD-SA)
Compound
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 . 3-Dichlorobeniene
1 ,4-Dichlorobenzene
Ethylbenzene
Toluene
Average anaiyte
Water
Regression
slope
9
9
17
15
15
17
9
13
1
Average
% RSD-SA
16
12
17
14
20
23
15
17
Water
Regression
slope
11
10
10
8
9
10
10
10
2
Average
% RSD-SA
11
:i2
15
13
14
13
13
13
Water 3
Regress
slope
8
8
10
10
12
8
8
9
ion Average
% RSD-SA
11
10
11
M
11
12
11
11
(continued)
-------
TABL2 20 (continued)
Compound
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichlorobenzene
Ethylbenzene
Toluene
Average analyte
Water
Regression
slope
13
8C
11
15
7
12
11
11
4
Average
% RSD-SA
21
31C
22
17
18
17
23
21
Water
Regression
slope
9
9C
10
10
10
11
18°
13
5
Average
% RSD-SA
23
44C
20
16
20
18
33C
25
Water
Regression
slope
10
10
15
12
9
13
ioc
11
6
Average
% RSD-SA
15
17
17
is
14
20
23°
17
Average all
Regression
slope
10
9
12
12
10
12
11
waters
Average
% RSD-SA
16
21
17
15
16
17
20
Slope of regression equation for S in Table 36.
L- r
Average of %RSD-SA values in Tables 29 through 35.
Differences in precision values exceed 15 units.
-------
These same analyte/water combinations exhibit the largest inter-
cepts in the linear regression equations for S and SR as shown
later in Table 23. In each of these cases the intercepts exceed
5% of the average values of S and SR calculated from the data in
Tables 11 through 17.
The preceding regression equations presented in Table 1 assume a
linear relationship between the precision of the data and the con-
centration of the analytes. A summary of % RSD and % RSD-SA in
each of the Youden-pair concentrations is presented in Tables 21
and 22, in order to examine the assumption of a linear relation-
ship. It is apparent from these tables that the average precision
is low for the low ifouden-pair samples (high values of % RSD and
% RSD-SA), but that the precision values for the medium and high
Youden-pair concentrations are comparable. The low precision
values at low concentrations are especially evident in the cases
of the wastewater matrices (waters 4 through 6). In these cases
a curvalinier relationship for % RSD and % RSD-SA appears to exist.
As a test of the relative magnitudes of the intercept values,
average values of S, SR, and X were calculated from the data in
Tables 11 through 17 over the three concentration levels report-
ed in this study. Table 23 presents the average values for the
statistical quantities and the percentage of these averages repre-
sented by the intercepts from the linear regression equations
presented in Table 1. From the data presented in Table 23, it is
apparent that non-negligible values of the intercepts occur for
chlorobenzene in wastewaters 1 and 2 (waters 4 and 5), and for
toluene in wastewater 2 (water 5). These cases and other scat-
tered cases in the table bring to question whether the slopes of
the linear regression equations represent good approximations of
the accuracy and/or precision of Method 602 over the concentra-
tion range investigated.
55
-------
TABLE 21. SUMMARY OF PRECISION (% RSD) BY ANALYTE,
WATER TYPE, AND CONCENTRATION LEVEL
Water type Analyte
Distilled water Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorr.senzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Tap water Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
i , 3-Dichlorobenzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Surface water Benzene '
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Aver eg? of all analytes
Low
Youden
pair
42.7
20.9
39.9
23.1
38.0
34.4
40.9
34.3
55.0
30.0
28.1
27.2
29.3
44.2
26.9
34.4
33.2
29.0
25.0
46.8
50.7
35.6
43.2
37.6
Medium
Youden
pair
16.0
18.9
22.6
21.0
22.5
32.1
17.0
21.4
9.9
16.9
14.2
13.7
11.9
21.4
19.3
15.3
13.0
21.4
14.2
16.0
14.1
20.7
23.2
17.5
High
Youden
pair
23.9
15.3
21.8
17.4
19.8
21.6
20.3
20.0
26.8
17.0
22.1
17.6
18.7
21.0
23.4
20.9
26.6
17.4
20.8
22.1
21.4
22.5
22.6
21.9
(continued)
56
-------
TABLE 21 (continued)
Water type Analyte
Wastewater 1 Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Wastewater 2 Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4-Di chloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Wastewater 3 Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Low
Youden
pair
55.2
84.8
43.7
60.4
39.2
35.7
47.0
52.3
63.7
88.8
51.8
47.8
41.8
48.5
90.5
61.8
45.4
50.5
46.5
33.0
30.5
47.4
69.9
46.2
Medium
Youden
pair
29.3
26.8
17.5
39.8
17.4
23.7
22.3
25.3
20.3
61.6
18.2
16.9
14.9
27.2
30.0
27.0
26.5
20.5
18.1
15.3
12.2
24.3
24.1
20.1
High
Youden
pair
23.3
16.7
29.0
26.7
20.1
20.4
27.0
23.3
30.3
26.5
20.0
21.9
19.4
22.8
28.4
24.2
23..?
13.6
18.2
17.9
16.4
17.9
20.2
18.2
Grand Average
44.4
21.1
21.4
57
-------
TABLE 22. SUMMARY OF PRECISION (% RSD-SA) BY ANALYTE,
WATER TYPE, AND CONCENTRATION LEVEL
Water type Analvte
Distilled water Benzene
Chlorobenzene
1 ,2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Tap water Benzene
Chlorobenzene
1 ,2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Surface water Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Low
Youden
pair
29.2
18.3
15.7
.10.9
27.3
33.7
25.6
23.0
9.0
14.7
25.6
21.0
24.0
16.8
17.0
1H.3
14. *»
14.4
11.2
10.9
9.4
20.4
15.9
13.8
Medium
Youden
pair
7.9
8.7
18.6
18.4
13.0
26.1
8.7
15.2
13.6
13.3
8.8
8.6
9.6
10.9
12.6
11.0
8.2
7.8
8.6
9.8
12.0
8.2
7.8
8.?
High
Youden
pair
12.2
9.7
15.7
11.7
13.4
9.6
10.9
11.9
8.2
7.1
12.0
8.3
9.2
10.3
8.1
9.0
9.1
8.3
11.0
10.9
11.1
7.8
9.2
9.6
(continued)
58
-------
TABLE 22 (continued)
Water type Analyte
Wastewater 1 Benzene
Chlorobenzene
1 ,2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Wastewater 2 Benzene
Chlorobenzene
1 ,2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Wastewater 3 Benzene
Chlorobenzene
1 ,2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichloorbenzene
Ethylbenzene
Toluene
Average of all analytes
Low
Youden
pair
36.1
70.7
43.5
20.9
37.2
26.1
44.3
39.8
43.8
83.3
38.7
28.8
38.5
30.1
54.5
45.4
24.1
28.1
21.8
22.8
22.7
31.4
46.5
28.2
Medium
Youden
pair
12.1
13.0
11.1
19.2
6.1
13.8
13.2
12.6
11.0
32.5
11.8
7.6
11.0
12.0
31.8
16.8
11.3
12.0
17.6
12.9
9.6
17.3
14.0
13.5
High
Youden
pair
14.5
10.2
12.3
11.6
10.6
11.9
11.6
11.8
10.0
15.6
10.5
12.9
11.0
10.7
13.4
12.0
8.9
9.9
12.0
11.3
9.7
10.3
8.9
10.1
Grand Average
28.1
13.0
10.1
59
-------
TABLE 23. RELATIVE MAGNITUDE OF INTERCEPTS IN THE LINEAR REGRESSION EQUATIONS
Benzene
Distilled water
X
S
SR
Tap water
X
S
SR
Surface water
X
S
SR
Average
value
168
39.0
20.6
174
43.5
15.2
169
41.7
15.3
Intercept
as percent
of average
value
0
1
2
0
2
0
0
0
1
.34
.44
.86
.49
.5S
.40
.51
.91
.11
Chlorcbenzene
Average
value
174
26.7
16.8
167
28.6
13.0
163
29.1
13.5
Intercept
as percent
of average
value
0
0
1
0
1
0
0
0
1
.01
.37
.37
.07
.26
.92
.09
.69
.04
1 ,2-Dichlorobenzene
Average
value
175
38.9
27.9
161
36.3
20.0
159
32.0
17.2
Intercept
as percent
of average
value
0
1
0
0
0
2
0
0
0
.30
.36
,14
.27
.77
.10
.13
.37
.23
1 ,3-Dichlorobenzene
Average
value
169
30.1
21.0
164
28.5
13.8
167
36.0
18.1
Intercept
as percent
of average
value
0
0
0
0
1
2
0
2
0
.02
.30
.48
.13
.16
.40
.24
.22
.06
(continued)
-------
TABLE 23 (continued)
cr>
Benzene
Wastewater 1
X
S
SR
Wastewater 2
X
S
SR
Wastewater 3
X
S
SR
Average
value
169
40.7
24.3
162
48.2
i6.7
174
41.2
15.9
Intercept
as percent
of average
value
0
I
2
0
2
S
0
1
3
.04
.70
.30
.22
.01
.81°
.29
.41
.64
Chlorobenzene
Average
value
"*
169
30.6
18.6
169
54.9
33.8
167
24.3
17.0
Intercept
as percent
of average
value
1 . 10
7.60b
16. 3C
U-7b
21.5
43. 9C
0.09
3.51
2.53
1 , 2-Dichlorobenzene
Average
value
164
45.9
20.2
180
35.8
19.4
164
30.0
20.5
Intercept
as percent
of average
value
0
I
4
0
3
4
0
1
0
.23
.03
.60
.38
.13
.64
.24
.70
.68
1,3 Dichlorobenzene
Average
value
171
48.2
21.2
172
37.1
21.6
168
29.5
19.3
Intercept
as percent
of average
value
1
1
2
0
2
2
0
1
1
.963
.72
.17
.29
.13
.40
.10
.46
.51
(continued)
-------
TABLE 23 (continued)
1 ,4-Dichlorbenzene
Distilled water
X
S
SR
Tap water
X
S
SR
Surface water
X
S
SR
Average
value
166
33.9
23.2
160
29.1
14.9
154
31.9
17.2
Intercept
as percent
of average
value
0
1
1
0
1
2
0
2
0
.05
.21
.25
.16
.34
.62
.18
.66
.35
Ethylbenzene
Average
value
166
37.7
18.9
170
36.0
17.6
164
36.7
13.0
Intercept
as percent
of average
value
0
0
2
0
1
1
0
0
2
.19
.61
.44
.24
.89
.02
.12
.98
.54
Toluene
Average
value
177
38.5
19.0
167
38.4
14.4
169
38.2
19.4
Intercept
as percent
of average
value
0
1
2
0
0
1
0
0
1
.37
.98
.53
.10 .
.42
.25
.01
.86
.17
(continued)
-------
TABLE 23 (continued)
U)
1 ,4-Dichlorbe. zene
Wastewater
X
S
SR
Wastewater
X
S
SR
Wastewater
X
S
SR
Average
value
1
162
32.0
16.6
2
169
32.1
18.9
3
163
26.0
15.9
Inte cept
as percent
of average
value
0.33
1.84
c
5.11
0.20
1.53
4.50
0.07
1.27
2.14
Ethylbenzene
Average
value
167
35.0
20.4
157
36.9
17.2
168
31.3
18.6
Intercept
as percent
of average
value
0.23
1.14
1.87
0.09
1.44
2.62
0.44
2.50
2.80
Toluene
Average
value
162
43.3
19.4
169
50.5
26.8
171
35.5
16.4
Intercept
as percent
of average
value
0.61
1.55
c
5.40
5.12*
8.63
13. 0C
0.59
4.36
7.33°
Intercepts
b
Intercepts
exceed 1 percent
exceed S percent
of average
of S.
X.
Intercepts exceed 5 percent of SR.
-------
Table 24 presents a comparison of the accuracy and precision
(single analyst) obtained in this interlaboratory study versus
those values reported by EPA in the description of the Test
Method (Appendix A).
TABLE 24. COMPARISON OF SINGLE OPERATOR
ACCURACY AND PRECISION
Average percent Percent standard
recovery deviation
Analyte
Ben;:ene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Toluene
EPAa
91
97
104
97
120
98
77
This Studyb
92
88
91
95
91
92
88
EPA3
10.0
9.4
27.7
20.0
20.4
12.4
12.1
This Studyb
10.0
9.0
12.2
10.0
10.3
11.8
10.5
Average of three matrix types (Table 2 - Appendix A).
Average of six matrix types (Table 1 - this report).
In all cases except for toluene this study reports lower accuracies
than the original EPA results. The single operator precision
values for this study are equal or better than the EPA figures
(lower % standard deviation).
EFFECTS OF WATER TYPES
The comparison of accuracy and precision across water types is
summarized in Table 25, where the observed F values and the prob-
ability of exceeding the F values are entered for each of the
seven analytes.
For every analyte except ethylbenzene and 1,4-dichlorobenzene, the
F-test suggests a statistically significant effect due to water
type (P[F>observed F]<0.05). The null hypothesis test indicates
64
-------
TABLE 25. SUMMARY OF THE TESTS FOR DIFFERENCE ACROSS WATER TYPES
o>
o>
Compound
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 ,4-Dichlorobenzene
Ethylbenzene
Toluene
Observed
F-value
3.87
10.03
4.41
4.61
1.49
1.83
5.13
P[F >observed F]
0.000
0.000
0.000
0.000
0.138
0.053
0.000
F test
statistically
significant
at the 5%
level
Yes
Yes
Yes
Yes
No
No
Yes
Statistical
significance
established
by the 95%
confidence
limit Waters
Yes 4, 5
Yes S
Yes 6
Yes 4
-
-
Yes 5
Practical
significance
established
by the 95%
confidence
lin.it
No
Yes
No
No
-
-
Yes
Waters
-
5
-
-
-
-
5
-------
that a statistically significant effect has been established at
the 95% confidence limit for the following analyte - water com-
binations: benzene in waters 4 and 5; chlorobenzer.e in water 5;
1,2-dichlorobenzene in water 6; 1,3-dichlorobenzene in water 4;
and toluene in water 5. These effects are indicated since zero
is not contained within the confidence limits for (£n 3. - £n3,)
for the above analyte-water combinations.
The practical significance of these effects was determined by
applying equations (21) and (22). In this case, a practical
significance was established for only two cases: that of chloro-
benzene and toluene in wastewater 5. These analyte-water com-
binations coincide with those which exhibited abnormally low
slopes in the regression equations presented earlier in Table 1.
RESPONSES TO QUESTIONNAIRE
A Method 602 questionnaire was provided to all participating
laboratories. Ten of twenty laboratories completed the question-
naire. Table 26 summarizes the analytical conditions employed by
the responding laboratories. As shown in Table 26, laboratories
4 and 6 used SP-2100 rather than SP-1200 in their column pack-
aging; in addition, all but four of the reporting laboratories
used Tenax GC® only as the trap material. Omission of the OV-1
material specified by Method 602 could have adversely affected
the precision of benzene and toluene analyses due to poorer
desorption profiles. Laboratory 1 reported that negative peaks
were caused by water when a Tenax/silica gel trap was employed;
elimination of the silica gel cured this problem. Only three of
the laboratories us&d a post-purge drying cycle. Laboratory 19
encountered some difficulties in using the drying cycle, but
reported no problems when it was omitted.
66
-------
TABLE 26. LABORATORY ANALYTICAL CONDITIONS
Laboratory
code
1
3a
4
5
6
7
8
9^
ioa
11
14
17
18
19
20°
Gas
chromatcgram
H-P 5880A
Tracor 700A
5711
PE Sigma I
H-P 5750
PE 900
Varian 37006C
PE 39206C
-
Tracor 560A
Fisher 24UO
H-P 5840
Microtech
Tracor MT220
Temperature
program,
°C
50°-2 min
6°/min to 90°
50°-2 min
4°/min to 90°
50°-6 min
30/min to 90°
50°-2 min
6°/min to 90°
50°-2 min
6°/min to 90°
50%-2 min
6°/min to 90°
-
-
50°-3 min
6°/min to 100°
51°-2 min
8°/min to' 93°
-
50°-2 min
7.5°/min to 90°
50°-2 min
7.5%/min to 90°
Carrii-r gas/
flow rate,
mL/min
N2/40
He/36.8
He/20
He/40
he/ 40
He/40
He
-
He/30
He/ 40
-
He/20
He/20
Column packing
5% SP-1200/
I .75% Bentone 34
rj% S»'-2100/
1.75% Bentone 34
5% SP-1200/
1 .75% Bentone 34
5% SP-2100/
1.75% Bentone 34
5% SP-1200/
1 .75% Bentone 34
5% SP-120C/
1.75% Bentone 34
-
-
5% SP-1200/
1.75% Bentone 34
5% SP-1200/
1 .76% Bentone 34
-
5% SP-1200/
1.75% Bentone 34
5% SP-1200/
1 .75% Bentone 34
Column
-
6' x 1/8"
stainless
6' x 2 mm
glass
6' x 1/8"
6' x 0.085
stainless
6' 2 mm I .
-
-
-
6' x 1/8"
-
6' ? ? ? ?
6 ' x 2 mm
glass
t _
size
O.D.
1.0.
stainless
" I.D.
D. glass
stainless
I.D.
(continued)
-------
TABLE 26 (continued)
i
s
0
Laboratory
code
1
3*
4
5
6
7
8
9a
ioa
11
14
17
18
19
20a
Detector
temperature. Lamp Purge/ trap
°C intensity instrument Mode
225 - Tekmar LSC-2 Manual
Takmar LSC-2
160 5 Tekmar LSC-1 Manual
200 5 CDS 310 Manual
250 7.5 Takmar LSC-2 Automatic
230 5.5 Tekmar LSC-2 Automatic
150 4
Homemade
Tekmar
150 - Homemade Manual
160 3 Homemade Manual
Tekmar LSC-2 -
240 5 Tekmar Manual
220 5 Tekmar LSC-2 Automatic
Tekmar LSC-2 Automatic
Purge, dry,
desorb, bake
cycle, min 1 • nateri . .
P-12, DE-4, B-" Tenax
-
P-12, D-6, Tenax
DE-4, 13-7
P-12, D-5, Tenax
D£-7(Burn-180°C)
P-ll, DE-7, B-4 50/5"' Tenax, charcoal
P-12, D-6. T»nax
DE-4, 13-15
P-12, DE-4, B->7 -.ax
~. - . OV-1 , silicia
... charcoal
-
P-I2, DE-3, B-20 Tenax, 3% OV-1, silicia
gel, charcoal
P-12, DE-4, B-7 Tenax, 3% OV-1
" 4
P-12, DE-4, B-10 Tenax
P-12, DE-5, B-35 Tenax
-
Information from original proposed approach.
-------
Nine of the ten responding laboratories reported no problems in
the preparation of star.dards. Laboratory 6 stated that baseline
drift at low concentration levels made them resort to manual
quantitation of data. Eight of the laboratories reported no prob-
lems encountered in detection limits for the volatile aromatics.
One .of the laboratories reported poor detector sensitivity and
the need for frequent lamp replacement. Laboratory 19 had diffi-
culty detecting the lowest concentration? of 1,2-dichlorobenzene.
As regards the linearity of detector response, seven of the
responding laboratories observed good linearity over the entire
concentration range. Laboratory 1 reported excellent linearity
up to 50 pg/L. Laboratory 19 encountered problems at high con-
centrations because the upper limit of the integrator had reached
its capacity. Laboratory 5 reported erratic results at low con-
centrations and observed poor linearity for toluene.
A wide variety of calibration methods were reported by the
responding laboratories. These ranged from employing five con-
centrations of external standards plus a blank to running one
near point concentration. Seven of the responding laboratories
reported no problems in day-to-day variation in detector sensi-
tivity. Three laboratories that did find variations attributed
this to either changes in flow rate (Laboratory 6) or to clouding
up of the detector lamp and the need for frequent cleaning
(Laboratories 1 and 5). Laboratory 5 reported a 10%/day drop in
sensitivity if the lamp was not cleaned.
Seven of the responding laboratories stated that no particular
compound prejentei more problems than others. As mentioned abov-,
Laboratory 19 had sensitivity problems for low concentrations of
1,2-dichlorobenzene. Laboratory 5 felt that laboratory air in-
terferences and contamination of water matrices resulted in more
problems in analyses of benzene compared to the other volatile
69
-------
aromatics. Laboratory 14 which employed a "homemade" purge/trap
unit experienced carry-over problems with all the compounds when
concentrations exceeded 50 pg/L.
Four of the responding laboratories reported no problems related
to water types employed in the study. The other six laboratories
experienced problems with the high background concentration of
the volatile aromatics and other contaminants in the wastewaters.
This was especially evident with wastewater 2 (water 5) where
intt rfering peaks caused quantitation problems for low levels of
toluene and the chlorobenzenes. The high J~vels of contaminants
required the running of more blanks to check for carry-over from
the purge/trap device.
In the category of miscellaneous comments and recommended improve-
ments in Method 602, Laboratory 5 suggested a more detailed method
for preparation of distilled water to avoid contamination due to
laboratory air impurities. This method involves boiling water for
30 minutes, filling a 100-mL Erlenmeyer flask above the mark with
boiling water, rapidly cooling in an ice bath, and immediately
spiking and analyzing the resultant solution. Another criticism
of the current procedure was the necessity of replacing the HNU
detector lamp every one to two months (Laboratory 1). A long-
lived lamp would alleviate this expensive problem. Laboratory 19
recommended omission of the post-purge drying step from the purge/
trap cycle.
OTHER MONSANTO COMPANY FINDINGS DURING PRELIMINARY STUDIES
Some of the problems encountered by Monsanto Company during the
preliminary studies and their potential solutions are presented
below:
(1) Initial checkout of the HP 7675A purge/trap sampler
showed random ghost peaks during the purge of
70
-------
distilled water. Steam cleaning of the purge path
seemed to alleviate the problem. This was accom-
plished during the purge mode by heating distilled
water to boiling. The heating was continued for five
minutes after steam became visible at the vent.
(2) The metal injection port (direct injection mode) was
found to affect all dichlorobenzene area counts. Low
counts for these compounds were corrected through the
use of a glass liner packed with glass wool.
(3) Organic-free water blanks were needed after the anal-
ysis of wastewaters having water soluble materials
and purgeable compounds that did not elute during
standard program. It also was necessary to increase
the. column temperature for these blank runs.
(4) Detector quenching and gradual loss of response were
two major problems. The qusnching was minimized by
increasing the post-purge time. However, the longer
time almost doubled the purge volume. This may have
caused another problem of analyte loss due to partial
breakthrough. A possible example of this was noted
in the 1000 x the minimum detectable level of the
analytical curve. Comparisons of direct injection vs.
purge/trap showed the greatest deviation of the diverg-
ing lines for benzene. The deviation became smaller
through 1,2-dichlorobenzene where it was a near match.
EPA in-house experience suggests that detector fouling
could be caused by heating the column in excess of the
90°C temperature specified by Method 602 and venting
through the detector.
71
-------
REFERENCES
1. Youden, W. J. Statistical Techniques for Collaborative Tests.
Association of Official Analytical Chemists, Inc., Washington,
D.C., 1969. 64 pp.
2. Outler, E.G. and McCreary, J.H., Interlaboratory Method Vali-
dation 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 E178-80, 1980 Annual Book of ASTM Standards, Part 41,
pp. 206-231, American Society for Testing and Materials,
Philadelphia, Pa.
5. Youden, W.J. "Statistical Manual of the AOAC," The Associa-
tion of Official Analytical Chemists, Washington, DC, 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.
72
-------
APPENDIX A
PURGEABLE AROMATICS
METHOD 602
73
-------
EPA
United Slates
Environmental Protection
Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/4-82-057 July 1982
Test Method
Purgeable Aromatics-
Method 602
1. Scope and Application
1.1 This method covers the determi-
nation of various pu'geable aromatics.
The following parameters may be
determined by this method:
Parameter
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1.4-Dichlorobenzene
Ethylbenzene
Toluene
STORET No.
T.4030
34301
34536
34566
34571
34371
34010
CAS No.
71-43-2
108 90-7
95-50-1
541-73-1
106-46-7
100-41-4
108-88-3
1.2 This is a purge and trap gas
chromatographic method applicable to
the determination of the compounds
listed above in municipal and industrial
discharges as provided under 40 CFR
136.1. When this method is used to
analyze unfamiliar samples for any or
all of the compounds above, compound
identifications should be supported by
at least one additional qualitative
technique. This method describes
analytical conditions for a second gas
chromatographic column that can be
used to confirm measurements made
with the primary column. Method 624
provides gas chromatograph/mass
spectrometer (GC/MS) conditions
appropriate for the qualitative and
quantitative confirmation of results for
all of the parameters listed above.
1.3 The method detection limit (MOL,
defined in Section 12.1 <1') for each
parameter is listed in Table 1. The MOL
for a specific wastewater may differ
from these listed depending upon the
nature of interferences in the sample
matrix.
1.4 Any modification of this method,
beyond those expressly permitted,
shall be considered as major modifica-
tions subject to application and
approval for alternate test procedures
under 40 CFR 1 36.4 and 136.5
1.5 Tliis method is restricted to use
by or under the supervision of analysts
experienced in the operation of a purge
and trap system and a gas chromato-
graph and in the interpretation of
chromatograms. Each analyst nr.ust
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 water sample contained in a
specially-designed purging chamber at
ambient temperature. The aromatics
are efficiently transferred from the
aqueous phase to the vapor phase. The
vapor is swept through a sorbent trap
where the aromitics are trapped. After
74
-------
pu'ping is completed, the trap is heated
and backdushed with the inert gas to
desorb the aronutics onto a gas
chroniatogiaphic column. The gas
chromatog'aph is temperature pro-
grammed to separate the aromatics
which are then detected with a photo-
ionization detector'? 3>
2 2 The method provides an optional
gas chromatographic column that may
be helpful in resolving the compounds
of interest from interferences that may
occur.
3. Interferences
3.1 Impurities m the purge gas and
organic compounds out-gassing from
the plumbing ahead of the trap account
for the majority of contamination
problems. The analytical system must
be demonstrated to be free from
contamination under the conditirns of
the analysis by running laboratory
reagent blanks as described in Section
8 5. The use of non-TFE plas'ic tubing,
non-TFE thread sealants, or 'low
controllers with rubber components in
the purging device should be avoided.
3.2 Samples can be contaminated by
diffusion of vo'aiiie organics 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-ove', 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
aromatic levels, it may be necessary to
wash out the purging device with a
detergent solu'ion, rinse it with distilled
water, and then dry it in an oven at
105 °C between analyses. The trap
and other parts of the system are also
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 compouno should be
treated as a potential health ha/ard.
From this viewpoint, exposure to thess
chemicals must be reduced to the
lowest possible level by whatever
means available. The laboratory is
responsible for ti^'ntaining a current
awareness file of OSHA regulations
regarding the safe hondhrg 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 identified14 6| for the
information of the analyst.
4.2 The following parame.ers covered
by this method have been tentatively
classified as known or suspected,
human or mammaiian carcinogens:
benzene and 1,4-dichlorobenzene.
Primary standards of these toxic
compounds should be prepared in a
hood. An NIOSH'MESA approved toxic
gas respirator should be worn when the
analyst handles high concentrations of
these tnxic compounds.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete
sampling.
5.1.1 Vial— 25-mL capacity or larger,
equipped with a screw cap with hole in
center (Pierce tt\ 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 »12722 or equivalent).
Detergent wash, rinse with tap and
distilled water, &n Section 10.1. .
5.3.2 Column 2 — 8 ft long x 0.1 in
ID stainless steel or glass, packed with
5% 1,2.3-Tris(2-cyanoethoxylpropane
on Chromosorb W-AW (60/80 mesh)
or equivalent.
5.3.3 Detector—Photoior.ization
detector (h-nu Systems, Inc. Model
PI-51-02 or equivalent). This type of
detector has been proven effective ii.
the analysis of wastewaters for the
parameters listed in the scope, and
was used to develop the performance
statements in Section 12. Guidelines
for the use of alternate detectors are
provided in Section 10.1.
5.4 Syringes—5-mL glass
hypodermic with Luerlok tip (two each),
if applicable to the purge device.
-------
5.5 Micro syringes-25 pL, 0.006 in
ID needle.
5.6 Syringe valve-2-way, with Luer
ends (three each).
5.7 Bottle- 15-mL screw-cap with
Teflon cap liner.
5.8 Balance-Analytical, capable of
accurately weighing 0.0001 g.
6. Reagents
6.1 Reagent water-Reagent water is
defined as a \ .4 Trap Materials
H.4.1 2,6-Diphenylene oxide
polymer-Tenax, (60/60 mesh) chroma-
tographic grade or equivalent.
6.4.2 Methyl silicone-3% OV-1 on
Chromosorb-W (60/80 mesh) or
equivalent.
6.5 Methyl alcohol-Pesticide quality
or equivalent.
6.6 Stock standard solutions-Stock
standard solutions may be prepared
from pure standard materials or
purchased as certified solutions.
Prepare stock standard solutions in
methyl alcohol using assayed liquids.
Because benzene and 1,4-dichloro-
benjsne are suspected carcinogens.
primary dilutions of these materials
should be prepared in 3 hood.
6.6.1 Place about 9.8 ml of methyl
clcohol into a 10-rr.L ground glass
stoppered volumetric flask. Allow the
flask to stand, uns'oppered, for about
10 minutes or until a!! alcohol wetted
surfaces have dried. Weiyh the flask to
the nearest 0.1 mg.
66"..2 Using a 100-pL syringe.
immediately add two or more drops of
assayed leference material to the flask,
then reweigh. Be sure that the drops
fall directly into the alcohol without
contacting the neck of the flask.
6.6.3 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 certified at 96% or greater,
the weight can be used without correc-
tion to calculate the concentration of
the stock standard. Commercially
prepared stock standards can be used,
at any concentration, if they are
certified by the manufacturer or by an
independent source.
6.6.4 Transfer the stock standard
solution into a Teflon-sealed screw-cap
bottle. Stor-; at 4 °C and protect from
light.
fi.6.5 All standards -rust be replaced
after one month, or sooner if compari-
son with check standards indicate a
problem.
6.7 Secondary dilution standards-
Using stock standard solutions, prepare
secondary dilution standards in methyl
alcohol 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
Sections 7.3.1 or 7.4.1 will bracket
the working range of the analytical
system. Secondary solution standards
must be stored with zero headspace
and should be checked frequently for
signs of degradation or evaporation,
especially just prior :o preparing
calibration standards from them.
Quality control check standards that
can be used to determine the accuracy
of calibration standards will be
available from the U.S. Environmental
Protection Agency, Environmental
Monitoring and Support Laboratory, in
Cincinnati, Ohio.
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 backflushing with
an inert gas flow of at least 20 mL/min.
Prior to use, daily condition traps 10
minutes while backf lushing 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-gas
chromatographic system using either
the external standard 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 ihree concentration
levels for each parameter by carefully
adding 20.0 /jL of one or more second-
ary dilution standards to 100, 500. or
1000 ml of reagent water. A 25-pL
syringe with a 0.006 inch ID needb
should be used for this operation. One
of the external standards should be at a
concentration near, but above, the
MDL (see Table 1) and the other
concentrations should correspond to
the expected range of concentrations •
found in real samples or should define
the working range of the detector.
These aqueous standaros must be
prepared fresh daily.
7.3.2 Analyze each calibration
standard according to Section 10, and
tabulate peak height or area responses
versus the concentration in the
standard The results can be used to
prepare e 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 :n
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
76
-------
is applicable to all samples. The
compound, n .ii,«.
8.2 To establish the ab->2p
or |X - R, =»• 2p. review potential
problem areas and repeat the test
8.2.5 The U.S. Environmental
Protection Agency plans to establish
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 and define
'he performance of the laboratory for
each spike concentration and parameter
being measured.
8.3.1 Calculate upper and lower
control limits for method performance:
Upper Control Limit IUCLI = R + 3',
Lower Control Limit (LCL.I = R - 3s
where R and s are calculated as in
Section 8.2.3
The UCL and LCL can be used to
construct control charts'7' that are use-
ful in observing trends in performance.
The control limits above must be
replaced by method performance
criteria as they become available from
the U.S. Environmental Protection
Agency.
8.3.2 The laboratory must develop
and maintain separate accuracy state-
ments 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
calculation of R and s. Alternately, the
analyst may use four wastewater data
points gathered through the requirement
for continuing quality control ir, Section
8.4. The accuracy statements should
be updated regularly!?'.
8.4 The laboratory is require 1 to
collect a portion of their samp<:<: in
duplicate to monitor spike recoveries.
The frequency of spiked sample
analysis must be at least 10% of all
samples or one sample per month,
whichever is greater. One aliquot of the
sample must be spiked and analyzed as
described in Section 8.2. If the
recovery for a particular parameter
does not fall within the control limits
for method performance, the results
77
-------
repoited for nat parameter in all
samples processed as pan of the same
set must be qualifier) as described in
Section 11.3 The laboratory should
monitor the frequency of data so
qualified to ensure that it remains at or
below 5%.
8.5 Each day. the analysl must
demonstrate through the analysis of
reagent water, that interferences from
the analytical system are under control.
1 6 It is recommended that the
Moratory adopt additional quality
assurance ptactices for use with this
method. The specific practices that are
most productive depend upon the
needs of the laboratory and the nature
of the samples. Field duplicates may be
analyzed 'o monitor the precision of
the sampling technique. When doubt
exists over the identification of a peak
on the chromatogram. confirmatory
techniques such as gas chromatography
with a dissimilar column, specific
element detector, or mass spectrometer
must be used. Whenever possible, the
laboratory should perform analysis cf
standard reference mjterials and
participate in relevant performance
evaluation studies.
8.7 The analyst should maintain
constant surveillance of both the per-
formance of the analytical system and
the effectiveness of the method in
dealing with each sample matrix by
spiking each sample, standard and
blank with surrogate compounds (e.g.
o.o.a.-trifluorotoluene). From stock
standard solutions prepared as above.
add a volume to give 7500 yg of each
surrogate to 45 mL of organic-free
water contained in a 50-mL volumetric
flask, mix and dilute to volume (1 5
ng'yll. If the internal standard calibra-
tion procedure is being used, the
surrogate compounds may be added
directly to the internal standard spiking
solution (Section 7.4.2). Dose lO^iL
of this surrogate spiking solution
directly into the 5-mL syringe with
every sample and reference standard
analyzed. Prepare a fresh surrogate
spiking solution on a weekly basis.
9. Sample Collection,
Praservation, and Handling
9.1 The samples must be iced or
refrigerated from the time of collection
until extraction. If the sample contains
free or combined chlorine, add sodium
thiosulfate preservative (10 mg/40 ml
.s sufficient for up to 5 ppm CI2I to the
empty sample bottles just prior to
shipping to the sampling site. USEPA
Methods 330.4 or 330.5 may be used
to measure residual chlorine181. Field
Test Kits are available for this purpose.
9.2 Collect ebout 500 ml sample ir,
a clean container. Adjust the pH of the
sample to about 2 by adding ' + 1 HCI
while stirrinp gently. Fill the sample
bottle 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.
Maintain the hermetic seal on the
sample bottle until time of analysis.
9.3 All samples must be analyzed
within 1 4 days of collection.131
10. Sample Extraction and
Gas Chromatography
10.1 Table 1 summarizes the
recommended operating conditions for
the gas chromitograph. Included in this
table are estimated retention times and
method detection limits that can be
achieved by this method. An example
of the separations achieved by Co:umn
1 is shown in Figure 6. Other packed
columns, chromatographic conditions,
or detectors may be used if the
requirements of Section 3.2 are met.
10.2 Calibrate the system daily as
described in Section 7.
10.3 Adjust the purge gas (nitrogen
or helium) flow rate to 4Q 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.
10.4 Allow sample to come to
ambient temperature prior to introduc-
ing it into the syrir.ye. Remove the
plunger from a 5-mL syringe and attach
a closed syringe valve. Open the
sample bottle (or standard) and care-
fully 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 o1 the
sample for future analysis, the analyst
should fill a second syringe at Mis time
to protect against possible loss of data.
Add 10.0 yL of the surrogate spiking
solution (Section 8.7) and 10.0 jiL of
the internal standard spiking solution
(Section 7.4.2), if applicable, through
the valve bore, then close the valve.
10.5 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.
10.6 Close both valves and purge the
sample for 12.0 ±0.1 minutes at
ambie.M temperature.
10.7 After the • 2-minute purge time,
disconnect ihe purge chamber fiom the
trap. Dry the trap by maintaining a flow
of 40 mL/min of dry purge gas through
it 'or six minutes. See Figure 4. A dry
purger should be inserted into the
device to minimize moisture in the gas.
Atu-ch the trap to the chromatograph,
acijust the device to the desorb mode,
and begin to temperature program the
gas chromatograph. Introduce the
trapped materials to the GC column by
rapidly heating the trap to 1 80 °C
while backflushing the trap with an
inert gos between 20 and 60 mL/min
for four minutes. If rapid heating
cannot be achieved, the gas
chromatographic column must be used
as a secondary trap by cooling it to
30 °C (subambient temperature, if poor
peak geometry and random retention
time problems persist) instead of the
initial program temperature of 50 °C.
10 R While the trap is being desorbed
onto the GC column, empty the
purging chamber using the sample
introduction syringe. Wash the
chamber with two 5-mL flushes of
reagent water.
10.9 After oesorbing the sample for
fcur 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 180 °C. After approxi-
mately 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.
10.10 The width of the retention
time window used to make identifica-
tions should be based upon measure-
ments of actual retention time variations
of standards over the course ot a day.
Three times the standard deviation of a
retention time for a compound can be
used to calculate a suggested window
size; however, the experience of the
analyst should weigh heavily in the
interpretation of chromatograms.
10.11 If the response for the peak
exceeds the working range of the
system, prepare a dilution of the
sample with reagent water from the
aliquot in the second syringe and
reanalyze.
11. Calculations
111 Determine the concentration of
individual compounds in the sample.
78
-------
11.1.1 If the external standard cali-
bration ptoredure is used, calculate the
concentration of material from the peak
tesponse using the calibration curve or
calibration facto, determined in Section
7.3.2.
11.1.2 If the internal standard cali-
bration procedure was used, calculate
the concentration in the sample using
the response factor (RFl determined in
Section 7.4.3 and equation 2.
ta 2.
Concentration/jg'L = |A,C,,)/(AI$)(RF)
where:
A, = Response for the parameter to
be measured.
A,s = Response for the internal
standard.
C1$ = Concentration of the internal
standard.
11 2 Heport results in microgiams
pet liter. When duplicate and spiked
samples are analyzed, report all data
obtained with the sample results.
11.3 For samples processed as part
of a set where the spiked sample
recovery falls outside of the control
limits which were described in Section
8.3. data for the affected parameters
must be labeled as suspect.
12. Method Performance
12.1 The method detection limit
(MDL) is defined as the minimum con-
centration of a substance that can be
neasured and reported with 99%
confidence that the value is above
zero'1'. The MDL concentrations listed
in Table 1 were obtained using reagent
water'9 . Similar results were achieved
using representative wastewaters.
12.2 This method has been demon-
strated to be applicable for the concen-
tration range from the MDL up to 1000
x MDL'9'. Direct aaueous injection
techniques should be used to measure
concentration levels above 1000 x
MDL.
12.3 In a single laboratory (Monsanto
Research), using reagent water and
wastewaters spiked at or near
background levels, the average
recoveries presented in Table 2 were
obtained'9'. The standard deviation of
the measurement in percent recovery is
also included in Table 2.
12.4 The Environmental Protection
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 Lichtenberg, J.J.
Journal American Water Works
Association, 66, 739. (1974).
3. Bellai. T.A., and Lichtenberg. J.J.
"Semi-Automated Headspace Analysis
Of Drinking Waters and Industrial
Waters for Purgeable Volatile Organic
Compunds." Proceedings of Sym-
posium on Measurement of Organic
Pollutants in Water and Wastewater.
American Society for Testing and
Materials. STP 686, C.E. Van Hall.
editor, 1978.
4. "Carcinogens —Working witf
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, August 1977.
5. "OGHA Safety and Health
Standards. General Industry." (29 CFR
1910), Occupational Safety and
Health Administration. OSHA 2206,
(Revised January 1976).
6. "Safety in Academic Chemistry
Laboratories." American Chemical
Society Publication. Committee on
Safety. 3rd Edition, 1979.
7. "Handbook for Analytical Quality
Control in Water jnd Wastewater
Laboratories," EPA-600'4-79-01 9.
U.S. Environmental Protection Agc-ncy,
Office of Resea'ch and Development.
tnvironmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268.
Merch 1979.
8. "Methods 330.4 (Titrimetric, DPD-
FAS) and 330.5 (Spectrophotometric,
DPD) for Chlorine, Total Residual,"
Methods for Chemical Analysis of
Water and Wastes, EPA 600/4-79-020.
U.S. Environmental Protection Agency,
Office of Research and Development,
Environmental Monitoring and Support
Laboratory, Cincinnati. Ohio 45268.
March 1979.
9. "EPA Method Validation Study 24,
Method 602 (Purgeable Aromaticsl."
Report for EPA Contract 68-03-2856
(In preparation).
79
-------
Table 1. Chromatographic Conditions and Me/hod Detection Limits
Retention T,me Method
»*pn r>" n'°~ Tied at 2°C/min to 100°C for a final hold.
Table 2. Single Operator Accuracy and Precision
Parameter
Benzene
Chlorobenzene
1 . 2- Dichlorobemene
1. 3-Dichlorobenzene
1 ,4-Dichlorobemens
Ethylbcmene
Toluene
A verage
Percent
Recovery
91
97
104
97
120
98
77
Standard
Deviation
%
10.0
9.4
27.7
20.0
20.4
12.4
12.1
Spike Number
flange of
f^g/LI Analyses
0.5-9.7
0.5-100
0.5-10.0
0.5-4.8
0.5-10.0
0.5-9.9
0.5-100
21
21
21
21
21
21
21
Matrix
Types
3
3
3
3
3
3
3
80
-------
Optional
Foam
Trap
i
\
;">- Exit V, in \
^ OD. !
"14mm 0 D
, « *
v. t /n/cf V4 (n.
o- O.D.
OD e*it
Sample Inlet
• ^
~. - 2-way Syringe valve
''— 17cm 20 gauge syringe needle
•» I' /T -v 6mm 0 O. Rubber Septum
Q
d
E
•k.
I
10mm O.D.
P- Inlet
V,, /n. 0.0.
- ^Stainless Steel
\ .•
,r
10mm glass frit '
medium porosity
~ ' - 13X molecular
; sieve purge
.; gas filter
Wow control
Figure V Purging device
Packing procedure
Glass .
Construction
Tena* 23cm
G/«« wool
Compression fitting
" — nut and ferrules
14ft 7"v/ foot resistance
~~~~ wire wrapped solid
Thermocouple/controller
• sensor
Tubing 25 cm.
0.105 in. I.D.
0.125 in. O.D.
stainless steel
Trap inlet
Figur* 2. Trap pickings and construction to include dusorb capability
61
-------
Carrier gas flow control Liquid m,ect,on ports
9 v~ .—i / .. Column oven
Pressure regulator . • t-^4 _-=n / [ i „
~L> n fl (1 II J - Confirmatory column
!fflj!..JU '\Jrodeitxor
I ~^~~~ Analytical column
Valve 3
optional 4-port column
selection valve
Trap inlet (Tena* end,1
v control >v,—|, Purging '| i' 7>»p /n/cf /Tena* end
I «f .-
•molecular $% U /W t-,«o>*-H WC '• /
e M« —% " !: ^----5ni ib ^-y
Het'er contiol
|L-_.-jT Va/ve-2
Figure 3. Purge-Hep system (Purge-sorb Mcdel
Note All lines between
trap and GC
should he heated
to 80-C
Carrier gas flow control
Pressure
Liquid injection ports
Column oven
Purge gas \\
flo w control \r~jl Purging
Ljf device
13X mol»cular_
sieve filter
^— Confirmatory column
a detector
J "*" Ar,alyticel column
Valve-1
Va/ve-3
opticnal 4-port column
seleition valve
Trap inlet (Tenax end>
Resistance wire
Heater control
Note: All lines between
trap and GC
should be heated
to 80°C
Figure 4. Purge-trap system (Trap-dry Model.
82
-------
Camer gas flow control Liquid m/ection ports
, , / Column oven
sure regulator v. *: _^U _. , i i-"^
_•_ „_ Confirmatory column
K- Mil'"' ^ I0>rec""'
Q:pj 11 U U J ""--. Analytical column
op'ional 4 port column
i selection valve
Purgmg )' r /n/p,
va/k-e-'
e pss
control \ i
13X molecular _
j(ev« filter
Valve-2
Figure 6. Purge-trap system iDesorb Mode/
w,re
,'
re-; ' t^ ,j). . Trap '
u
Heater control
Not? All lines between
trap and GC
shou/J be heated
to 80°C
Column 5% SP 1200->-
1.75% Bentone-3* on Supekoport
Program 50CC for 2 mm. 6° per mm to 50°C
Detector: Photoionitetion. 10.2 volts
02 4 6 8 10 12 14 16 18 20 22 24 26 28
Retention time, minutes
Figur* 6. Gas chromatogrim of purgeablt. aromatics
83
-------
APPENDIX B
ADDITIONAL NOTES ON METHOD 602
84
-------
APPENDIX B
ADDITIONAL NOTES ON METHOD 602
(For Analysis Prestudy Conference Samples)
3.1* Steam cleaning of the purge path may help to rid system from
a buildup of impurities. This can be accomplished during the
purge mode by heating organic-free water in the purge vessel
to boiling. The heating should continue for approximately 5
minutes after steam becomes visible at the purge vent.
3.3 Cross contamination can occur in two primary areas: the
purge path and the analytical column. Suggestions listed
in the 3 December 1978 Federal Register (Section 3.3) and
the above steam cleaning method can be used for the purge
path. (Steam cleaning should be used only if other methods
fail.) It may become necessary to increase the analytical
column temperature to 150°C after elution of the last
analyte in order to eliminate a buildup of high boiling
compounds (wastewaters).
Caution: The upper limit for Bentone-34 is 180°C. (See note
in Section 8.5 of these notes, regarding loss of PID
sensitivity.)
5.2 Appropriate purge/trap samplers are those such as the Hewlett-
Packard with up to a 15-mL purging vessel or the Tekmar with
5-mL purging vessel. Do not use Tekmar with a 25-mL purging
vessel.
NOTE: The preliminary investigation of Method 602 (see Appendic C)
was conducted employing a Hewlett-Packard purge/trap device which
does not meet the specifications stated in Method 602, Section
5.2.2 (see Appendix A).
*Section numbers refer to sections in Method 602 description
presented in Appendix A.
85
-------
5.7 A 10- to 15-mL screw-cap is acceptable. We have found a
10-mL cap to be preferable.
6.2/9.1
Any sodium thiosulfate needed in the wastewater samples has already
been added by MRC.
6.4/7.1
The general purpose trap conV.aining 1.3 cc of Tenax G.C.® used in
the Hewlett-Packard purge/trap sampler showed acceptable effi-
ciency without the use of the small amount of 3% OV-1. Either
trap is acceptable. (Note: The inclusion of OV-1 is to help
improve the desorption of certain compounds. Deletion of this
material can adversely affect the precision of benzene and
toluene analyses.)
6.1.1
The organic-free water should be used as soon as possible after it
has passed through the carbon filter bed. Trace impurities can be
picked up from even a brief exposure to lab air. Try to minimize
the number of transfers to other vessels and the time required for
each transfer.
7.2/10.1
We have been informed that the column material cited in the
Federal Register (Vol. 44) was a typing error. It should have
read 5% SP-1200 instead of SP-2100.
NOTE: We have evaluated Method 602 using SP-2100. The SP-2100,
however, appears to give a better resolution than the SP-1200.
All compounds eluted from 1 min (benzene) to as much as 8 min
86
-------
(1,2-DCB) earlier under the following conditions of analysis.
(EPA cites xylene interferences as the reason for the choice
of SP-1200.)
Column gas flow: Helium, 40 mL/min
Column: 6' x 0.085" I.D. SS packed with 5% SP-2100 and
1.75% Bentone-34 on Suppelcoport 100/120
Column program: 50°C for 2 min, programmed at 8°/min to 90°C,
with a 16-min hold
7. Note: All standards and samples are to be analyzed by purge/
trap. Determination of purging efficiency or recovery by
direct .injection is not required for this study. Method
precision and sensitivity limits will bt determined by multiple
laboratory results and do not need to be determined by indivi-
dual laboratories.
8.5 Standard quality assurance practices should be used. In the
conduct of this work, it is recommended that a blank and a
three point calibration curve be analyzed on the first day.
On following days, a blank and one point should be sufficient
if the point falls within 10% of the previously generated
calibration curve.
NOTE: The photoionization detector will show a continual loss in
response due to the deposition of high boiling compounds (includ-
ing column bleed) onto the PID lamp window. (Window cleaning
becomes necessary when MDLs cannot be achieved or when a signifi-
cant decrease in sensitivities is noted.)
8.6 For the purpose of this study do not add surrogate compounds.
9.1 Samples should be refrigerated until analysis.
87
-------
9.3 Delete (for Round-Kobin Only)
10.0 Sample extraction and gas chromatography for users of the
purge device shown in Figure 1 page 69477 of the Federal
Register, Vol. 44, No. 233/12-3-79.
10.4 Delete last sentence concerning surrogates.
10.8 We recommend a minimum of three washes.
11.1 Refer to Section 7.2 of these notes.
10.2 No duplicate analyses are required for this study.
The Notes for Section 10.3 and 10.4 have been generated using a
Hewlett-Packard 7675A P/T Sampler but also may be applicable
for other P/T devices.
10.3 Keeping an empty purge vessel or one containing organic-free
water on sampler when not in use may reduce contaminatioa.
10.4 The purge vessel design is quite different from that
described in Federal Register Method 602. The HP7675A uses
a 15-mL threaded test tube as the purge vessel. The design
allows one to change the vessel after each analysis thus
minimizing cross contamination. Blanks, standards, and
field-type samples can be introduced as per instructions
listed in 9.2 of the Federal Register or by filling to the
mark on a precalibrated purge vessel. All purge vessels
should be sealed with a Teflon®-lined screw cap if not
attached to sampler immediately after filling.
NOTE: Surrogates will not be used for Round-Robin Study.
88
-------
10.5-10.9
HP7675-A F/T Samplers.
Attach the purge vessel containing 5 mL of sample to P/T sampler.
Start the following automated or semi-automated sequence for
analysis. The following conditions have been found to give good
results:
TABLE 27. AUTOMATED (5830/40) GAS CHROMATOGRAPHS
Time,
Event min
Purge cycle 12
Post-purge cycle (pre-purge valve settings) 6
Desorb cycle 4
Vent cycle 7
Semi-Automated 7675A (Stand-Alone Version)
Initial set points are as follows:
TABLE 28. INITIAL SET POINTS
Time,
Event min
Pre-purge cycle 0
Purge cycle 13
Desorb cycle 4
Vent cycle 7
89
-------
Attach purge vessel and press Start Run on the 7675A. Set a time
of 6 min on Pre-Purge Cycle (this becomes "post purge1' time after
next step). At 1.2 minutes into run, press Stop Run followed Ly
Start Run on 7675A sampler. (Unit should now be under Pre-Purge
Timer.) During this Post-Purge Cycle, reduce Purge Time to zero
(0). At the end of the six-minute "Post Purge", the sampler will
automatically proceed through the desorb and vent cycles.
Upon completion of vent cycle, the trap is automatically cooled to
make ready for the next sample (purge vessel).
Description of Events
Purge Cycle (12 min)
\
Volatiles are purged '"rcm sample onto the Tenax® trap which is at
or below ambient.
Post-Purge Cycle (6 min)
Purge Vessel is switched out of system (flow path), and trap is
dried by maintaining a 40-mL/min dry purge for 6 minutes.
Desorb Cycle (4 min)
Trapped materials are introduced to the G.C. Column by rapidly
heating trap to 180°C while backflushing trap with an inert gas
at 40 mL/min for 4 minutes.
Vent Cycle (7 min)
Trap is reconditioned by increasing trap temperatures by 50°C (to
230°C) while venting to atmosphere (hood).
90
-------
10.1 Refer to Section 7.2 of these notes tor comments.
11.2 No duplicate analyses are required for this study.
91
-------
APPENDIX C
PRELIMINARY INVESTIGATION OF METHOD 602
92
-------
APPENDIX C
PRELIMINARY INVESTIGATION OF METHOD 602
Before initiation of the interlaboratory study of EPA Method 602,
Monanto Research Corporation (MRC) conducted an evaluation of the
method. The objective of these preliminary studies was to develop
a detailed knowledge of the Method 602 procedure before the 20
participating laboratories began their analysis effort. Any prob-
lems and solutions to problems could then be transmitted to the
participating laboratories before their work was initiated. In
addition, MRC would then be in a position to offer real assistance
to these laboratories if they experienced difficulties during the
method validation effort. The tasks in these preliminary studies
included:
• An evaluation of Method 602, including shakeaown runs of
equipment and the total analytical procedure, purge
efficiency.
• Stability studies of concentrated (spike) solutions of
the seven aromatic compounds.
• A determination of Method Detection Limits (MDL) in
interference-free water and two wastewaters.
• A determination of the analytical curves for analysis
of the aromatic compounds.
• The preparation of a summary of problems encountered by
MRC in the conduct of Method 602 and the development of
recommended solutions to these problems.
In this investigation a Hewlett-packard purge/trap device was
employed which does not meet the specifications for Method 602
(Appendix A).
93
-------
The results of these preliminary studies are summarized below.
Evaluation of Method 602 - Purgeable Aromatics
Two sets of ampuls were prepared containing the seven aromatic
compounds such that the spiked water would contain either 0.2
M9/L or 50 \ig/L of each compound. Method 602 was run using these
ampuls, and analyes of the concentrates were performed by direct
injection chromatography for future comparison as a stability
test. Any problems encountered in the conduct of the teste were
noted.
Recovery studies comparing purge/trap results to direct injection
of purgeable aromatics at the 5-pg/L level indicated purge effi-
ciencies exceeding 90 percent for all compounds (average of 97.5
percent). Purge gas volumes were 480 mL with no post-purge time.
Using post-purge cycle times of 6 and 10 minutes, the percent
recovery fell to an average of 90 percent and 86 percent, respec-
tively. The reduction of percent recovery is not necessarily
related to poor purge efficiency, because a repurge of standard
samples indicated residual content of all compounds to be less
than 1 percent of the original purge values.
Stability Studies
Stability studies of the concentrated standards in the sealed
ampuls were plagued by operational difficulties encountered with
the HNU PHotoionization Detector (PID). The detector demonstra-
ted a loss in sensitivity with time, and a new 10.2-eV UV lamp
had to be obtained to complete the stablity studies. Despite
these difficulties, the 79-day and 96-day stabilities of the
sealed ampul standards appeared to be very acceptable.
94
-------
Determination of Method Detection Limits (MDL)
The method detection limits (MDL) were determined according to
Procedure A of Revision 1.7 EMSL-Ci, dated 1-15-80. Organic-free
water and two different wastewaters were spiked and purged em-
ploying Method 602 with minor modifications. The resu] -,ant MDL
values for these three waters are presented in Table 29.
TABLE 29. SUMMARY OF METHOD 602 DETECTION LIMIT DATA
(pg/L)
compound
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Toluene
Organic-free
water
0
0
0
0
0
0
0
.2
.2
.4
.4
.3
.2
.2
Wastewater
1
>1
0
>24
0
0
0
2
.0
.2
.3
.3
.2
.2
2
>26
>120
>6
2
6
>20
>164
.4
.0
.1
Determination of the Analytical Curves
The analytical curves of each of the seven purgeable aromatic com-
pounds were determined by both Method 602 and direct injection
chromatography employing solutions at approximately 4, 7, 10,
and 100 times the minimum detection limits. Using both methods,
excellent linearity was obtaned after plotting peak area counts
versus concentration. For Method 602, the minimum correlation of
slope and intercept was 0.9994 for a single aromatic compound.
95
-------
APPENDIX. D
ANALYSES OF STANDARD SPIKING SOLUTIONS
EMPLOYED IN METHOD 602
96
-------
APPENDIX D
ANALYSES OF STANDARD SPIKING SOLUTIONS
EMPLOYED IN METHOD 602
The six concentrated purgeable aromatic standards shipped to the
participating laboratories in sealed glass ampuls were analyzed
by direct injection chromatography for each of the seven aromatic
compounds. In each case, a Perkin-Elmer Model 3920 B chromato-
graph was employed with a flame ionization detector. Three
different chromatographic columns were used: a Tenax& column for
analysis of benzene and toluene in the low concentration Youden
pair (solutions 1 and 2); a FFAP column for the remaining purge-
able aromatics in the low concentration Youden pair; and a 5% SP-
1200/5% Bentone-34 on 100/120 mesh Supelcoport column for analy-
sis of all the purgeable aromatics in the intermediate (solutions
3 and 4) and high (solutions 5 and 6) Youden-pair standards. The
instrumental conditions are summarized in Table 30.
The Tenax® column separated the methanol solvent from the aromatic
compounds, but would not. resolve the dichlorobenzene isomers. The
FFAP column resolved the isomers without significant bleed, but
the benzene and toluene peaks were lost in the methanol solvent
peak.
The results of the analyses are presented in Table 31 in terms
of the equivalent concentrations of the analytes in the water
matrices after spiking with the ampul contents.
The mean recoveries generated from the regression equation by the
twenty laboratories also support the statement that the ampul
concentrations are correct.
97
-------
TABLE 30. CHROMATOGRAPHIC CONDITIONS
00
Chroma tograph:
Columns:
Temperatures:
Column .-
Perkin-Elmer 3920B with
flame ionization
detector (FID)
6' x 1/4" stainless
Tenax® 35-60 mesh
100-150°C by 4°C/min
Injection port: 250°C
Detector: 250°C
Carrier gas: He at 30 mL/min
20' x 1/4" stainless
FFAP
60-»135°C, hold for 4
min, then 4°C/min
250°C
250°C
He at max. flow
10" x 1/8" 5% SP1200/5% Bentone 34
on 100/120 mesh Supelcoport
(stainless steel)
90°C/8 min to 115°C/20 min by
32°C/min
250°C
250°C
He at 30 mL/min
-------
TABLE 31. STABILITY DATA
Ampul TV AV TV AV TV AV TV AV TV AV TV AV
Benzene 2.2 2.5 3.0 3.1 46 44 54 53 450 330 550 444
Chlorobenzene 2.2 2.6 3.0 3.5 46 46 54 53 450 474 551 600
1,2-Dichlorobenzene 2.2 2.4 3.0 3.6 46 45 54 53 449 504 600 636
1,3-Dichlorobenzene 2.2 2.8 3.0 4.1 46 41 54 51 450 486 550 630
1,4-Dichlorobenzene 2.2 2.4 3.0 3.2 46 48 54 58 450 524 550 666
Ethylbenzene 2.2 2.3 3.0 3.0 46 38 54 44 452 404 551 600
Toluene 2.1 2.3 3.0 3.2 46 44 54 53 450 402 550 540
Note: TV = true value, pg/L; AV = analytical value, M9/L-
99
-------
APPENDIX E
RAW DATA: METHOD 602
100
-------
TABLE 32. RAW DATA FOR BENZENE ANALYSIS BY WATER TYPE
DISTILLED WAItK
[AC WATEK
SUKFACE WATEK
WASTE WAFEK 1
AMPUL NO:
TMOE CONC:
LAB NUMBLK
1
2
3
4
b
6
7
8
9
10
11
12
13
H
Ib
16
17
1«
19
20
1
2.20
2.39
3.28
1.64
2.37
1.28
2.14
2.02
1.36
6.bb*
2.02
1.91
•
11.90*
2.b8
2.10
3.19
9.b9*
3.bO
4.2/'
2.86
2
3.00
2.89
4.76
2.13
3.01
1.71
2.21
2.92
l.BH
8.48
2.79
2.9b
*
13.90*
4.07
6.62
4.72
12.10*
1.80
b.7b
2.97
1
2.20
2.26
1.00
l.ll!
2.06
2.37
2. XI
1.98
l.b/
S.?b
2.07
2.20
I.JO
H.6X
5. 38
3.2H
1.23'
6.66
1.29
4.96
I.b2
2
3.00
2.71
3.86
1.76
2.7b
j.i 3
2.93
2.87
2.03
b.63
3.10
2.28
*
9.b7*
b.96
2. HO
1.60*
6.87
2.26
b.20
2.6b
1
2.20
2.26
4.09
1.H4
2.22
2. Ob
2.?9
'£. \t
I.b2
4.64
2.09
1.74
*
1.37
3.48
71.00*
I.b4*
7.19*
3.67
2.04
2.11
2
3.00
2.49
4.b7
2.06
2.91
2.6b
?. > \
2.99
1.92
4.97
2.71
3.bj
3.12*
14.70*
3.b8
82. UO*
0.00*
8.2/*
2.88
2.46
3,4b
1
2.20
0.81
2.32
1.6?
1.H3
j.lb
2.71
3.7b
2.b4
9.16'
2.26
1.00
<
1.31
1.10
0.00'
1.69
4.^2
3.07
1.33
O.bb
2
3.00
0.78
4.41
0.77
2.bO
1.64
4.14
b.>b
i. bo
3./H
0.48
l.ll
*
13.40*
3.2b
0.72
2.89
4. HI
3.94
3.11
2.14
1
2.20
0.83
2.42
0.74
1.82
2.29
b.3b
2.17
1.07
0.00'
3.02
1.38
b.20
19.00'
O.B6
7.00'
2.19
2.30
b.42
1.64
2.81
WASTE WATEK 2
2
3.00
0.34
3.43
0.69
2.38
3.6;
3.2H
0.00*
3.24
0.00*
3.06
2.08
0.00*
WASTE WAfEK 3
l.bb
4.13*
/.IO
3.40
5.92
O.O'I
0.00*
1
2.20
0.77*
2.89
1.41
2.16
2.00
1.60
0.00*
3.32
1.33
8.9b*
4.61
0.00*
3.1b
4.70
2.H7
1.81
1.38
2
3.00
0.7b*
3.i8
2.24
2.4b
2.16
1.64
3.14
2.24
0.00*
b.Ob
0.00*
*
16.10*
b.30
0.00*
3.1b
6.44
b.92
1.70
2.63
-------
TABLE 32 (continued)
OIS1ILLEO WATEK
TAP WATEK
SOKFACE WATEH
UASTE WAItK 1
WASTE UAFEK 2
WAS It WAftK 3
AMPUL NO:
TKUt CONC:
LAU NUMBEK
1
2
3
4
b
6
7
8
9
10
11
12
13
14
Ib
16
i;
18
19
20
3
46. 00
33.70
SO. HO
128.00'
43.10
46.40
40.00
41.70
43.30
•J9.20
48.70
4b.4U
163.00*
12b.OO*
44. ao
4U.UO
3b.70
94.30*
bH.bU
41.60
33.10
4
b4.UO
41.30
b4.60
111.00*
b2.70
48.60
42.00
b2.20
41.00
b8.30
bl.OO
40.10
400.00*
128.00*
bl.UO
63.20
37.i>0
37.30
61.10
46.10
42.20
3
46.00
34.90
45. bO
126.0(1*
46. OU
44. 70
40. bO
41.30
47.20
b3.40
46.30
bb.OO
IbO.OO*
81.00*
47.90
b7.20
34.40*
107.00*
6U.30
J/.70
34.70
4
b4.uO
44.00
b6.80
127.00*
b3.bO
66.00
48.40
49.00
39.80
63.40
b3.00
41.10
200.00*
81.40
bl./O
6H.6U
26.80*
77.00
62.70
6b.lO
49.00
3
46.1'0
30.'."
4t>.10
19.10*
47.10
37.10
40.00
4b.30
bU.10
b3.00
bl./O
46.70
169.00*
127.00*
44. HO
Ib9.0l;«
jJ.UO*
bb.bO
b2./0
3b.HO
41.70
4
b4.00
40.10
bO.70
20.70*
bb.10
43.31)
4H.90
bl.30
44. iO
bo. 20
b8.90
41.30
30b.OO*
124.110*
bl.40
87.00*
3U.OO*
b6.bO
bb.W)
b3.20
4b.70
3
46.00
37.70
42.30
19.10
46. bO
47.411
42.10
49.20
49.20
bl.bO
bb.bO
3b.20
IbO.OO*
63.10
bO.80
b4.40
24. 70
b 1.1)1)
62.90
29. bO
19.10
4
b4.IJO
3b.bl)
4U.4D
21.00
b4.HO
b3.00
bO.OO
bb.20
43.40
b2.30
44. bO
33. HO
1H8.00*
47.00
bO.10
b2.40
37. bO
4b.70
/'4.20
3b.20
21. bO
3
4b.UO
3H.20
39.60
1H.4G*
41.80
41. bO
44.70
3H.60
4b.O')
49.0C
bb.OO
40.00
18H.OO*
9b.8l)'
4b.OO
b4.30«
33.10
41.90
49.40
3b.OO
4rt.70
4
b4.00
33.00
4b.40
20.00
b3.00
4/.90
bb.80
44.10
42.00
bb-80
4/.40
41.60
363.00*
23.70
42.40
71.00*
2b.40
39.00
bb.10
39.90
b9.70
3
46.00
32.40*
4b.bO
IH.20
47.80
40.60
41.60
43.80
4b.lO
61.90
bO.60
40.00
104.00*
121.00*
44.10
bH.bO
2b./0
49.30
M.90
30.10
44.00
4
b4.00
42.20*
b4.30
2l.bO
b4.bO
44.10
48.90
b3.00
39. bO
68.00
b2.00
31.30
438.00*
li/.OO*
b3.40
64.30
«b.90
b/.OU
6b.bO
3b.lO
39.10
-------
TABLE 32 (continued)
DISTILLED WATEK
IAP WAUK
SOKFACE WATIK
WASTE WATEH 1
WASTE WATEK 2
WASTE WATCH 3
AMPUL NO:
TKUE CONC:
LAB NUHBtK
1
2
3
4
b
b
7
8
9
ID
11
12
13
14
Ib
16
17
la
19
20
b
4bU.OO
33b.0()
blb.OU
609.00
44U.UU
47b.UU
324. UU
43b.UU
b/8.00
244. UU
4/6. UU
364. UU
IbUO.OO*
741.00*
470.00
b28.00
402.00
347.00
464. UU
3/b.UO
227.00
b
bbU.OO
402.00
bbb.OO
b9b.OO
b38.0U
460. UU
404.00
b44.00
bib. 00
276.00
b48.00
4b2.00
137b.OU*
bib. 00*
bb7.00
b%.00
398. UU
279.00
631.00
429.00
497.00
b
4bO.OO
.jbO.OO
bb7.00
b/b.OO
439.00
3S9.UU
3H/.UO
417.00
bSb.OO
228.00
4bb.OO
3b2.L'0
237b.UO«
3/8.00
4bH.IIO
640. IK)
292.00*
4J6.UU
410. UO
327.00
38fc.oO
6
bbO.UO
3b4.00
62/.UU
718.00
b38.00
446.01)
393.00
b42.0U
b28.00
283.00
b02.00
443.00
IbOO.OO*
400.00
b70.00
79b.OO
382. UO*
46H.UU
481.00
3b9.UO
47b.OO
b
4bO.OO
289.00
49b.llO
63H.UO
44H.IIU
412. OU
3b2.;;u
424.UO
b43.UO
244. UO
382. OU
3bb.UO
2UUO.UO*
b2b.OO
4bt..l)0
723.00*
281.00*
3Ub . 00
382.00
414.00
36b.UO
6
ObO.OO
3b3.00
t39.00
tilb.OU
b48.()0
b40.00
389. t)')
b22.00
b2/.00
2'jU.UU
b'j2.UU
418.00
I7b0.00*
b44.00
b4b.OO
Bbb.OO*
17 1. 00*
330.00
4b7.00
4bl.OO
374.00
b
460.00
b!9.0U
4llb.OO
b92.0U
411.00
4?b.UO
392.00
3b4.UO
Dfil.OU
333.00
466. UU
3/4.00
13/b.OO*
31b.OU
486.00
6IH.UO
4b7.00
28/.00
427.00
326.00
42/.00
b
bbO.UO
J48.00
bt>8.00
'j^b.UO
bJ7.00
41)8.1.0
419.00
bJ8.l)U
b24.UO
Jbl.OO
t)67.UO
4b9.00
iM/b.OO*
JU3.00
497.00
.'83.00
4J4.UO
310. (ID
b4b.OO
3l!b.OO
b!2.00
b
4bO.OO
317.00
4bJ.OO
6lh.OO
4b/.OU
434.00
37^.00
406. OU
b44.00
322.00
448.UO
3b4.00
IbOU.OO*
13b.OO
b!2.UO
6/b.OO*
388.00
229.00
4/0.00
2/9.00
43J.OO
b
bbO.OO
363.00
b43.00
732.00
bbl.OU
bOl.OO
393.00
493.00
b36.UO
403.00
b.'8.00
427.00
137b.OO*
100.00
b98.00
/86-OU*
b83.UO
?b?.00
bb2.UO
382. UU
499.00
b
4^0.00
2bb.OU*
b!3.00
bb7.00
448.00
431.00
3/0.00
43b.OO
bOb.OO
342.00
401. OU
3b8.00
13/b.OO*
771.00*
4/b.OO
bbl.OO
331.00
312.00
399.00
3/3.00
3/9.00
6
bbO.OO
3b4.00*
639.00
Obb.OO
b3b.OO
b32.00
393.00
b39.00
b03.00
401.00
b24.00
422.00
IbOO.OO*
816.00*
6Ub.CO
801.01!
380.00
332.00
4i!b.OO
409.00
499.00
-------
TABLE 33. RAW DATA FOR CHLOROBC^ZENE ANALYSIS BY WATER TYPE
DISTILLED UATEK
TAP WATEK
SUKFACE UATEK
WASTE WATEK 1
WASTE WATEK 2
AMPUL NO:
TKJE CONC:
LAB NIMBEK
1
2
3
4
b
6
7
a
9
10
11
12
13
14
Ib
16
17
ID
19
20
1
2.20
2.13
2.11
2.08
2.21
1.79
2.1,2
2.07
1.56
6.34*
2.11
0.97
2.97
2.80
2.81
2.b5
2.30
9.90*
1.89
2.41
2.2b
2
3.00
2.75
3.62
2.64
2.99
2.32
2.62
3.16
2.02
8.26*
2.73
2.97
2.37
5.44*
3.37
3.33
2.40
12.40*
1.3b
2. 68
2.92
1
2.20
2.21
1./5
1.75
2.30
1.56
1.69
3.67
1.49
4.10
2.36
1.08
2.97*
1.62
2.83
2.95
0.98*
16.60*
2.59
1.81
3.37
2
3.00
2.61
2.52
2.54
3.22
2.02
2.62
3.28
2.14
6.78*
3.60
1.8b
3. ID*
1.95
4.23
2.75
0.82*
17. HO*
3.0*
2.bl
2.96
1
2.20
2.25
2.72
1.51
2.13
2.09
1.69
2.10
1.75
4.01*
2.45
0.96
Z.b7*
1.49
2.83
2.12
1.83
13.70*
1.31'
1.5'.
2.?2
2
3.UU
2.46
3.60
2.52
3.18
3.UO
2.46
3.U1
2.13
6.26*
2.^1
1.18
3.37*
1.H2
3.73
2.87
1.72
15.60*
U.HI
2.U3
3.11
1
2.20
).6b
J.30
0.60
0.00*
0.00*
2.46
1.30
2. 20
0.00*
2.30
7.80
0.00*
0.00*
2.20
9.30*
3.0U
8.70
0.00*
O.bl)
O.OU*
2
3.00
0.00*
7.40
0.00*
0.00*
0.91
3.07
4.40
0.00*
0.00*
0.00*
3.70
0.00*
7.H4
7.20
1 1 . 30*
14.00
14.20
0.00*
0.00*
0.00*
1
2.20
0.00*
3.00
0.00*
0.00*
0.00*
C.'JO*
o.eo*
38.00
0.00*
o.ou*
52.00
O.OU*
0.00*
3.00
46.00*
0.00*
21.00
O.OU*
0-00*
0.00*
2
3.00
0.00*
11.00
o.oo*
0.00*
0.00*
0.00*
0.00*
0.00*
o.oo*
2.00
14.00
O.uO*
0.00*
6.00
59.00*
35.00
37.00
0.00*
0.00*
o.oo*
1
2.20
1.72
0.91
1.44
3.42
2.32
1.80
0.32
0.00
3.69
4.80
1.81
5.74
3.69
2.93
3.14'
2.05
5.10
0.65
1.61
1.71
WAS It WATEK 3
2
3.00
1.50
1.25
2.07
3.91
2.63
o.oo*
2.46
2.90
0.00*
8.90*
3.09
6.34*
4.98
3.17
3.96*
,52
10
.21
.52
2.56
-------
TABLE 33 (continued)
UlSTIlUl) WATIK
TAP WATtK
SOKFACt WAItK
UAblt WAFIK 1
WATEK 2
o
m
AMPUL NO:
TrtUE CUNC:
LAU NUMbtK
1
2
3
4
5
b
7
a
9
10
n
12
13
14
Ib
16
17
ia
19
20
3
46. UU
41.10
4b.20
86. ;o*
44.90
48. bO
44.30
41.60
4b.60
bO.50
46.30
42.00
172.00*
63.00
S2.60
43.60
26.70
101.00*
3h.2i:
40. BO
43. BO
4
b4.00
44.10
bO.90
bl.DO
b3.30
49.40
bU.OO
SO. 40
41.40
66.40
b7.10
43.10
182.00*
67. HO
6U.40
62.70
42.00
4?. BO
3K.HO
44.70
bl.10
3
46. 00
.14.60
39.90
84.00*
4b.HO
43.60
42. SO
41.20
47.30
69.30
4b.40
bH.bO
160.00*
4b.lO
b4.40
bb./O
31.60*
103.00*
b4.20
37.60
39.30
4
b4.00
46.20
b2.00
B9.bO*
b3.40
b3.30
b2.90
46. bO
3H.OO
6U.10
b9.60
43.90
IBb.OO*
bO.10
61.10
60.70
21.40*
76.10*
bO.20
61.30
bl.OO
3
4b.OO
34. HO
40.20
23.40
46.10
39. 90
42. MO
41.90
bl.40
62.90
b3.40
4b.20
1HJ.OO*
61.3!)
53.00
bb.30
36.60
91. bO*
4b.90
3/.60
46.00
4
b4.00
41.40
47. bO
2b.70
b3.90
45.10
54.30
48. UO
48.30
63.90
61.40
43.80
196. UO*
63.90
60.90
60.80
29. HO
96.40'
bb.30
b2.40
49.70
3
46.00
71.20
41.10
19.60
3b.30
44.40
44.30
4/.40
40.60
37. bO
bb.20
b2.00
23b.OO*
34.40
b/.40
64.70*
3b.bO
4H. 70
44. bO
28.00
3i.au
4
b4.C'>
b2.00
49.90
20.20
43.40
b2.lO
bb.70
bb.20
41.30
3H.10
60.30
bl./O
263.00*
32.10
64.80
73.20*
b4.IIO
44.40
38. bO
2H.60
37.00
3
46.00
77.70
23.00
111.00
33. bO
21.60
43.30
9.00
73.00
28.20
39.00
61.00
146.00
106.00
60.00
123.00*
62.00
27.00
0.00*
38.00
30.00
4
b4.00
3?. 70
27.00
90.60
29.70
23.60
62.30
13.00
4b.OO
4b.8l<
b4.00
6U.OO
103.00
56.40
61.00
118.00*
16. OU
14.00
0.00*
43.00
29.00
3
46.00
Ib.lO
•19.80
24.10
«9.bO
42.40
43.30
4J.bO
bb.70
b7.80
60.30
42.20
138.00*
Sb.OO
D4.80
69.00*
41.20
36.80
47.30
31.70
4X.OG
4
b4.00
b6.bO
44. 7'J
28.40
54.20
4b.30
49.00
b3.0U
bH.fO
60. 0
44. i')
bl.4 '
141.00*
45.20
64.00
62. 4J*
61.10
40. iu
U5.60
3D.30
42.70
-------
TABLE 33 (continued)
DISTILLED UAILK
TAP UATtK
MIKFACt WATLK
WASTL WARM 1
WASIE UATLK 2
WASTE UATEK 3
AMPUL NO:
TKUE CUNC:
LAB NUHUEK
1
2
3
4
b
6
7
«
9
10
r.
12
13
14
Ib
16
i;
ia
19
20
s
450.00
366.00
414.00
522.00
446.00
438.00
4UU.OU
437. UO
894. Ou*
323.00
469.00
375.00
mo.oo*
531. OC
S04.00
457.00
430.00
746.00*
499.00
388.00
418.00
6
551.00
438. UU
4bl.OO
bbl.OO
b4b.OO
516.00
40U.OO
b4b.OO
*60.00
354. OC
508.00
485.00
1861.00*
475.00
622.00
572.00
40H.OO
b88.00
720.00
426.00
447.00
b
4bO.OO
298.00
43b 00
b02.00
443.00
392.00
4.<4.00
416.00
91b.OO*
296.00
4/0.00
404.01)
1900.00*
3S4.00
4U3.00
bl3.00
^67.00*
bBl.OO*
416.00
341.00
2U6.00
6
bbl.OO
406.00
b03.00
bb9.00
b46.00
468.00
<00.00
b3H.OO
b44.00
360.00
b68.00
499.00
2316.00*
370.00
621.00
634.00
413.00*
b4L'.00*
479.00
3/8.00
41b.OO
b
4bO.OO
312.00
39H.UO
4HI.UO
4b^.OO
41H.OO
400.00
402.00
863.00*
2/4. (10
369.00
401.00
316H.OO*
428.00
498.00
529.011
291.00
383.00
342.00
431.00
299.00
6
bbl.OO
384.00
b04.00
b/1.00
bbO.OO
bOb.OO
391.MO
blH.OO
534.00
31; 7. oo
418.00
bl'4.00
326 /'.UO*
458.00
6U5.00
6U.OO
bi/.OO
415.00
4H1.00
4//.00
406.00
b
4SO.OO
476.00
341.00
494.00
406.00
399. 'JO
451. OJ
360.00
8/4.00*
311.00
409.00
419.00
i:039.00«
152.00*
515.00
515.00*
440.00
318.00
453.00
340.00
402.00
0
bbl.OO
533.00
485.00
540.00
533.00
4hO.OO
4 36 . 00
52/.00
62/.00
348.00
496.00
b!3.00
24b5.0(l*
152.00*
596.00
653.00*
692.00
37?. 00
49/.00
410.00
44/.00
b
4VJ.UO
667. CO
3b3.00
307.00
461.00
4?1.00
429.0'J
3W.OO
823.00*
289.00
424.00
424.00
2768.00*
358.00
522.00
514.00*
370.00
268.00
532.00
215.00
397.00
6
551.00
S81.00
548.00
340.00
545.00
501.00
376.00
454.00
519.00
424.00
4/t.OO
498.00
2826.00*
239.00
629.00
565.00*
602.00
277.00
693.00
371.00
407.00
b
450.00
416.00
395.00
4b«.00
452.00
414.00
406.00
436.00
863.00*
487.00
390.00
406.00
149M.OO*
396.00
516.00
546.00*
317,00
317.00
397.00
411.00
364.00
6
551.00
469.00
486. UO
537.0')
543.00
509.00
410.00
539. UO
578.00
473.00
4b2.00
490.0D
2277. 00*
45/.00
655.00
664.00*
587.00
352.00
452.00
422.00
448.00
-------
TABLE 34. RAW DATA FOR 1,2-DICHLORO3ENZENE ANALYSIS BY WATER TYPE
WATEK
TAP WAVER
SUKKACt WATEK
WASH WATEK 1
WASH. UAUK 2
WASTE UATtK 3
AMHOL NO:
TKOE CONC:
LAB fUMHEH
1
2
3
4
5
6
7
d
9
10
11
12
13
14
Ib
16
17
18
19
20
1
2.20
1.93
1.80
2.60
2.16
1.53
2.82
2.31
1.29
4.72
2.3C
0.00*
12.30*
1.47
2.28
3.88
6.12
11.50*
5.11
0.00*
2.21
2
3.00
2.62
3.10
3.37
2.89
1.83
2.59
2.93
1.99
6.37'
2.76
0.00'
12.30'
1.91
2.eo
4.54
4.68
9.70'
0.00'
O.UO'
2. HI
1
2.20
1.97
2.08
2.17
2.06
2.42
1.88
3.H5
1.54
3.99
2.58
0.00*
5.48*
1.39
2.06
4.03
0./8*
3.38
2.69 -
0.00*
2.92
2
3.00
2.4?
3.11
3.32
2.84
:.'.33
2.59
2.82
1.80
1.51
3.50
O.UO1
5.48'
2.65
3.32
3.bb
0.31'
3.57
3.36
0.00'
3.41
1.97
2.65
1.76*
2.12
2.19
2.18
1.H3
1.77
5.65*
2.35
0.00*
4.11*
1.33
2.33
3.70*
2.18
6.56*
3.53*
11.00*
i. 17
2
3. 00
2.41
3.61
1.58*
2.91
3.02
2. by
2.95
2.t>0
9.71*
2.U7
0.00"
4.11*
l.HU
3. Ob
4.48*
2.13
4.96
5.29
0.00*
2.61
1
2.2C
1.38
0.00*
i./;
1./8
!.IK
2.47
2.32
1.H3
10.60*
2.74
0.00*
2.74*
2.32
2.17
b.60*
3.67
1.38
0.00*
0.00*
2.03
2
3.00
1.48
3.%
2.24
2.3b
3.11
3.18
3.07
2.27
7.b3
8.30
0.00*
b.48*
2.b3
3.H7
4.61*
3.23
b.60
O.OU*
1.9M
2.61
1
2.20
1.25*
3.04
1.27
2.07
1.82
4.12
2.00
1.92
0-00*
6.26
O.Ob
4.11*
17.60*
3.3b
6.84
2.63
13.10*
2.44
0.00*
1.17
2
3.00
1.02*
4.23
2.b3
2.55
2.01
2.94
2.bl
2.11
0.00*
b.93
• 0.00*
5.33*
18.60*
4.93
3.64
2./M
0.00*
3.66
0.00*
b.6b
1
2.20
1.19
2.04
1.41
1.81
2.34
4.1,9*
l.bl
I.b6
0,31
7.?C*
0.00*
4.11*
0..12
2.06
3.b9*
2.6b
1.63
0.00*
O.UO*
2.20
2
3.00
O.b7
2.89
i.64
2.77
3.12
1.30
2.64
2.05
0.00'
10.90'
0.81
b.48'
1.82
2.78
4.40'
3.41
1.99
0.23
0.00'
3.63
-------
TABLE 34 (continued)
DISTILLED UATEK
TAP UATtK
SUKFACE WATEK
WASTE WATEH 1
WASTE WATEK 2
WASTE WATEK 3
O
OD
iVMPUL NO:
T
-------
TABLE 34 (continued)
DISTILLED WATEK
TAP UATEK
SURFACE WATEK
WASTE WATEK 1
WASTE WATEK 2
WASTE WATEK 3
O
vO
AMPUL NO:
TKUE CUNC:
LAB NUMUEK
1
2
3
4
b
6
7
8
9
10
11
12
13
14
15
16
17
IB
19
20
5
440. UU
301. 00
4Z7.00
492.00
431.00
419.00
436.00
430.UO
bbO.OO
328.00
610.00
611.00
1356.00*
b42.00
427.00
512.00
408.00
432.00
43b.OO
384.00*
328.00
6
6UU.OO
3b9.00
468.00
476.00
530.00
bb9.00
400.00
b59.00
SIB. 00
376. (JO
700.00
b87.00
1356.00*
473.00
546. UO
6b2.00
33H.OO
313.00
775.00
41U.OO*
374.00
b
449.00
267.00
419.00
42b.OO
436.00
431.00
4b2.00
408.00
b73.00
324.00
b92.00
387.00
1356.00*
352.00
406.00
5b3.00
234. OU*
b64.00
403.00
361.00
333.00
6
600.00
344.00
487.00
490.00
b26.00
491.00
39b.OO
631.00
b47.00
380.00
729.00
607.00
1695.00*
361.00
b!3.00
693.00
337.00*
453.00
bOl.OO
39H.OO
340.00
b
449.00
263.00
398.00
342.00*
447.00
431.00
400.00
392.00
bb4.00
394.00
507.00
444.00
Ib82.00*
376.00
434.00
b74.00*
22b.OO
392.00
353.00
4bU.OO
232.00
6
600.00
313.00
504.00
437.00*
640.00
548.00
384.00
507.00
543.00
357.00
826.00*
698.00
1921.00*
432.00
615.00
698.00*
444.00
476.00
491.00
615.00
295.00
5
449.00
257.00
421.00
361.00
408.00
459.00
472.00
306.00
671.00
402.00
715.00
488.00
1682.00*
137.00
473.00
534.00*
440.00
324.00
427.00
368.00
338.00
6
600.00
476.00
472.00
430.00
516.00
606.00
405.00
622.00
535. UO
382.00
796.00
592.00
1808.00*
l?a.oo
5 30. Or,
689. UO*
581.00
414.00
531.00
408.00
372.00
b
449.00
295.00*
430.00
363.00
428.00
448.00
440.00
407.00
619.00
401.00
631.00
624.00
1469.00*
621.00
444.00
572.00
328.00
264.00
509.00
296.00*
34S.UU
6
600.00
374.00*
636.00
461.00
519.00
553.00
411.00
491.00
565.00
513.00
694.00
633.00
1695.00*
427.00
666.00
697.00
534.00
421.00
634.00
410.00*
343.00
5
449.00
377.00
407.00
34b.OO
416.00
442.00
421.00
429.00
b77.00
452.00
485.00*
591.00
1469.00*
433. GO
453.00
^85.00*
271.00
376.00
41". 00
36i .00*
32 / .00
6
6 0.00
315.00
502.00
440. 00
508.00
549.00
408.00
534.00
497.00
364.00
638.00'
601.00
1921.00'
4/2.00
568.00
715.00'
431.00
416.00
608.00
134.00'
361.00
-------
TABLE 35. RAW DATA FOR 1,3-DICHLOROBENZENE ANALYSIS BY WATER TYPE
DISTILLED wATtK
FAR WATtK
SUKtACL UATEK
WASTE UATEK 1
WASTE WATEK 2
HASTE WATEK 3
AMPUL NO:
TKUE CONC:
LAB NUMBEK
1
2
3
4
5
6
7
8
9
10
11
12
13
14
ib
16
17
18
19
20
1
2.20
2.08
1.76
2.40
2.38
l.bl
1.66
2.08
1.44
9.b3*
2.26
0.00*
b.41*
1.74
2.63
2.87
2.63
11.00*
4.98*
1.47
2.20
2
3.00
2.73
3.29
3.22
3.10
1.80
2.28
3.09
1.88
10.70*
2.60
0.03*
6.76*
2.28
3.47
3.46
4.18
6.70*
2.28
2.04
2.83
1
2.20
2.1b
1.92
2.22
2.26
2.34
I.b9
4.46
1.64
11.40*
2.09
0.00*
4.06*
1.38
2.b9
3.6b
1.60*
9.14*
2.28
1.60
3.18
2
3.00
2.bb
2.70
3.23
3. Ob
2.82
2. 48
2.88
2.2b
b.3b*
3.10
0.00*
4.06*
1.74
3.96
2.68
1.3b*
9.94*
2.91)
2.39
3.bl
1
2.20
2.18
3.02
1.6V
2.34
1.97
1.66
2.20
1.24
6.19
2.b3
0.28
3.38'
1.39
2.97
3.14
3.62
b.»6
2.61
1.60
1.97
2
3.00
2.43
3.9b
1.87*
3.11
2.8b
2.28
2.87
2.4b
9.61*
2.82
0.33
4.06*
1.77
3.61
3.b6
3.29
b.b7
3. Ob
2.b9
2.6b
1
2.20
1.44
0.00*
0.00*
0.00*
0.00*
0.00*
3.78
0.00*
0.00*
1.93
1.8b
0.00*
0.00*
3.90
6.bO
11. bO*
*
4.40
0.00*
0.00*
2
3.00
0.00*
9.bO
O.OU*
0.00*
0.00*
0.00"
4. HO
18.00
0.00*
6.90
2.14
0.00*
20. HO
3.80
8./0
18.90
*
0.00*
(1.00*
0.00*
1
2.20
1.47*
b.13
1.6b
2.24
1.14
0.00*
3.bb
3.38
0.00*
2.62
2.44
2.70*
23.111*
3.4(1
8.6b*
2.62
13.9(<*
b.8H
l.SM
1.42
2
3.00
1.41*
7.46*
2.30
2.81
1.80
0.00*
2.44
3.33
0.2b
0.00J
0.00*
4.43*
2b.90*
4.32
3.73
1.4b
*
10.10*
2.36
3.93
1
2.20
1.34*
2.08
2.04
2.21
1.69
0.96
1.67
1.24
1.44
3.24
0.00*
0.00*
2.71
2.70
3.6b*
3.99
2.67
2.29
0.00*
1.74
2
3.00
1.26*
3.31
2.0/
17
31
17
BO
76
0.00*
34
07
76*
00
08
21*
3.72
2.b7
3. Ob
0.00*
2 90
-------
TABLE 35 (continued)
OISTILUU WATEK
TAP WATEK
SOKFACE WATEK
WASTE WATEK 1
WASTE WATEK 2
WASTE WATLK 3
AMPUL NO:
TKUE CUNC:
LAB NUMBEK
1
'I
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
It)
19
20
3
46. DO
42.60
46.10
6U.OO
46.40
42.60
44.10
41.30
43.40
54.70
47.80
44.90
187.00*
68.30
52.30
40.70
23.30
74. 7U
48.50
13.10
40.50
4
b4.UO
4/.00
52.40
62.10
56.00
46.10
bU.UO
52.20
4U.bO
68.30
47.80
bU.UO
2U1.00*
68.30
61.50
60.70
39.40
3D. DO
54.20
49. HO
45. yi)
3
40.00
34.90
41.50
57.00
48.50
37.90
42.30
41.20
4/./H
59.10
46. BO
46.90
169.00*
45.40
53.60
4U.10
29.00*
106.00*
43.80
40.80
46.10
4
54.00
48.80
53. 80
64.20
56.70
46.10
48.80
47.60
46.60
68.10
52.30
54.00
222.00*
50.20
62.00
57.30
19.50*
75.40*
50.50
69.3l>
50.60
3
46.00
35.10
42.10
34. /O*
47.50
40.30
41.20
43. HO
42. 4J
59.30
40.40
49.10
180.00*
63.50
53.60
50.90
43.70
49.20
43.40
41.00
43.70
4
54.00
44.20
48.80
38.50*
57.00
47.50
52.90
49.80
41.80
67.00
46.70
52.20
318.00*
62.60
62.00
5«.00
31.40
51.60
61.70
58.60
50.20
3
46.00
132.50*
42.30
31.70
44.00
41.50
42.50
67.50
68.00
21.70
46.70
64.90
291.00*
37.00
58.40
48.60
51.00
8.90
244.00*
27.90
25.80
4
54.00
1J7.00
56.50
32.40
48.60
45.10
57.60
53.80
53.00
42.00
62.10
76.30
347.00*
33.40
66.40
55.60
94.00
19.50
267.00*
32.20
34.30
3
46.00
37.50*
45.30
37.90
44.30
42.50
42.50
42.30
42.90
45.80
43.80
49.30
312.00*
28.00
56.20
52.50
38.10
42.70
52.30
40.00
43.10
4
54.00
36.10*
43.30
42.20
54.30
49.40
90.00*
50.00
46.10
53. 7.0
49.00
54.0'!
173.00*
32.30
65.80
58.00
31.80
40.00
65.10
50.50
50.30
3
46.00
34.80*
43.50
37.10
47.80
42.00
42.50
46.80
49.30
43.20
47.30
42.80
208.00*
43.40
55.30
64.80*
38.70
41.40
51.80
32.80
41. 20
4
54.00
43.60'
48.00
48.90
54.40
4?.dO
48.70
55.30
49.70
46.90
43.30
66.40
166.00'
49.40
65.00
62.20'
71.80
48.50
69.60
39.00
45.10
-------
TABLE 35 (continued)
DISTILLED UATLK
TAP UATLK
SUKFACL UATEK
WASIt UATEK 1
UASTE MATLK 2
WASTE UATtK 3
AHPUL NO:
TKOE CONC:
LAB NUMUEK
1
2
3
4
b
6
7
8
9
10
11
12
13
14
Ib
16
17
18
19
20
b
4bO.OO
33.60*
441.00
bOl.OO
460.00
434.00
416.00
443.00
613.00
307.00
392.00
444.00
180b.OO*
b!2.00
4b4.00
437.00
449.00
4bO.O!)
b()8.00
409.00
320.00
b
bbO.OO
411.00
492.00
480.00
bbb.OO
bJO.UO
396.00
b//.00
bb8.0U
343.00
426.00
b/2.00
1736.00*
466.00
b82.00
b84.00
404.00
344.00
792.00*
431.00
3b4.00
b
4bO.OO
2/9.00
4b6.00
43b.OO
4b8.00
393.00
429.00
423.00
64b.OO*
298.00
3/b.OO
446.00
1666.00*
316.00
434.00
49/.00
24b.OO*
6Ul'.00*
40b.OO
398.00
3i?0.00
6
bbO.OO
370.00
b20.UO
b03.00
b64.00
4b2.00
392.00
b47.00
b/4.00
346.00
48/.00
bi(8.00
2291.00*
3b8.00
bb3.00
630.00
418.00*
b!6.00*
bOb.OO
42/.00
326.00
b
4bO.OO
28b.OO
4b2.00
3b/.00*
4/3.00
41b.OO
408.00
430.00
642.00
377. !M)
3b3.00
480.00
2013.00*
39/.00
461.00
bl'f.OO
2b/.00
414.00
341.00
49!>.00
223.00
6
bbO.OO
339.00
b2H.OO
442.00*
t-82.00
bOl.OO
392.00
b32.00
b81.00
336.00
4f,3.00
b8I.OJ
2429.00*
4MI.OO
b49.00
636.00
bl)4.00
4/0.00
4H/.00
b60.00
27/.00
b
4bO.OO
1670.00*
413.00
368.00
413.00
418.00
444.00
419.00
64b.OO
280.00
3b3.00
b34.00
2083.00*
o0.30
49b.OO
41.6.01)
463.00
331.00
614.00
388.00
32b.OO
b
bbO.OO
16bO.OO*
481.00
429.00
bbO.OO
4hD.Hl)
407. 00
bOl.OO
b32.00
293.00
42b.OU
602.00
2430.00"
80.30*
bbb.OO
610.00
64/.00
40/.00
/23.00
433.00
3bl.OO
b
4bO.OO
302.00*
42/.00
3/9.00
4/7.00
427.00
417.00
41b.OO
b99.00
3b/.()0
41'J.U'J
b40.00
18/4.00*
bfcH.OU
b()8.00
b22.00
3bb.OO
206.00
bl8.00
330.00
333.00
6
bbO.OO
369.00*
b49.00
471.00
583.00
b21.00
384.00
b08.00
b29.00
498.00
413.00
606.0(>
2290.00*
430.00
634.00
636.00
bbO.OO
288.00
647.00
466.00
322.00
5
4bO.OO
402.00*
408.00
367. 00
467.00
403.00
407.00
448.00
b02.00
4D3.00
310.00
bMJ.OO
19*3.00*
42b.OO
4//.00
b30.00*
300.00
361.00
411.00
430.00
322.00
6
bbO.OO
328.00'
b2b.OO
4/3.00
bb..OU
b09.00
4U'!.00
b49.00
b82.00
366.00
398.00
b42.0U
i>44H.lilJ'
448.00
bOb.UO
6b2.l'>')'
bU2.0C
407.00
bll.OO
460.00
343.00
-------
TABLE 36. RAW DATA FOR 1,4-DICHLOROBENZENE ANALYSIS BY WATER TYPE
DISTILLED WATEK
TAP WATEK
AMPUL NO:
TKUE CONC:
LAB MUMBEH
1
2
3
4
b
6
7
8
9
10
11
12
13
14
Ib
16
17
18
19
20
1
2.20
2.02
1.4b
2.b5
2.26
1.43
2.00
1.98
1.36
5.79*
1.86
0.00*
4.27*
1.92
2.16
3.27
0.11
14.70*
4.29
I.b8
2.3b
2
3.00
2.76
2.86
J.39
3.16
1.69
2.93
3.11
1.98
7.bO*
2.46
0.00*
b.10*
2.b4
2.78
3.89
O.b2
11.00*
1.6b
2.19
3.14
1
2.20
2.04
..49
2.23
2.21
2.6b
1.87
4.37
1.4b
0.00*
2.29
0.00*
4.27*
1.42
1.9b
3.68
0.92*
7.88*
1.99
1.74
3.46
2
3.00
2.b4
2.3b
3.41
3.12
2.70
3.07
2.81
1.61
2.83
3.70
0.28'
4.27'
1.79
3.3b
2.69
0.42'
y.38'
3.38
2.49
3.b7
SOKFACE WATEK
1
2.20
2.03
2.bl
I.b9
2.21
l.bl
2.00
WASTE WATEK 1
WASTE WATtK 2
WASTE WATEK 3
2.12
1.19
b.06
1.97
0.3b
.Ob*
.37
3.
1.
2.34
3.19*
3.66
b.29
1.93
O.H4
1.B7
2
3.00
2.42
3.bl
1.95
3.16
2.b8
2.93
2.91
1.96
b.66
2.78
0.34
3.97*
1.81
3.08
3.77*
3.69
5.32
2.63
1.71
2.60
1
2.20
1.34
3.10
4.71
1.28
2.43
2.40
2.13
0.00'
0.00'
18.00'
0.00'
0.00'
1.89
1.84
3. Ob
0.00'
7.03'
0.00'
0.00'
0.00'
2
3.00
1.43
4.94
2.89
2.04
3.72
3.20
4.48
0.00*
0.00*
0.00*
0.00*
0.00*
4.20
b.Ob
2.44
0.00*
8.94*
0.00*
0.00*
2.4b
1
2.20
1.3b*
2.6?
1.88
2.11
5.14
2.86
3.08
1.42
0.00*
6.b9*
0.00*
3. Ob*
16.40*
2.24
8.09*
0.00*
27.80*
I.Ob
1.40
2.29
2
3.00
1.44'
3.29
2.70
2. HI
l.bl
4.27
1.99
3.30
0.00'
7.78
0.00'
b.12'
20.90'
3.b8
3.88
3.13
7.67
6.b7
2.44
4.31
1
2.20
1.31*
2.14
1.87
2.19
2.14
2.40
1.77
1.84
0.00*
4.01*
0.00*
0.00*
l.bl
2.20
4.14*
2.66
3.11
1.57
1.42
1.97
2
3.00
1.32*
3.73
1.72
2.82
3.61
2.00
3.3b
l.bO
0.00*
b.27
0.00*
00
00
87
90*
73
2.6b
10
26
3.23
-------
TABLE 36 (continued)
imTILLEU WATEK
TAP WATEK
SUKFACt WAFEK
WAS ft WAFLK 1
WASTE WATEK 2
WASTE HATER 3
AMPUL NO:
THUE CUNC:
LAB NUMBtK
1
2
3
4
5
6
7
8
9
10
11
12
13
M
Ib
Ib
17
id
19
20
3
46.00
41.40
44. 80
bb.OO
43.10
4b.OO
41. 70
41.30
41.30
bO.30
4b.OO
4?. 30
lbb.00*
71.10
46.80
42.10
19.70
77.90
48.80
40.10
44.60
4
b4.UO
4b.20
SO. 60
6b.90
bi.90
47. bO
bO.OO
bl.70
38.60
b9.bl>
4b.OO
47.20
16b.OU*
71.60
b4.90
bb.bG
37.80
34.40
bl.ilO
4b.40
bl.20
3
4S..OO
34.70
40.40
61. HO*
4b.lO
40.40
43. bO
41.40
46.30
b3.6U
46. UO
40.80
201. Oil*
4/.70
44. bO
48.70
311.10*
104.00*
43. bO
38.00
46.. 40
4
b4.00
46.70
bl.60
68.40
b3.00
49.30
bO.40
47.20
36.90
b4.10
49.30
bl..'0
180.00*
b2.20
bb.bO
b8.00
19.20*
72.80*
49.110
61.90
b3.lO
3
46.00
:4.40
41.00
36.10
4b.6Q
42.0H
4 3. SO
43.90
44.60
b3.70
bl.80
bO.20
18b.OO*
b/.lO
47.80
b2.IO*
44.00
49.40
38.70
3t>.80
4b.i'0
4
54.00
43.20
47.00
39.90
b3.80
48.90
b3.00
49. bO
40.10
bH.20
bb.10
bO.70
270.00*
43.10
bb.20
b^.10*
3o.bO
bl.60
b4.40
SI. HI
bl.10
3
46.00
39.70
4b.OO
41.80
49.70
49.10
4b.20
44.80
37.70
3U.90
34.00
3b.bO
237.00*
42. bO
bO.HO
42.20
0.00*
bb.20
10. bU*
31.20
41.40
4
b4.00
40. bO
b2.30
46.00
b4.90
bb.70
48.70
b3.60
42.70
4b.3()
39.00
48.70
230.00*
b7.70
b8.U)
49. bi)
0.00*
61. bO
28.00
36. bO
47.10
3
46.00
32. bO*
40.40
39.70
42. HO
43. 9U
4b.20
41.80
48.70
46.60
bb.OO
44.20
240.00*
73. tO*
bl.10
b3.10
41.10
b3.bO
4b.90
3b.80
49. bO
4
b4.00
31.30*
42.90
43. bO
b2.00
bO.70
b8.00
49.20
41.40
b3.00
40.30
47. bO
IJb.OO*
72.30
61.10
60.00
34.40
bl.20
b9.3U
44.20
b/.20
3
46.00
2SJ.20*
40.80
37.20
46.00
43.60
46.10
46.30
42.40
47.90
36.40
39.40
I6b.00*
43.00
44.00
64. bO*
34.00
44.00
46.60
30.60
42.40
4
b4.00
37.70*
46.80
46.30
b2.30
47.80
bO. 00
b4.bO
49.00
b2.90
44.70
63.20
13b.OU"
49.80
b8.2l)
61.20"
63.30
bO.20
61.40
3b.80
48. UO
-------
TABLE 36 (continued)
imuiuu UAILH
IAI' UAttK
bUlU ACL UAflK
UASTt WATLK 1
WAflK 2
WASTE WATEH 3
cn
AMPUL NO:
TKUE CUNC:
LAB NUMUCK
1
2
3
4
b
6
7
a
9
lu
11
12
13
14
15
16
I/
Ib
IV
20
b
4 '.,0.00
313. 00
432.00
bOO.OO
441.00
4b4.0U
4J6.UO
443.00
489.00
273.00
342.00
445.00
1350.00*
b44.UU
425.00
4b7.UO
448.00
3M6.0U
4bH.OO
3bb.OO
3bl.OO
b
biO. 00
37H.OO
473.00
492.00
b39.00
bbb.OO
40'J.OO
b7/.00
b2b.OO
304.00
343.00
b7b.0<)
13bO.OO*
494.00
b42.00
b/b.UO
391.00
300. UO
741.00
3H6.00
3/b.UU
b
4bU.OO
^67.00
44b.OU
44M.IH)
434.00
409.00
4/b.OO
422.00
472. UO
2bO.O()
328.00
442.00
12bO.OO»
3bl.OO
40b.l)0
444.00
2b/.OU*
44b.0'.i'
JbH.OO
J4-J.OO
J43.00
b
bbO.UI)
3bO.OO
bib. 00
b02.00
b3'KOO
471.00
394.00
b4b.OO
b37.00
31H.UO
440.00
b92.00
1700.00*
372.00
bU.UO
b21.00
404.00*
4bH.O(l*
4bb.OO
34X.OO
34b.OO
b
4bO.OO
2b9.00
419.00
3/b.OO
4bO.JO
441.00
440.00
40H.OO
b04 . 00
2bLl.OO
3b4.00
473.00
IbbO.OO*
3U7.00
429.00
b!3.00*
2b2.00
340.00
32U.IIO
430.00
1 234.00
b
bbO.OO
319.00
bkl.OO ~~
4bH.OO
bbb.OO
b 39.01)
3H3.00
b29.00
blO.OO
319.00
294.00
bH/.OO
IHbO.OO*
431.01)
b!2.00
b26,00*
4bb.OO
3/7.00
4bO.OO
493.00
293.00
b
4bO.OO
1240.00*
391.00
394.00
419.00
437.00
4HO.CO
3b9.00
bll.OO
2b7.00
428.00
b07.00
IbOO.OO*
177. Od
40b.OO
4fa3.0U
437.00
317.00
3bO.OO
349.00
346.00
b
bbO.Oi)
1230.01)*
biO. 00
448.00
b40.00
499.00
411.00
b3H.OO
SOH.OO
308. UO
4?0.00
b7b.OO
1800.00*
14b.OO*
539.00
602.00
627.00
383.00
43H.OO
400.00
380.00
b
4bO.OO
219.00*
418.00
396.00
447.00
446.00
468.00
414.00
509. JO
386.00
312.00
b31.00
'.'•">0.!>0*
b4c.OO
443.00
WI.UO
3«d.ou
2X2.00
4b4.00
291.00
3b4.0u
6
bbO.OO
302.00*
b37.00
487.00
b50.00
530.00
417.00
506. UO
540.00
468.00
425.00
609. '»0
1751:. 00*
434.00
553.00
1*28.00
55, '.00
301.00
558.00
407.00
351.00
b
4bO.OO
315.00*
421.00
3/5. UO
440.00
420.00
4b6.00
44b.OO
b07.00
334.00
299.00
581.00
IbOO.OO*
422.00
446.00
b2b.OO*
278.00
343.00
377.00
372.00
341.00
6
5bO.OO
247.00'
521. OU
4bfa.OO
533.00
bbU.OO
423.00
549.00
537.00
428.00
345.00
557. UO
19UU.OO
460.00
564.00
644.00'
494.00
380.00
472.00
408.00
3/0.00
-------
TABLE 37. RAW DATA FOR ETHYLBENZENE ANALYSIS BY WATER TYPE
DISTILLED WATEK
IAP WATEK
SUKFACE WAFER
WASTE WATEK 1
WASTE WATEK 2
WASTE WATEK 3
AMHUL NO:
TKUE CONC:
LAB NUMbEK
1
2
3
4
b
b
7
a
4
3.83
4.98
2.75
2.94
3.116
2.94
1.76
13.00'
2.42
0.93
3. 84'
14.20'
3.66
3.97
.2.23'
7.36'
4.54
2.31
2.96
1
2.20
3.91
2.76
2.4b
l.OH
1.97
2.3b
1.97
2.96
4.25
3.28
0.81*
5.49*
J.lb*
1.98
3.81
2.40
2.62
O.b3
1.82
2.2/
2
3.UU
3.50
4.24
1.7K
l.yu
2.84
2.28
3.08
2.19
4.89
2.34
1.11*
7.93*
2.44*
4.79
3.12
3.50
4.UJ
U.UO*
2. OH
2.b2
1
2.20
2.H6
2.32
1.30
1.83
2.5i)
2.0U
2.26
2.55
0.00*
3.86
0.77
5.31*
9.59*
3.35
6.82*
1.15
5.58*
,31
.14
2
3.0U
1.29
3.41
1.29
2.38
3.7b
1.76
0.44
3.09
0.76
4.66
0.9U
33*
80*
29
4.b6*
1.43
2.02
4.68
3.94
2.46
0.77
1
2.20
2.19
0.00*
2.61
3.61
4.10
3.06
0.00*
5.30
0.00*
3.10
2.41
10.00*
0.00*
14
92*
7t>
20
10
3.37
1.19
2
3.00
O.b9
U.OO*
3.08
3.70
2.98
1.8d
2.03
4.40
0.00*
5.30
2.16
10.60*
0.00*
2.33
4.H8*
1.72
0.70
13.00*
2.77
1.87
-------
TABLE 37 (continued)
imTIUEO UATEK I AH HATtM SUKFACE UATLK WASTE WATLK 1 HAbtE WATEK 2 WASH WAILK 3
AMPUL NO:
TKUE CUNC:
LAB NUMriEK
1
2
3
4
b
6
1
8
9
1U
11
12
13
14
Ib
16
17
Id
19
2(1
3
46. UU
4U.SU
4b.60
26.20
41. 7U
47. 7U
41.SU
42. UU
47.80
bb.4U
47. 60
37. 10*
120.00*
H4.1U
b4.8U
43.40
24.30
80.70
2b.40
41. SO
44.10
4
b4.00
44.60
bl.80
MO. 40
bO.90
bl.40
b0.9U
b2.UO
tb.20
bH.10
bb.30
32.70*
133.00*
92.90
64.60
61. bO
3b.70
31.00
28.40
44.40
b2.00
3
46. OU
32. HU
41. bU
83. SO*
44. 1U
42.90
43. UU
4 1 . JU
4b.HU
61. 3U
4b.6U
44. bU
Ibb.UU*
61. OU
bb.10
bl.UO
2').1U*
loa.oo*
b4.KO
37. 1U
42. 1U
4
b4.UU
47.20
b3.7U
89. 6U
b2 40
bJ.UU
bl.10
47.40
41.40
69. 6U
bJ.20
33.611
198. OU*
bll.7U
bb.10
60. bO
22.20*
81. bO
63.70
63.00
b2.90
3
46. 00
34.60
41. 4U
27. 1U
4b.3U
40. 30
42. 2U
43. bO
44.30
61.10
60.00
42. bO
244.UU*
97. 4U*
bb.40
b4.l>0
33. 1U*
bb.2U
b9.3U
37.40
43. 7U
4
b4.0U
4U.30
49.00
29.80
b3.bU
47. 2U
b2.6U
bU.60
43.4U
66,00
b4.20
34.2H
213. IK)'
102.00*
6b.UU
60.80
-------
TABLE 37 (continued)
imriuiu HATLK
IAH WATIK
MWACE WAItH
HASTE UAILK 1
UAbFE HA TEX 2
WAbTE MAFEK 3
CO
AM'UL NO:
TKUE CUNC:
LAB NUNBIK
i
2
3
4
b
6
7
8
9
1U
11
12
13
14
Ib
16
i;
la
19
20
b
4b2.00
344. UU
384.00
bJl.UO
416. UO
434. UO
444. 00
423.00
b62.UO
281.00
448-00
29b.OO*
140b.OO*
bib. 00
488.00
4bl.OO
333. 00
2b9.0U
bb/.OO
339.00
3bb.OO
6
bbl.OO
4bl.OO
422. OU
b49.00
b27.00
b39.00
400.00
bbb.OO
b94.00
326. UO
b31.00
384.00*
1346.00*
44b.OO
628.00
by3.UO
341.00
309.00
881.00*
3U1.UO
412.00
b
4b2.UO
2b4.00
40t>.00
bl)4.00
416. UU
401.00
4HO.IIO
4l)6.00
bU2.00
2b9.00
462.00
311.00
2036.00*
4bS.(IO
4tS.I)U
biib.llO
228. UU*
4/H.U"
4bb.OO
346. UO
346.00
6
bbl.OO
369.00
484.00
b63.00
b29.00
488.00
400. 00
b4b.OO
613.00
328.00
603.00
396.00
2626.00*
423.00
620.00
6bH.OO
3b/.00*
4b8.00
b43.00
390.00
370.00
b
412.00
2H2.0U
3/2.00
4bb.OO
42b.UO
426.00
444. OL1
393.00
b/2.UO
249.00
414.00
309.00
2bO/.OU*
b3H.OO*
4//.00
b2b.OO
262.00*
341.00
389.00
421.00
2S4.UO
6
bbl.OO
3b3.UO
488.00
b68.0U
b4b.OII
b32.00
390.01)
!>'J4.(IO
638. OU
303.0U
473.00
400.01!
2bbb.OU*
621.00'
606.00
666.01)
427. OU*
3114.UU
b38.0U
482.00
341.0U
5
4b2.00
319.00
316.00
4dl.OO
3116.00
4Ub.OO
487.00
3b6.00
b4h.OO
292.00
417.00
318.00*
20H8.00*
68.5(1*
b2b.OO
49b.OO
387.0U
336.00
463.00
320.00
370.00
b
bbl.OO
330. (JO
b02.00
b41.00
b27.00
501.00
410. OU
•jJb.UO
bb9.UO
339.00
469.00
40b.OU*
2697. UO*
82 . 00*
622.00
bb4.00
bHl.OO
3/0.00
bi?3.0()
368.00
424. UU
b
4b2.00
341.00
360.00
467.00
43b.OO
4bl.OO
469.00
379.00
b/3.00
342.00
4bb.OO
310.00
2154.00*
3U4.UO
5U6.00
b23.00*
3J9.UU
222.00
424.00
2Hb.OU
363.00
b
bbl.OO
390.00
49b.OO
bb7.00
b4b.UO
b41.00
410.0U
480.00
bb9.UU
421.00
513.00
388. UU
2124.00*
234.00
b47.UO
bb/.UU*
bUb.UO
267. UO
b09.UU
407. UO
3K9.UU
b
4b2.00
328.00
36b.UU
449. UO
427.00
4D9.00
4bb.O')
424.00
b66.UU
b27.UO
363.00
310.00
21b3.0U*
478.00
bUO.UO
b39.00*
314.00
328. OU
410. OU
428.00
3bO.OO
6
bbl.OO
316.00
471.00
b3b.OU
530.UO
b21.00
421.00
b4b.OO
b87.00
541.UU
b29.00
387.00
2b07.00'
bb8.00
662.00
S41.UU'
542.00
3b8.00
blJb.OO
458. UO
4UO.OO
-------
TABLE 38. RAW DATA FOR TOLUENE ANALYSIS BY WATER TYPE
UISTILIEU WATEH
TAP WATER
SURFACt UATEK
WASTE W.TEK 1
MASTC WATEK 2
WASTE WATtH 3
AMPUL NO:
TKUE CONC:
LAB NOMBEH
1
2
3
4
b
6
7
8
9
1U
11
12
13
14
Ib
16
17
18
It
20
1
2.10
2.15
2.38
1.70
2.b2
2.69
2.18
1.7b
l.bO
6.64
1.48*
1.37
2.64
2.11
2.47
2.98
b.04
7.18
1.42
2.62
2. Ob
2
3. DO
2.73
3.88
3.8U
3.28
3.b2
1.76
J.lb
3.6b
6.91*
2.0U*
2.91
1.92
3.79
3. Ob
3.86
3.13
lb.8U*
1.93
9.H2*
2.89
1
2.10
2.22
2.29
i.9b
2.bb
1.6b
2.12
2.97
I.b3
b.10*
I.b4
1.2/
2.7b*
I.b2
2.20
3. hi
O.M/*
13. bO*
2.11
3. IK
1. 48
2
3.00
2.64
2.99
2.34
3.43
2.63
2.94
3.II2
3.88
4.23
2.2b
2.06
3. 12*
1.611
3.b9
3.2H
1.01*
12. HO*
3.00
3.61
2.6H
1
2.10
2.22
l.blJ
1.22
2.41
l.bH
2.24
2.09
1.73
7.11*
I.b3
l.SH
2.H.*
/.Ob»
2.60
i!.97
l.bl
H.6b*
2.12
1.21
1.90
2
3.00
2.44
2.06
1.33
3.31
2.21
3.06
2.94
3.21
7.46
l./b
1.78
3.12*
6.91
3.46
4.03
0.')4
8.96*
1.74
1.3b
2.8b
1
2.10
3.16
1.96
2.29
2.b2
2.97
2.24
/.62*
2.18
4.6b
2.31
0.00*
0.00*
1.24
0.00*
3.2ii
3.97
0.00*
b.29
20. HO*
1.98
t
3.00
'
2.22
4.01
0.21
3.b7
2.b4
I.b3
7.60
b.14
I.h3
3.00
4.H9
0.00'
4.0h
3.00
3-Hb
10.70*
7.00
2.27
24. ?0*
2.61
1
2.10
b.4b
0.00*
O.OU*
0.00*
0.00*
2.00
20.00
0.00*
0.00*
0.00*
30.60
13.80
0.00*
0.00*
69.00*
0.00*
*
0.00*
3.00
0.00*
2
3.00
4.26
11.00
0.00'
0.00'
0.00'
1.76
0.00'
12.00
0.00'
3.00
Ib.bO
0.00'
0.00'
1.00
69.00'
3.00
O.OO1
2.00
0.00'
1
2.10
1.21
0.46
3.61
0.00*
2.b9
0.00*
5.80
I'.OO*
1. 10
6.60
0.00*
3. JO
2.40
3.64
3.33
2.10
2.20
0.90
2
3.00
0.60
0.82
3.19
0.00*
1.65
0.00*
G.uO
0.00*
i.tiG
o.oo*
0.00*
b.06
H.HO
b.07
1.43
*
21.90*
2.30
l.OJ
-------
TABLE 38 (continued)
UlSTllLEO HATEK
1AI> WATCH
SOKFACE UATEK
WASTE MATEK 1
WASTE WATEH 2
WASTE WATEK 3
to
o
AMPUL NO:
TKOE COIC:
LAB NUMdEtt
1
2
3
4
5
6
7
8
9
10
11
12
13
14
IS
16
17
18
19
20
3
46.00
39.40
41.40
102.00*
48.00
45.60
40.80
40.60
42.70
51.40
33.40*
42.90
149.00*
55.80
50.10
42.50
29.50
81.00*
55.60
40.90
41.80
4
54.00
43.80
46.70
91.80*
59.40
50.70
46.40
Si. 20
42.70
63.30
43.40*
36.60
180.00*
65.40
59.20
61.40
44.10
34. 3C
62.80
44.60
49.60
3
46.00
32.30
38.10
99.90*
51.20
45.00
41.50
40.40
44.90
57.00
35.00
51.20
154.00*
41.20
51.90
48.20
31.10*
106.00*
64.70
36.60
38.00
4
54.00
45.90
50.10
71,70
61.10
53. /O
45.40
46.40
39.60
69.90
4j.20
36.60
178.00*
49.00
60.40
54.60
23.30*
77.30*
64.70
61.30
49.50
3
46.00
33.50
36.20
21.10
51.90
40.90
'10.00
44.20
46.20
54.80
37.60
42.60
155.00*
65.70
50.90
51.90
3h.4u
60.70*
53.90
35.30
44.60
4
54.00
39.70
42.50
23.20
62.30
48.40
46.10
51.30
46. 'JO
59.90
48.60
38.30
205.00*
70.30
59.90
59.90
33.70
64.30*
56.90
53.40
49.60
3
46.00
49.10
36.00
?1.90
SO. 10
47.10
40.00
50.70
46.30
35.20
30.30
39.50
152.00*
31.60
42.90
46.60
39.50
34.80
48.90
45.20
45.50
4
54.00
44.70
42.70
24.30
62.00
53.60
SO. 90
C kl f "
43.00
36.00
50.60
41.50
198. L'O*
32.00
52.70
51.90
52.20
21.60
59.10
41.90
63.10
3
46.00
106.00
25.00
83.70
35.60
26.70
40.80
34^00
56.00
66.60
59.00
65.60
70.80
69.20
53.00
149.00*
21.00
*
0.00*
41.00
39.00
4
54.00
46.00
38.00
72.00*
43.80
31.80
53.60
38.00
44.00
87.30*
33.00
54.60
39.80
36.50
50.00
148.00*
0.00*
•
0.00*
45.00
44.00
3
46.00
45.60
37.10
19.40
51.90
40.00
40.80
37.40
53.20
61.40
30.20
31.40
100.00*
32.80
54.10
56.90
36.90
21.50*
56.40
41.30
41.10
4
54.00
57.20
45.90
23.70
57.00
42.20
50.90
47.60
48.90
54.10
50.40
34.20
196.00'
45.70
65.10
51.90
63.10
25.00'
60.60
38. SO
36.30
-------
TABLE 38 (continued)
UISTIULO UATIM
TAP UAUK
WA1EK
WAilL HARK 1
WASTE UAIIK 2
WAS ft MATEK 3
AMPUL NU:
TKOE CONC:
LAD NUMtftK
|
2
J
4
%
6
7
a
9
1U
ll
12
13
14
Ib
16
17
18
14
2U
b
4bO.OO
37b.OO
416. 00
b47.0U
499.00
439.00
4U4.00
431.00
637.00
287.00
336.00*
3bb.OO
1728.00*
4b9.00
bUl.OO
48b.OO
440.00
Bbb.OO*
bll?.l'U
380.00
341.00
6
bbO.OO
4b2.00
444.00
b9b.OO
609.00
b!4.00
400.00
b3b.OO
bbl.UU
32b.OO
380.00*
410.00
1680.00*
427.00
60'. 00
b9b.0'l
430.00
713.00
7bb.OO
427. 00
467.00
b
4bO.OO
278.00
441.00
bHl.OO
bOO.OO
408.00
440.00
41b.OO
bib. 00
2b9.00
31b.OO
3b2.00
1800.00*
317.00
482.00
b4b.OO
2/3.00'
llbb.OO*
410.00
343.00
3^2.00
6
bbO.UO
390.00
497.00
638.00
609.00
4H1.00
389.00
b3b.OO
bUO.OO
330.00
40b.OO
440.00
22bb.OO*
3bl.OO
bOb.OO
682.00
434.00*
768.00*
46/.00
386.00
429.00
b
2. 110
b41.UO
ZbH.IIO
331.01)
3 (j 1.1 K)
2b44.0U*
421.00
4Mb. 00
bb3.UO
317. 1)0
1399.110*
3/H.OO
42H.OO
317.00
6
bbO.OO
383.00
499.00
b/7.00
b^O.OO
b34.00
389.00
blM.OO
b89.00
32b.OO
3b9.00
44b.OO
24/2.0'J*
433.00
b93.00
blM.OO
bbO.OO
lb09.0U*
4bO.OO
4b8.00
424.00
b
4bO-00
188.00
311.00
b42.00
471.00
420.00
440.00
364.00
b?0.00
2Hb.OO
31b.OO
3/7.00
1/82.00*
iJb.OO
49b.OO
b!4.00
4bH.OO
328.00
416. UU
337.00
428.00
6
bbO.OO
49/.00
484. JO
b/2.00
bib. 00
483.00
400.00
bJ2.00
b3J.WJ
32b.OO
249.00
4b2.()0
202^.00*
133. UO
b/b.OO
bb7.()0
b93.00
3/b.OO
b41.00
391.00
4H9.00
b
4bO.OO
809.00*
3'.'/.00
3bl.OO
b2/.00
390.00
429.00
391.00
6b7.00
318.00
324.00
38b.OO
223/.00*
311.00
b31.00
646.00'
3bb.OO
2/S.OO
b!9.00
?bb.OO
43b.OO
6
bbO.OO
812.00
419.00
44b.OO
620.00
b39.00
*
47b.OO
b84.00
448.00
3/2. -M
»'.)0.0'1
2141.00*
2i'0.'JO
7b^.OO
74/.00*
bb3.00
320.00
b9b.OO
3H2.00
4b9.00
b
4bO.OO
333. 0'J
407.00
bOb.OO
b!2.00
428.00
42b.OO
42b.OO
601.00
421.00
267.00
3bb.O'J
18b2.00«
36b.OO
b09.00
bb9.00
339.00
309.00*
388.00
423.00
382.00
b
bbO.UU
398.00
4H9.00
630.00
510.00
b.'9.00
41. .00
b2b.OO
b42.00
430.00
314.00
424.00
1924. OU*
42?. 00
64H.OO
712.00
b21.00
3bH.OO*
4bH.UO
464.UO
4/8.00
-------
TABLE 39. BLANK VALUES IN DISTILLED WATER
(pg/L)
Lab
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
B
NDb
ND
0.34
0.57
0
0
ND
0
0
0
0
ND
13.9
ND
0
0
0.21
0
0
0.84
CB
ND
ND
0.06
0.17
0
0
ND
0
0.34
0
1.62
ND
0
ND
0.75
0.69
8.89
0.81
0
<0.20
1,2-DCB
ND
ND
<0.03C
0
0
0
ND
0
1.21
0
3.50
ND
0
ND
0
0
0.01
0
0
<0.40
An-ilytea
1,3-DCB
ND
ND
<0.03
C
0
0
ND
0
0.44
0
2.76
ND
0
ND
0.35
0
4.10
0
0
<0.40
1,4-DCB
ND
ND
<0.03
0
0
0
ND
0
1.86
0
2.37
ND
0
ND
0.36
4.42
0.70
0
0
<0.30
EB
ND
ND
0.04
0.18
0
0
ND
0
0.37
0
.1.11
ND
U.*
ND
0.30
4.71
6.49
2.23
0
<0.20
T
ND
ND
0
0
0
0
ND
0
0
C
0
I;D
0
ND
0
0
4
0
0
0
.16
.31
.86
.60
.17
.42
.72
aAnalytes: B = benzene; CB = chlorobenzene;
1,2-DCB = 1,2-dichlorobenzene;
1.3-DCB = 1,3-dichlorobenzene;
1,4-DCB = 1,4-dichlorobenzene;
EB = ethylbenzene,- and T = toluene.
ND - not detected.
< = less than.
122
-------
TABLE 40. BLANK VALUES IN TAP WATER
(M9/L)
Lab
number
1
2
3
4
5
6
7
6
9
10
11
12
13
14
15
16
17
18
19
20
B
tnb
K>..-
0.46
0.49
0
0
ND
0
0.34
0
0
ND
2.17
ND
0
0
0.37
0
0
<0.20
CB
ND
ND
0.06
0.21
0
0
ND
0
1.16
0
1.12
ND
0
ND
0.52
1.69
2.98
0
0
<0.20
1,2-DCB
ND
ND
<0.03C
0
0.84
C
NL
0
3.00
0
2.51
ND
0
ND
0.05
0.95
3.00
0
C
0.53
Analyte
1,3-DCB
ND
ND
<0.03
0
0.64
0
ND
0
2. '3
0
1.89
ND
0
ND
0
0
2.46
0
0
<0.40
1,4-DCB
ND
ND
<0.03
0
0.76
0
ND
0
4.01
0
1.56
ND
0
ND
0.07
0.98
4.32
0
0
<0.30
EB
ND
ND
<0.03
0.14
0
0
ND
0
0.75
0
0.54
KD
6.07
ND
0.27
0.66
1.13
5.40
0
<0.20
T
ND
ND
0.13
0.25
0
0
ND
0
0.76
0
0
ND
0
ND
0.40
0
<0.01
0
0
0.58
Analytes: B = benzene; CB = chlorobenzene;
1,2-DCB = 1,2-dichlorober.zene ,-
1,3-DCB = 1,3-dichlorobenzene,-
1,4-DCB = 1,4-dichlorobenzene;
EB - ethylbenzene; and T = toluene.
bND = not detected.
C< = less than.
123
-------
TABLE 41. BLANK VALUES IN SURFACE WATER
(M9/L)
Lab
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
B
NDb
ND
<0.3C
0.23
0
0
ND
0
0.19
0
0
ND
0
ND
1.65
0
<0.10
0.74
0.13
0.57
CB
ND
ND
0.02
0.11
0.12
0
ND
0
0
0
1.24
ND
0
ND
1.24
0
2.20
1.01
0.37
<0.20
1,2-DCB
:ID
ND
0.06
0
0.03
0
ND
0
0.30
0
2.93
ND
0
ND
0.08
1.18
0.98
0
0
<0.40
Analyte3
1,3-DCB
ND
ND
0.18
0
0.04
0
ND
0
0
0
2.11
ND
0
ND
0.18
0.30
3.21
0
0
<0.40
1.4-DCB
ND
ND
0.19
0
0.41
0
ND
0
2.60
0
1.89
ND
0
ND
0.15
0.68
3.91
0.52
1.01
0.31
EB
ND
ND
0.09
0.18
0
0
ND
0
0.35
0
0.78
ND
2.73
ND
0.36
1.11
1.17
0
0.30
<0.20
T
ND
1.82
1.46
0.44
0.33
0
ND
0
0.92
0
0
ND
0
ND
0.70
0
0.85
0
1.67
0.30
Analytes: B = benzene; CB - chlorobenzene;
1,2-DCB = 1,2-dichlorobenzene;
1,3-DCB = 1,3-dichlorobenzene,-
1,4-DCB = 1,4-dichlorobenzene,-
EB = «thylbenzene; and T = toluene.
°ND = not detected.
< = less than.
124
-------
TABLE 42. BLANK VALUES IN WASTEWATER 1
Lab
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
aAnalytes
B CB
1.05 28.3
2.52 27.8
1.81 20.6
0.92 41.0
1.91 31.4
0 0
NDb 30.9
1.54 53.7
4.77 34.9
1.88 72.4
1.49 18.9
ND 20.3
2.19 23.9
3.01 35.2
2.46 28.8
0.43 21.3
1.76 2.53
1.10 24.1
1.83 29.9
2.04 32.4
: B = benzene
1,2-DCB = 1
1.3-DCB = 1
1.4-DCB = 1
Analyte3
1,2-DCB 1,3-DCB
0.67 3.45
5.75 46.5
<0.03C 44.7
0 72.5
0 46.8
0 25.1
ND ND
0 162
0 43.6
0 0
2.32 7.52
ND ND
0 50.2
ND 53.6
0 53.4
0.30 43.6
3.40 90.5
4.42 7.20
0 54.3
<0.40 50.4
; CB = chlorobenzrne ;
, 2-dichlorobenzene ;
, 3-dichlorobenzene ;
,4-dichlorobenzene ;
1,4-DCB
37.5
0.54
0.05
0
0.80
0
ND
0
0
103
1.94
ND
0
ND
0
0
<0.01
62.0
0
<0.30
EB
1.27
0.46
1.19
1.53
0.36
0
0.45
0.50
0.92
1.25
0.38
ND
6.89
0.65
1.07
1.77
2.39
2.80
0.15
0.36
T
2.12
£.59
5.05
2.34
3.19
0
ND
2.49
8.48
5.20
0
18.0
3.17
10.4
0
0
55.4
0.86
8.77
0.94
EB = ethylbenzene ; and T = toluene.
bND = not
detected.
"< = less than.
125
-------
TABLE 43. BLANK VALUES IN WASTEWATER 2
(pg/L)
Lab
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Analyte8
2
5
353
3
4
0
4
5
12
7
3
ND
42
7
2
2
10
2
5
4
B
.95
.02
.76
.30
.61
.71
.6
.58
.54
.2
.15
.92
.57
.3
.52
.73
.33
CB
186
215
255
229
217
114
238
467
168
421
175
144
276
278
236
201
111
175
188
234
1,2-DCB
0
<0
0
0
0
ND
0
3
1
2
ND
0
ND
1
1
1
0
0
1
.49
b
.03C
.61
.52
.14
.54
.24
.98
.33
.99
.00
1,3-DCB
0
ND
0
0
0
170
ND
7
1
0
4
ND
0
ND
0
2
11
0
0
0
.13
.36
.48
.72
.82
.45
.11
.49
.60
.2
.47
1,4-DCB
ND
ND
<0.03
0
0.79
0
ND
0
3.55
0
2.12
ND
0
ND
0.12
0
<0.01
1.31
0
<0.30
EB
1.
2.
2.
2.
3.
0
2.
4.
3.
6.
0.
ND
12.
3.
2.
4.
7.
4.
1.
2.
68
72
78
66
42
95
24
67
64
98
0
37
78
25
22
62
97
95
T
85.0
145
221
143
131
0
135
192
77.5
161
86.4
91.2
165
150
116
138
132
132
110
136
Analytes: B = benzene; CB = chlorobenzene;
1,7-nCB = 1,2-dichlorobenzene;
1,3-DCB = 1,3-dichlorobenzene;
1,4-I>CB = 1,4-dichlorobenzene,-
EB = ethylbcnzene; and T = toluene.
BND - not detected.
c< = less than.
126
-------
TABLE 44. BLANK VALUES IN WASTEWATER 3
(M9/L)
Lab
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
R
0.47
0.07
0.48
0.65
0.64
0
0.22
0
13.4
1.06
1.46
ND
0
3.48
0
0
0.82
4.03
0.37
4.10
CB
2.81
3.64
2.02
3.81
3.22
16.7
3.59
17.9
7.49
5.67
5.77
ND
1.44
4.20
4. 65
2.94
11.2
5.07
2.30
3.21
1,2-DCB
0.43
ND
<0.03°
0.86
0
2.70
ND
0
2.57
0
2.08
ND
0
ND
0.88
0
4.38
2.42
0
<0.40
Analyte
1,3-DCB
0.23
0.05
<0.03
0
0.34
4.00
ND
0
4.15
1.96
2.94
ND
0
ND
0.82
0.33
8.93
0
0
0.68
1 ,4-DCB
NDb
0.24
<0.03
0.27
0.11
0
ND
0
2.22
3.29
2.05
ND
0
ND
0
0.45
5.41
0.35
0
<0.30
EB
5.73
11.1
4.89
4.36
5.37
0
6.49
10.6
16.4
12.6
2.15
ND
21.6
8.77
7.90
6.49
16.1
10.9
5.83
7.68
T
7.62
6.11
5.66
11.8
15.4
0
15.5
22.4
18.1
18.3
7.40
20.0
8.75
12.2
18.8
9.17
47.8
16.3
8.00
17.9
8Analytes: B = benzene; CB = chlorobenzene;
1,2-DCB = 1,2-dichlorobenzene;
1,3-DCB = 1,3-dichlorobenzene;
1,4-DCB = 1,4-dichlorobenzene;
EB ~ ethylbenzene; and T = toluene.
bND = not detected.
< - less than.
127
-------
APPENDIX F
REVISED DATA FROM LABORATORY 12
128
-------
TABLE 45. REVISED DATA FROM LABORATORY 12
(M9/L)
K)
vO
Water Matrix
Distilled water
Tap water
Surface water
Ampul
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
Benzene
ND
ND
40.0
100
375
344
1.30
0
34.5
50.0
594
375
ND
0.75
42.3
76.3
500
438
Chlorobenzene
2.V7
2.37
43.0
45.5
495
465
2.97
3.66
40.0
46.5
475
599
3.25
•J.25
45 8
49.0
792
B17
1.2-DCB
12.3
12.3
43.5
42.5
339
339
5.48
5. 48
48.0
45.3
I
424
0.75
0.75
63.5
36.3
396
4P.O
1,3-DCB
S.41
6.76
47.8
50.2
451
434
4.06
4.06
42.3
55. S
417
543
1.25
1.50
45.0
79.5
503
607
1,4-DCB
4.27
6.10
38.8
41.3
338
338
4.27
4.27
50.3
45.0
313
427
1.25
1.63
46.3
67.5
388
463
Ethylbenzene
2.44
2.23
30.0
23.3
351
334
3 60
3.90
41.3
49.5
509
657
2.50
3.25
61 .0
53.3
627
6',2
Toluene
2.64
1.92
34.3
45.0
432
420
2.76
3.12
38.5
44.5
450
5b4
2.25
3.25
38.8
51.3
637
618
(continued)
-------
TABLE 45 (continued)
(pg/L)
u>
o
Hater Mtrix
Wastewater 1
Wastewater 2
Wastewater 3
Anpul
1
2
3
4
S
6
1
2
3
4
S
6
1
2
3
4
5
6
Benzene
0
0
37.5
47.0
344
469
5.2
ND
47.0
90.8
375
244
0
0
26.0
110
347
I
Chlorobenzene
0
0
63
70
515
619
1
4
72
61
728
743
1
1
34
(20.3)a
.8
.8
.41 (144)
.34
.5
.8
.44
.59
.5
35.3
491
569
1,2-DCB
2.74
5.48
53.5
59.3
396
452
4.11
5.33
70.5
33. B
367
424
1.03
1.37
48.0
34.0
368
I
1,3-DCB
0
0
72.8
86.8
521
608
2.70
4.43
78.0
43.3
469
573
0
!.69
52 0
41.5
486
625
1,4-DCB
0
0
59.3
57.5
375
450
3.05
5.12
60.0
33.o
363
438
0
1.25
41.3
33.8
375
475
Ethylbenzene
5
7
70
52
522
674
5
•*
67
65
539
531
2
2
47
49
538
627
.49
93
.0
.3
.31
.33
.8
8
.50
.65
3
.3
Toluene
0
0
42.5
54.0
450
510
13.5
4.81
40.5
32.8
582
558
4.20
3.65
30.0
54.0
468
486
(18.0)
(91.2)
<20.0)
NOTE: 1,2-DCB = 1.2-DichTorobenzene; 1,3-DCB
ND = not detected; I = eligible.
\alues in parentheses are blank values.
= 1,3-Dichlorooenzene; 1,4-DCB = 1.4-DicIorobenzene:
-------
APPENDIX G
EFFECTS OF WATER TYPE ON PRECISION AND ACCURACY
131
-------
TABLE 46. EFFECT OF WATER TYPE ON BENZENE ANALYSIS
*• FGINT ESTIMATES ••
DISTILLED WATER SLOPE:GAMMA(1) =• .96259
WATEK INTERCEPT(UATER-DISTILLEO) jLOPE(WATER-OIST1LLEO)
2 .1009 -.0082
3 -.0162 .01)90
4 -.3490 .0636
8 -.32b7 .0502
6 -.0628 .0122
** ANALYSIS OF VARIANCE **
SOURCE OF SUM UF SQUARES MEAN SOUAH£ F PKOB
REG(DISTILLEO) 1 2714.78106 2714.781U6
REG(WATER/DISTILLED) 10 5.16795 .51680 3.87 .0000
ERKOK 578 77.12518 .13343
U)
TOTAL b89 2797.07419
TABLE OF 9EJ CONF1UENCE INTERVALS FOR THE DIFFERENCES BETWEEN INTERCEPTS AND THE DIFFERENCES BETWEEN SLOPES
INTEMCEPT(MATER-OISTIILED) SLOPE (WAIEK-OI STILLED)
WATER ESTIMATE INTERVAL ESTIMATE INTERVAL
2 .1009 ( -.1841 . .3859) -.0082 ( -.0740
3 -.0162 ( -.3094 . .2T70) .009U ( -.0583
4 -.3490 ( -.6331 , -.0649) .0636 ( -.0019
b -.3257 ( -.62111 . -.0314) .0502 ( -.01/1
6 -.0628 ( -.3601 . .2345} .0122 ( -.0559
6
.0576)
.0763)
.1290)
.1174)
.0802)
NOTE: IF ZERO IS CONTAINED WITHIN A UIVEN CONFIDENCE INTERVAL THEN THERE IS NO STATISTICAL SIliNif ICANCE BETWEEN
DISTILLED WATER AND THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PAKAMEIER(INTERCEPT/SLOPE).
THE SLOPE AND INTERCEPT ESTIMATES FHUM THIS ANALYSIS ARE NUT THE SAME AS THOSE U8IAINED FKUM THE PRECISION
AND ACCORACV REGRESSIONS PERFORMED EARLIER.
-------
TABLE 47. EFFECT OF WATER TYPE ON CHLOROBENZENE ANALYSIS
** POINT ESTIMATES ••
DISTILLED WATEK SLOPE:GAMHA(1) = 1.00365
WATEH INTEKCEPT(WATEM.01STILLEO) SLOPE(UATEK-UISTILLEi))
.Ob83
-.0962
.12bb
1.2b07
-.U8h3
-.0136
.00/9
-.0324
-.2b47
.011)9
U>
W
SOUKCE
•• ANALYSIS OF VARIANCE ••
OF SUM OF SQUARES MEAN SQUARE
HEG(OISTILLED)
REG(WATEH/DISTILLEO)
ERKOK
TOTAL
1
10
bbb
2433.11S9b
16.394/6
90.91787
2433.11b9b
1.63948
.163b2
bb7 2b40.428b8
PR08
10.03 .0000
** TABLE OF
CONFIOENCE INTERVALS FOR THE DIFFERENCES BETWEEN INTEKCEPTS ANU THE UimRtNCES BETWEEN SLOPES •«
WATER
INTERCEPT!WATEK-UISTILLEO)
ESTIMATE INTERVAL
SLOPE(WATER-OISTILLED)
ESTIMATE INTERVAL
2
3
4
b
b
.ObH3 (
-.0962 (
.12bb (
1.2bO? (
-.0863 (
-.2bSt>
-.4046
-.22b3
.H37b
-.4049
.37bl)
.2171)
.4/83)
I.bb39)
.2322)
-.0136 (
.0079 (
-.0324 (
-.2b47 (
.0109 (
-.087.".
-.0646
-.ll'.b
-.3430
-.Ob2b
.0601)
.0803)
.0466)
-.1663)
.0844)
NOTE: IF itKu IS CONTAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIf ICANCE BETWEEN
DISTILLED WATEH AND THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PARAMl TER( INKKCtPI/SLOPE).
THE SLOPE ADO INTERCEPT ESTIMATES FHOH THIS ANALYSIS ARE NOT THE SAME AS THOSE OHTAINEO FROM THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 48. EFFECT OF WATER TYPE ON 1,2-DICHLOROBENZENE ANALYSIS
** POINT ESTIMATES ••
DISTILLED HATER SLOPE:GAKMA(1) = .96849
UATEK INTERCEPT(WATER-DISTILLEO) SLOPE(WATEK-OISTILLED)
-.0544
-.0133
-.0944
-.5270
-.OU06
.0036
-.006b
.0194
.0929
SOURCE
ANALYSIS OF VARIANCE ••
Of SUM OF SQUARES MEAN SQOARE
REG(OISTILLEO) 1 2526.32257 2526.32257
REG(WATER/D1STILLEO) 10 4.803.16 .48034
ERROR bb3 60.22882 .10891
0)
TOTAL
564 2S91.3b4/6
f PROB
4.41 .0000
TABLE Of 951 CONFIDENCE INTERVALS FOR THE OIFKWNCES BETWEEN INTEKCEPIS AND THE DIFFERENCES BETWEEN SLOPES ••
HATER
INT£RCEPT(WATER-Olb1ILLED)
ESTIMATE I
5LOPE(HATEK-OISTILL£0)
ESTIMATE INTERVAL
2
3
4
5
6
-.0125 (
-.0544 {
-.0133 (
-.0944 (
-.52/0 (
-.278.'
-.32.1)
-.2Bb7
-.3704
-.H023
.2b32)
.2249)
.2591)
.1816)
-.2516)
-.0006
.OOJb
-.0065
.OIS4
.09/1
-.0610
-.0594
-.06/H
-.04?9
.'J3U5
.0599)
.0656)
.0549)
.OHlb)
.1554)
NOTE: IF tiM IS CONTAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE BETWEEN
DISTILLED WATER ANU THE CORRESPONDING WASTE WATER FOR IH> ASSOCIATED PAKAMETER(INTERCEPT/SLOPE).
THE SLOPE AND INTERCEPT ESTIMATES FROM THIS ANALYSIS AXE NOT THE SAME AS THOSE UHIAINLU (ROM THE PRECISION
ANU ACCURACY REGRESSIONS PERFORMED EARLIER.
-------
TABLE 49.
EFFECT OF WATER TYPE ON 1,3-DICHLOROBENZENE ANALYSIS
•• POINT ESTIMATES ••
DISTILLED WATER SLOPE:GAMMA(1) » 1.00173
UATEK INTERCEPT(WATF.R-UISTILLEO) SLOPE(WATER-OISTIlLEO)
.083a
.0393
.6491
-.0031
.0376
-.02U2
-.0118
-.1319
-.0049
-.0094
SOURCE
ANALYSIS Of VARIANCE ••
OF SUN OF SQUARES flFAN SQUARE
U)
01
HEG(OISTILLEC)
REG(WATER/OIST1LL£0)
ERROR
TOTAL
1
10
bbB
2438.20602
4.8b398
b«.80602
243B.20M2
.4Bb40
.10b39
b69 2b01.86602
PKOU
4.61 .0000
** TABLE UF 95% CONFIDENCE INTERVALS FOK THE OIFFEHENCES BETWEEN INTERCEPTS AND THE OIFFEKENCES BETW^N SLOPES
UATEK
INTERCEPT(WATEH-OISTILLEO)
ESTIMATE INTERVAL
SLOPL(WATER-l)ISTILLED)
ESTIMATE INTERVAL
2
3
4
b
0
.083b {
.0393 (
.6491 (
-.0031 (
.0376 (
-.1811 .
-.2166 ,
.1416 .
-.2H09 ,
-.2279 .
.3480)
.29*3)
,9b6b)
.2/47)
.3032)
-.0202 {
-.OI1H (
-.1319 (
-.0049 (
-.0094 (
-.0810
-.0709
-.1991
-.0672
-.0701
.0407)
.0472)
-.0647)
.Ob/4)
.Obl3)
NOTE: IF littd IS CONTAINED WITHIN A UIVEN CONFIDENCE INItKVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE BETWEEN
OlSTILLEO WATEH ANO THE CORRESPONUINU WASTE WATER FOR THE ASSOCIATED PARAMETER) INIERCEPI/SLOi'E).
THE SLOPE ANO INTERCEPT ESTIMATES FROM THIS ANALYSIS ARE NUT THE SAME AS THOSE OBTAINED FROH THE PV.EC!S!ON
ANO ACCURACY REGRESSIONS PLKFURMEU EARLIER.
-------
TABLE 50. EFFECT OF WATER TYPE ON 1,4-DICHLOROBENZENE ANALYSIS
•• POINT ESTIMATES ••
DISTILLED WATER SLOPE:GAMNA(1) * 1.021b6
WAILR INTERCEPT(UATER-DISTIUEO) SLOPE(WATER-DISTILLEO)
-.0441
.2074
.10b2
.2237
.2613
.I21b
-.O'jU
-.04/9
-.02bb
SOURCE
•• ANALYSIS OF VARIANCE ••
DF SUM I.'F bQUARES MEAK SQUARE F
U)
REG(OISTILLEO)
REli(WATER/01STILLEO)
ERROR
IOIAL
1
10
b69
2bb2.1oa>7
1.2//HH
48.b8/b3
2bb2.10267
.12//9
.OHbb/
b80 2hl2.0bU09
PKOU
1.49 .1378
fABLE UF 9bl CONFIDENCE INTEKVALS FOK THE DIKKKENCES UETUEEN INTEKCEHrS ANU THE DIFFERENCES BETWEEN SLOPES
UATEN
INTEHCEPT(WAT£f-01 STILLED)
ESTIMATE INTERVAL
SLUPL(UATER-UISHLLED)
ESTIMAIE INTERVAL
2
3
4
b
6
.2074 (
.10b2 (
.2237 (
.2613 (
.121b (
-.027b
-.1224
-.0340
.Olbb
-.11/4
.4424)
.3327)
.4813)
.bOb9)
. -b03)
.0098)
.02?b)
.00b9)
.0071)
-.0441 ( -.09/9 .
-.02-19 ( -.UH23 .
-.Ubl3 ( -.lOHb .
-.04/9 ( -.1030 .
-.02V, ( -.U799 ,
NOTE: IF ZERO IS CONTAINED WITHIN A UIVEN CONFIDENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE DETWltN
DISTILLED WATER AND THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PARAMtlEK( |~Nlli
-------
TABLE 51. EFFECT OF WATER TYPE ON ETHYLBENZENE ANALYSIS
*• POINT ESTIMATES ••
DISTILLED WATER SLOPE:GAMMA(1) » .97585
WATER INTERCEPT(WATER-DISTILLED) SLOPE(WATER-OISTILLED)
.0594
-.0331
.0187
-.2306
.0276
-.0021
.0074
-.0017
.0338
".0004
SOURCE
ANALrSIS OF VARIANCE •*
OF SUM OF SQUARES MEAN SQUARE
W
REG(l)ISTILLEn)
REGJWATER/DISTILLED)
ERROR
TOTAL
1
10
578
2642.15194
1.88110
59.52390
2642.1M94
.18811
.10298
589 2703.55693
f PR00
1.83 .0532
•* TABLE OF 951 CONFIDENCE INTERVALS FOR THE DIFFERENCES BETWEEN INTERCEPTS AND THE DIFFERENCES BETWEEN SLOPES
WATER
INTERCEPT(WATER-OISTILLED)
ESTIMATE INTERVAL
SLOPE(WATER-OIST'LLEO)
ESTIMATE INTERVAL
2
3
4
b
b
.0594 (
-.0331 (
.0187 (
-.2306 (
.0276 (
-.1974
-.2934
-.2357
-.4870
-.2362
.3162)
.2271)
.2732)
.0258)
.2914)
-.0021 (
.0074 (
-.0017 (
.0338 (
.0004 (
-.0610
-.0524
-.0607
-.0251
-.1)597
.0569)
.0672)
.0573)
.0927)
.0604)
NOT£: IF ZERO IS CONTAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE BETWEEN
LMSTILLED 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 ACCUKAIY KEGHESSIONS HERrORMEU EARLIER.
-------
TABLE 52. EFFECT OF WATER TYPE ON TOLUENE ANALYSIS
** POINT ESTIMATES **
DISTILLED WATEK SLOPE:GAMMA(1) = .9/114
WATEK INTERCtPT(WATER-DlSTILLED) SLOPE(WATER-OISTILLED)
-.0797
-.2191
.0196
.6483
-.0574
.0107
.0358
-.0208
-.1273
.00GB
u>
CD
SOURCE
ANALYSIS OF VARIANCE ••
OF SUM OF SQOARES MEAN SQUARE
REG(OISTILLED)
K-G(WATER/OISTILLED)
ERKOK
TOTAL
1
10
565
2486.53914
7.11968
78.42011
2486.53914
.71197
.13880
576 2572.07893
PROS
5.13 .0000
TABLE OF 95X CONFIDENCE INTERVALS FOR THE OIFCERENCES BETWEEN INTERCEPTS AND THE DIFFERENCES BETWEEN SLOPES ••
WATER
!NTERCEPT(WAT£R-DISTILLED)
ESTIMATE INTERVAL
SLOPE(WATER-OISTILLEO)
ESTIMATE INTERVAL
.0797 ( -.3705 . .2110)
.2191 ( -.5072 . .0689)
.0196 ( -.2740 , .3132)
.6483 ( .2932 , 1.0034)
.0574 ( -.?5»l> . .2431)
.0107 (
.0358 (
.0208 (
.1273 (
.0058 (
-.0568
-.0311
-.0882
-.2046
-.0629
.0782)
.1026)
.0466)
-.0500)
.0744)
NOTE: IF ZERO IS CONTAINED WITHIN A GIVEN CONFIDENCE INTERVAL THEN THERE IS NO STATISTICAL SIGNIFICANCE BETWEEN
DISTILLED WATER ANO THE CORRESPONDING WASTE WATER FOR THE ASSOCIATED PARAMtTER{INTERCEPT/SLOPE).
THE SLOPE ANO INTERCEPT ESTIMATES FROM THIS ANALYSIS ARE NOT IHt SAME AS THOSE OBTAINED FROM THE PRECISION
AND ACCURACY REGRESSIONS PERFORMED EARLIER.
------- |