EPA-650/4-75-001
JANUARY 1975
Environmental Monitoring Series




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                  RESEARCH REPORTING SERIES


Research reports of the Office of Research and Development, U.S. Environ-
mental Protection Agency, have been grouped into series.  These broad
categories were established to facilitate further development and applica-
tion of environmental technology. Elimination of traditional grouping was
consciously planned to foster technology transfer and maximum interface
in related fields. These series are:

          1. ENVIRONMENTAL HEALTH EFFECTS RESEARCH
          2. ENVIRONMENTAL PROTECTION TECHNOLOGY
          3. ECOLOGICAL RESEARCH

          4. ENVIRONMENTAL MONITORING

          5. SOCIOECONOMIC ENVIRONMENTAL STUDIES
          6. SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS
          9. MISCELLANEOUS

This report has been assigned to the ENVIRONMENTAL MONITORING
series.  This series describes research conducted to develop new or
improved methods and instrumentation for the identification and quanti-
fication of environmental pollutants at the lowest conceivably  significant
concentrations.  It also includes studies to determine the ambient con-
centrations of pollutants in the environment and/or the variance of
pollutants as a function of time or meteorological factors.

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                                     EPA-650/4-75-001
COLLABORATIVE  STUDY  OF METHOD 10 -
REFERENCE  METHOD  FOR  DETERMINATION
    OF CARBON MONOXIDE EMISSIONS
       FROM STATIONARY  SOURCES -
            REPORT  OF TESTING
                        by

                  Paul C. Constant, Jr. ,
              George Scheil, and Michael C. Sharp

                 Midwest Research Institute
                  425 Volker Boulevard
                 Kansas City, Missouri 64110
                  Contract No. 68-02-1098
                    ROAP No. 26AAG
                Program Element No. 1HA327
             EPA Project Officer: M. Rodney Midgett

       Quality Assurance and Environmental Monitoring Laboratory
             National Environmental Research Center
           Research Triangle Park, North Carolina 27711
                     Prepared for

            OFFICE OF RESEARCH AND DEVELOPMENT
           U.S. ENVIRONMENTAL PROTECTION AGENCY
                 WASHINGTON, D.C. 20460

                     January 1975

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                        EPA REVIEW NOTICE

This report has been reviewed by the National Environmental Research
Center - Research Triangle Park, Office of Research and Development,
EPA, and approved for publication.  Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
This document is available to the public for sale through the National
Technical Information Service, Springfield, Virginia  22161.
                                  11

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                              FOREWORD

     The collaborative study of "Method 10 - Determination of Carbon
Monoxide Emissions from Stationary Sources" was conducted under Tasks
3 and 5 of EPA Contract No. 68-02-1098, which is Midwest Research In-
stitute Project No. 3814-C, entitled "Standardization of Stationary
Sources Emission Measurement Methods."  Midwest Research Institute
acquired a sampling location and field facilities for the test, se-
lected seven collaborators to perform sampling according to its plan
of test, retrieved field data and analysis results from the collabo-
rators, statistically analyzed the results, and prepared this two-
volume report.

     This volume, Volume I, of the report of test, summarizes MRI's and
the collaborators' activities.  It just presents those activities that
were necessary in preparing for the field test--selection of the site,
design, construction and checkout at the field site of a manifold sam-
pling apparatus needed for the collaborative test, selection of the
collaborators and the experimental design.  This preliminary work is
then followed by a discussion of the field test, a summary of the re-
sults of the collaborators, MRI's statistical analyses of the collab-
orators' results, conclusions and recommendations.

     Volume II of this report contains results of the collaborators
that were submitted to MRI.

     The seven organizations that participated under subcontract to
Midwest Research Institute (MRI) in the test of Method 10 are Coors
Spectre-Chemical Company, Golden, Colorado; Ecology Audits (subsidiary
of Core Laboratories, Inc.), Dallas, Texas; Entropy Environmentalists,
Inc., Research Triangle Park, North Carolina; Environmental Triple S,
St. Louis, Missouri; Interpoll Incorporated, St. Paul, Minnesota;
Scott Environmental Technology, Inc., Plumsteadville, Pennsylvania;
and TRW, McLean, Virginia.
                                 iii

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     The following individuals of these organizations are acknowledged
for  their participation in the collaborative test:  Mr. Dan Briggs of
Coors Spectro-Chemical Company, Mr. Michael Hartman of TRW, Mr. Sam
Humphries of Ecology Audits, Inc., Mr. Maynard Johnson of Scott Envi-
ronmental Technology, Inc., Mr. Roger Johnson of Interpoll Incorporated,
Mr.  Bill McClarence of Environmental Triple S Company, and Mr. Joe
Schiappa of Entropy Environmentalists.

     Special acknowledgments are made to the El Dorado Refinery of the
American Petrofina of Texas, which is located in El Dorado, Kansas,
and  to Mr. Leon Randolph, Superintendent of the El Dorado Refinery for
providing the test location and for the excellent cooperation and cour-
tesies that were extended MRI and the collaborators; to Dr. John B.
Clements, Chief, Methods Standardization and Performance Evaluation
Branch, National Environmental Research Center,  Environmental Protec-
tion Agency, and Mr. M. Rodney Midgett, Government Project Officer,
Methods Standardization and Performance Evaluation Branch, for their
valuable suggestions in planning and reporting;  and to the National
Bureau of Standards (NBS) for supplying the tanks of standard gases.

     The MRI program is being conducted under the management and tech-
nical supervision of Mr. Paul C. Constant, Jr.,  Head, Environmental
Measurements Section of MRl's Physical Sciences  Division, who is pro-
gram manager.  Dr. George Scheil was MRI's field supervisor at El
Dorado, Kansas, during the 2-week test.  Mr. Michael Sharp was respon-
sible for the experimental design and statistical analyses.
Approved for:

MIDWEST RESEARCH II
H1. M. Hubbai
Physical Sciences Division
                                 iv

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                          TABLE OF CONTENTS

                                                                  Page

Summary	     1

I.      Introduction 	     4

II.     Test Site Selection and Description	     6

          Site Selection	     6
          Site Description 	     6

III.    Carbon Monoxide Sampling System	     9

          Design Factors 	     9
          Construction 	     9
          Preliminary Testing	    11

IV.     Experimental Design	    18

          General Considerations 	    18
          Formal Design	    19

V.      Field Test	    22

VI.     Results of Analyses	    32

          Collaborators'  Results 	    32
          Collaborators'  Instrumentation and Deviations from
            Method 10	    39
          MRI's Test Results	    42

VII.    Statistical Analysis of Collaborators' Results 	    44

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                    TABLE OF CONTENTS (Concluded)

                                                                  Page

          Sampling Data	   44
          Standard Analysis	   48
          Comparison Field Data Versus Standards Data	   50

VIII.   Conclusions	   52

IX.     Recommendations	   54

Appendix A - Method lO—Determination of Carbon Monoxide
               Emissions from Stationary Sources 	   55

Appendix B - Request for Proposal Sent to Candidate Collaborators
               for the Method 10 Collaborative Test	   63

Appendix C - Instructions for Collaborators, CO Collaborative
               Test—El Dorado, Kansas 	   71

Appendix D - Effects of Deleted Data	   77
                                  vi

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                             LIST OF FIGURES

No.                               Title                               Page

 1     Photo of CO Boiler Stack at El Dorado Refinery of American
         Petrofina of Texas, El Dorado, Kansas 	    7

 2     On Site General Test Setup	   10

 3     Photographs of Equipment Set Up for Preliminary Test	   12

 4     Drawing of Sampling Manifold	   13

 5     Pump and Water Condenser	   14

 6     Continuous CO Monitor	   15

 7     Results of Preliminary Test of Method 10	   17

 8     Block Diagram of Sampling Manifold	   22

 9     Photographs of the Test Site - CO Collaborative Test,
         El Dorado, Kansas	   24

10     Collaborators at Work	   25

11     Collaborators at Work	   26

12     Block Diagram of Sampling Manifold Used for Test 3A	   28

13     Block Diagram of Initial Sampling Manifold Used for All Tests
         After 3A	   29

14     Collaborators' Results for Block A (200-300 ppm CO)	   36
                                   vii

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                     LIST OF FIGURES (Concluded)




No.                             Title                             Page




15      Collaborators'  Results for Block B (400-600 ppm CO). . .   37




16      Collaborators'  Results of HBS Standard Gases 	   33




B-l     On Site General Test Setup	   57
                                 viii

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                             LIST OF TABLES

No.                               Title                              Page

 1     Expected Mean Squares (Whole Experiment) 	   21

 2     CO Emissions Sampling Schedule 	   27

 3     Collaborators' Results for Level A (200-300 ppm CO)	   33

 4     Collaborators' Results for Level B (400-600 ppm CO)	   34

 5     Collaborators' Results of NBS Standard Gases 	   35

 6     Summary of Results, MRl's Continuous CO Monitor	   43

 7     AOV Uncorrected CO Readings (ppm)	   45

 8     AOV Corrected CO Readings (ppm)	   45

 9     Components of Variance (ppm),,Uncorrected Data	   46

10     Components of Variance (ppm), Corrected Data 	   47

11     Kendall W Method (collaborators versus level)	   47

12     AOV Standards Data	   49

13     Components of Variance (ppm), Standards Data 	   49

14     Average Bias Versus CO Concentration 	   50

15     Field Data Versus Standards:  Components of Variance ....   51

D-l    Effects of Including Runs 1 to 3 and Collaborator 7 (field
         data)	   78
                                    ix

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                     LIST OF TABLES  (Concluded)




No.                             Title                              Page




D-2     Field Data Analyses of Variance	    79




0-3     Analyses of Variance (standards  data)	    80

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                               SUMMARY

     A collaborative test was conducted by MRI at the El Dorado Refinery
of American Petrofina of Texas during 3 to 14 June 1974.  Seven organi-
zations participated in the test of "Method 10 - Determination of Car-
bon Monoxide Emissions from Stationary Sources."  All collaborators
sampled simultaneously using the integrated bag method.  The sampling
manifold was connected to the CO boiler stack of the fluid catalytic
cracking unit.  All runs were of 60 min duration.  Each collaborator
obtained four samples per day—two in the morning and two in the after-
noon.  Sixteen runs were made at each of two CO levels.  MRI had an
NDIR operating in the continuous mode during each run to monitor the
CO concentration.  Each collaborator analyzed six cylinders of CO in
nitrogen which had been certified by the National Bureau of Standards.

     The collaborators submitted tentative readings after each test
and later sent to MRI their final results, which included the original
recorder charts.  MRI checked the collaborators' results and then sta-
tistically analyzed the collaborators' results.

     The collaborators' results from sampling the CO boiler stack were
analyzed to determine the precision of the method and the standard gas
results were used to determine the accuracy of the method.

     Pertinent statistical results from this collaborative test are:

     1.  For the field data:

           •  The within-collaborator standard deviation (o-e) is about
             13 ppm.*

           •  The collaborator-collaborator standard deviation (ac) is
             about 25 ppm.
*  The quantity actually estimated from the analysis of variance is
     o-2 + o?c  (35 ppm).  Indirect methods decompose this sum and re-
     sult in cie = 13 ppm.

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          •   In general, the collaborators'  calibration curves are
             suitably parallel but this is not true for all collabo-
             rators .

     2.  For the standards:

          •   The within-collaborator standard deviation (ae) is about
             4.5 ppm.

          •   The collaborator-collaborator standard deviation (crc) is
             about 22 ppm.

          •   Although the average bias is quite low (average overall
             levels, 7 ppm), the bias definitely varies according to
             the CO level.  The bias is, in general, larger at the
             lower CO levels (up to 24 ppm when CO = 239 ppm), but not
             all collaborators have parallel bias versus concentration
             curves.

     The principal conclusions that are drawn from the results of this
collaborative test are:

     1.  Method 10 as executed in this collaborative test will produce
results with only moderate accuracy of ± 87 ppm  (2a)  on the average.

     2.  The procedure as written in Method 10 is not adequate because:

          a.  The Ascarite weight gain method for measuring C02 content
on the sample is subject to large errors due to the difficulty of mea-
suring the small weight change obtained compared to the weight of the
impinger plus the Ascarite;

          b.  The use of an impinger or bottle for the Ascarite trap
causes great difficulties because the Ascarite tends to form a dense,
solid plug in and around the glass inlet tube which, in turn, blocks
the flow of the gas after a period of time;

          c.  Most commercial NDIR instruments have a significant
amount of curvature in the calibration curves, and many of the collab-
orators did not adequately correct for this nonlinearity of response;
and

          d.  Some calibration gas suppliers provide certificates of
analysis that show errors of as much as 30% when compared with stan-
dard gases.

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     Based upon the conclusions that have been drawn from the results
of this collaborative test, it is recommended that Method 10 be revised
to cover the following points:

     1.  All mention of the C02 determination by weight gain of the
Ascarite gas scrubber should be deleted.  Carbon dioxide should be
done by Method 3 (Orsat-type analysis) of the Federal Register.

     2.  The use of an impinger or bottle type of silica gel and
Ascarite gas scrubber should be deleted.  Sections of a flexible plas-
tic pipe, capped at the ends, should be used instead.  A minimum in-
ternal diameter of 2.5 cm is recommended to prevent blockage.

     3.  More explicit instructions on correcting for nonlinear re-
sponse of the instruments are desirable.

     4.  Analysis procedures of some calibration gas suppliers are
clearly inadequate.  Reliable calibration gases might require NBS cer-
tification or a requirement that gas suppliers follow specific guide-
lines in their analysis of calibration gases.

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                               SECTION I

                             INTRODUCTION

      The Methods  Standardization and  Performance Evaluation Branch,
 National Environmental  Research  Center of  the Environmental Protection
 Agency (EPA)  is engaged in a program  to  evaluate methods,  recommended
 and  promulgated by EPA, for the  measurement  of pollutant emissions from
 stationary  sources.  Midwest Research Institute (MRI)  is working  for
 EPA  under Contract No.  68-02-1098 to  provide data on the reliability
 and  bias of the methods.

      To achieve its objective, MRI plans and executes  a collaborative
 test and evaluation for each method submitted to it by EPA.  Briefly,
 in the execution  of a collaborative test, MRI performs an  in-house
 evaluation  of the method  (which  could  range  from a paper evaluation,
 such as  was the case for  this  test, to a ruggedness test), provides
 sampling locations and  facilities  relative to the test and analysis
 involved, coordinates the collaborative  test, retrieves field data and
 results  of  the collaborators'  chemical analyses of their samples, sta-
 tistically  analyzes results  received  from the collaborators, and  re-
 ports  results to  EPA.

      The work activities  described above were performed by MRI under
 Tasks  3  and 5 of  Contract No.  68-02-1098 on  the collaborative test of
 "Method  10  - Reference  Method  for  Determination of Carbon Monoxide
 Emissions from Stationary Sources," which is the subject of  this  report
 and  is  given on pages 9319 to  9321 of  the Federal Register.  3J9, No. 47,
 Friday,  8 March 1974.   (A copy of  Method 10  is given in Appendix A.)
 These  activities  started  in December  1973 with the review of the method.
 Following this the sampling manifold  to be used by the collaborators
 in the  field was  designed  and  fabricated.  Concurrently with this engi-
 neering  effort, the El  Dorado Refinery of American Petrofina of Texas
was  selected as the site  for the collaborative test.  The sampling man-
 ifold was then taken to the field  site and tested.  Seven collaborators

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were selected for the field test which took place during 3 to 14 June
1974.  During July, the collaborators submitted their results to MRI.
These results were checked for errors and then statistically analyzed.

     This report covers the collaborative test of Method 10 in the fol-
lowing order:  Section II discusses the selection of the site, speci-
fying the criteria followed and gives a description of the site that
was selected for the test.  Section III discusses the manifold sam-
pling apparatus that was constructed by MRI and used by the collabo-
rators.  Section IV presents the experimental design of the test.
Section V discusses the 2-week field test.  Section VI summarizes the
results of the test.  Section VII gives the statistical analysis of
the collaborators' results.  Section VIII presents the major conclu-
sions that were drawn from the results of the test.  Section IX gives
MRl's recommendations.  Appendices comprise the write-up of Method 10,
MRl's request for proposal that was sent to prospective collaborators,
MRl's instructions to the collaborators, and the effects of deleted
data from the principal analysis.

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                             SECTION II

                 TEST SITE SELECTION AND DESCRIPTION

SITE SELECTION

     The criteria for selection of a suitable refinery site are:

     1.  Sampling is to be done from the fluid catalytic cracking unit
incinerator-waste heat boiler, commonly known as the CO boiler.

     2.  Carbon monoxide (CO) emissions must be controllable at or
near the level of the EPA standard--500 ppm.

     3.  The site must provide sufficient area for testing and con-
venient access to the site must exist.

     4.  Necessary utilities, primarily electrical power, must be
available.

     5.  Facility should be representative of refineries in the United
States.

     Sites were sought from several different petroleum companies.
The El Dorado Refinery of American Petrofina of Texas, which is located
in El Dorado, Kansas, approximately 180 miles from MRI, was the only
one that accepted MRl's request.  Although the carbon monoxide levels
from the CO boiler at this facility are normally very low, approxi-
mately 30 ppm, refinery personnel believed that the desired levels of
CO could be achieved without suffering a flameout and could be main-
tained at a level near 500 ppm for the testing.

SITE DESCRIPTION

     While the El Dorado Refinery is a fairly small operation compared
to most of the oil industry, no unusual conditions are known to exist

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in the operation of the refinery that make it unrepresentative of nor-
mal industry practice.  As shown in the next section of this report,
CO levels of approximately 300 and 500 ppm are obtainable from the CO
boiler stacks without causing an unstable condition in the FCCU.

     The stack for the CO boiler at this site is approximately 100 ft
high and is 54 in. in diameter at the top.  A photograph of the stack
is shown in Figure 1.  The hot gases (500 to 900°F) from the CO boiler
enter the stack from the inlet duct shown in the lower left of the
photo approximately 20 ft from ground level.  Four sampling ports are
located approximately 60 ft from ground level.  The stack is located
adjacent to a refinery road and sufficient electrical power for the
sampling equipment is available at the site.  Ample ground area exists
around the stack to accommodate seven collaborators and their sampling
equipment.
      Figure 1.  Photo of CO boiler stack at El Dorado Refinery
          of American Petrofina of Texas, El Dorado,  Kansas

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     Although there are adequately located sampling ports on the CO
boiler stacks, it was not believed practical to place seven collabo-
rators and all their equipment at an elevated sampling platform near
these ports.  The principal reasons are that each of the seven sampling
probes would not necessarily be challenged with the same gas sample
because of their different locations within the stack, and the collab-
orators would not be able to work effectively within the space limita-
tions of a platform on top of scaffolding that would have to be erected.
Consequently, MRI decided, with approval from EPA, to run a sampling
line from one of the four existing ports to ground level and attach to
it a sampling manifold from which each collaborator could effectively
conduct sampling using Method 10 which would provide assurance that
each collaborator's sampling apparatus would receive the same type gas
sample.

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                             SECTION III

                   CARBON MONOXIDE SAMPLING SYSTEM

DESIGN FACTORS

     The initial field test setup is shown in Figure 2.  The principal
factors upon which this manifold system was designed to provide for
simultaneous uniform sampling by a multiplicity of collaborators are:

     1.  Number of collaborators - maximum of 10.

     2.  Materials of construction - not critical; CO is not reactive
or readily adsorbed or absorbed by most materials at moderate temper-
atures .

     3.  Gas stream flow rate - sufficient to assure each collaborator
receives the same gas sample.

     4.  Manifold geometry - identical parallel branches and limited
length for minimal pressure drop and gas flow transit time.

     5.  Water vapor - Method 10 does not require determination of
water and each collaborator must have a water condenser at inlet of
train.  (Therefore, line from stack is unheated and provision for a
drain made in system.)

     6.  Accessibility for sampling - ground-level sampling is far
superior to sampling directly from stack.

CONSTRUCTION

     All pipe in the sampling system from its intake point to the man-
ifold is 1/2-in. stainless steel for heat and corrosion resistance,
since these components are permanently mounted to the stack.  The
sample probe is mounted to a bulkhead fitting on the sample port.  The

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Sampling
Ports
                                            Stack Port
                                                                Intake Located
                                                                in CO Stack
                                                       Direction of
                                                   OQ|  Stack Gas Flow
                                       Moisture
                                       Drain Valve
                                    I   [Moisture
                                    I   I Col lector.
                      •Ground Level
 Sampling
' Ports
                         I  Pressure
                        O Gauge
                            Control
                            Valve
                                         Pump
                        Figure 2.   On site general test  setup
                                        10

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probe extends to the center of the stack with a bend at the end and a
6-in. section of pipe pointed downward.  From the exterior of the bulk-
head fitting, the pipe runs outward 1 ft, bends around the stack to
the steel supports shown in Figure 1 and then runs down to near ground
level.

     Photographs of the sampling manifold appear in Figure 3.  Figures
4 and 5 show the different components of the sampling manifold in de-
tail.

     Figure 4 shows the sampling manifold and the rotameters for mea-
suring flow rates in each branch of the manifold.  All components in
this section are 1/2-in. galvanized pipe and fittings.  The sample
outlet connections are 1/4-in. pipe nipples.

     Figure 5 shows the pump and water condenser.  The pump (A) is a
CAST Model 0822-103-G27/X, carbon vane pump with a capacity of 7 ft3/
min.  Control valve B regulates sample flow rate and the water trap
(C) is a 32-oz, wide-mouth bottle with matching stopper, and (D) is a
galvanized box with a 1/2-in. copper tubing coil inside.  The water
trap was not present in the preliminary test manifold.

     Figure 6 shows the NDIR used by MRI to monitor the CO level dur-
ing each test.  The filter (Part A of Figure 6) initially consisted of
two separate plastic bottles with about 200 g of silica gel and 500 g
of Ascarite, respectively.  As explained in Section V, the impingers
were replaced by the 1-in. diameter polyethylene tube shown.  It should
be noted that the needle valve had to be placed on the inlet side of
the pump (Part B of Figure 6) rather than the outlet, as shown in
Method 10.  This was necessary because the pump is designed to operate
with very little flow restriction on its exhaust side.  Also the
Millipore filter is needed to protect the nondispensive infrared (NDIR)
analysis cells from dust contamination which degrades the signal re-
sponse.  All connections between the downpipe, manifold and pump were
made with 1/2-in. galvanized pipe.

PRELIMINARY TESTING

     In February 1974, MRI installed the sample pipe running from the
stack to ground level and connected it to the sampling system shown in
Figure 2 to determine if a CO level of 500 ppm could be safely reached
and the CO concentration maintained at that level.
                                 11

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Photograph A.   CO boiler stack with
  sample line  on left side.
Photograph B.  Sampling manifold
  with MRI's NDIR on table.  CO
  boiler stack and cooling tower
  in background.
                       Photograph C.  Sampling manifold on table.
                         Pump under table, inlet line at far end
                         of table.

            Figure 3.  Photographs of equipment set up for preliminary test
                                         12

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                                                                                                     OUTLET
Figure A.  Drawing of sampling manifold, Fisher and Porter type FP-1/4-40-G-6 rotameters (A) were used  to
             monitor the flowrate in each branch of the manifold.  Sampling ports (B) were standard
             plumbing fittings with 1/4-in. pipe nipples attached.

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Legend:  The pump (A) is a CAST Model 0822-103-G27/X carbon vane pump with a
         capacity of 7 ftVmin.  Control valve (B) regulated sample flowrate.
         Water receiver (C) is a 32-oz jar and water condenser (D) is a
         galvanized box with a 1/2-in. copper tubing coil inside.

                        Figure 5.  Pump and water condenser
                                        14

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Legend:  Filter (A) is a polyethylene tube 1 in. in
         diameter and 3 ft in length.  Rubber stoppers
         are used at each end and tube is packed 50/50
         with silica gel and then with Ascarite.  Filter
         is then connected to micrometer valve on inlet
         of Thomas diaphragm pump (B).  Sample then goes
         to Matheson No. 602 rotameter (C), a Millipore
         filter (D) and then into Beckman No. 215A CO
         Analyzer (E).  Bausch and Lomb VOM-5 Recorder
         (F) is used for readout.  For calibration,
         gases were run into micrometer valve on pump.
                                Figure 6.  Continuous CO monitor

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With the NDIR connected to a crude version of the manifold, the plant
operators began reducing the excess air to the CO boiler until the CO
level reached 500 ppm.  This required a large deviation from normal
operating conditions, but was attained and varied ± 100 ppm over a
1-hr period.

     MRI personnel returned to the site in April with the manifold
assembly completed for more complete testing of the system.  After the
manifold was connected the downpipe from the stack was found to be
plugged.  The pipe was cleared by pressurizing to about 30 psig
briefly.  At the full rated flow rate of 100 liters/min the manifold
vacuum was about 250 mm Hg but the vacuum decreased to less than 80
mm at 80 liters/min total flow.  After the CO level had been stabi-
lized at about 500 ppm a run was made for about 45 min.  At that time
the manifold pump stalled due to water in the pump chamber.

     The recorder chart from this run is shown in Figure 7.  From the
weight changes of the filter traps, water was 5.0% and C02 was 9.1% in
the gas stream.  The average CO concentration was 452 ppm uncorrected
and 412 ppm corrected for CC>2 content.

     To protect the manifold pump from water condensate, the water con-
denser shown in Figure 5 was built upon returning to MRI.  When the
bath is filled with ice water, the gas at the exit from the trap is
cooled to below ambient and all components downstream remain dry.  The
trap collected 200 to 300 ml of water per hour during operation.
                                  16

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   550
   425
z
9.  300
I
z
LLJ
u
O  20°
   100
                                                                                                      Pump
                                                                                                     Stalled
                           10
15
20
       25
MINUTES
30
35
40
45
                          Figure 7.  Results of preliminary test of Method 10

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                              SECTION  IV

                         EXPERIMENTAL DESIGN

GENERAL  CONSIDERATIONS

     Major considerations  that entered  into the experimental design
of  the collaborative  test  are summarized below.

     1.  Analysis Method - All collaborators would be instructed to
follow the integrated sampling method of Method 10 as it appears in
the 8 March 1974 edition of the Federal Register.  Any deviations from
the method by the collaborators would be noted by the MRI test super-
visor.

     2.  Test Levels of CO -  Two levels of CO are required.  One level
is near  the proposed standard limit value—500 ppm.  The second level
is approximately half the concentration of the standard.

     3.  True Values of CO (determination of bias) - A set of six cyl-
inders of CO in nitrogen from the National Bureau of Standards (NBS)
would be sampled by the collaborators in the field.  The CO concen-
trations of these cylinders ranged from 200 to 900 ppm and were accu-
rate to < 1%.  The collaborators were to analyze each cylinder three
times.  Three cylinders were  to be analyzed on the first day of test-
ing and the other three on the last day of the field test.

     Since the test is designed to measure real samples at a refinery,
and since the CO levels from  the stack are not constant, a true value
cannot be assigned to each run from the sampling manifold.  MRI did
have an NDIR continuously sampling the manifold concentration.  The
readings from this instrument were used primarily to monitor the CO
levels during each test to ensure that the average CO level would be
within the proper range.  The values obtained from this instrument
cannot be assumed to be any more accurate than any of the collabo-
rators ' instruments.
                                    18

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     4.  Sampling Time - Method 10 states that the sampling time shall
be 1 hr.

     5.  Test Schedule - To obtain sufficient data for statistical
analysis a total of 16 runs were made at each level.  Four runs were
made each day.  Thus, the field sampling was arranged for two 5-day
weeks of testing.  The first day of testing was for setup and analysis
of three of the NBS-certified cylinders and the last day for cleanup
and analysis of the remaining NBS cylinders.

     6.  Number of Collaborators - The sampling manifold was designed
to accommodate a maximum of 10 collaborators.  Seven collaborators
were deemed sufficient to obtain a cross section of the organizations
involved with CO sampling, be within acceptable project costs, and
provide sufficient data for the statistical analysis.

     7.  Interferences - Due to its low reactivity, carbon monoxide
can be handled with most common materials of construction—glass, met-
als, plastic or rubber tubing.  Water and carbon dioxide are known in-
terferences in the NDIR analysis and these compounds are removed prior
to introduction into the instrument.  The method also measures the C02
content of the sample stream and corrects the NDIR concentration to
that in the stack before C02 removal.

FORMAL DESIGN

     The basic experimental model is:

       xijkl = u + ci + Bj + CBij + ^(j) + LCik(j) +

where

          Ci = ith collaborator, 1=1, . . ., 7;

          BJ = jth block of CO, j = 1, 2;

        CBj- = collaborator - block interaction;

               kth level nested within jth block,  k = 1
                 16 for every j;

               collaborator - level interaction;

           u = overall mean;
                                 19

-------
     el(ijk) = measurement error in the ijkth cell, 1=1 for every
                 ijk (not retrievable);

       Xiikl = iJk^*1 reading of CO (ppm).

     Block* is considered a fixed factor (since we select the values
of block), while collaborators and levels are considered to be random
factors.

     The expected mean squares are shown in Table 1.

     Since a collaborator never measures the same CO concentration
more than once, there is no direct estimate of o| , i.e., no direct
measure of the repeatability within collaborators.  Thus, the sum

-------
Table 1.  EXPECTED MEAN SQUARES (WHOLE EXPERIMENT)
Source
C
B
CB
L
LC
e
df
6
1
6
30
180
0
EMS
2 99
erg + 32 o^ + o£c
a| + 112 CT| + 16 o£B + 7 o£ + a^C
•J 92
—A L 1C — * 1 _^
0^ + lb CTpg + CTLC
Og + 7 0^ + CT£P
°J+°1C
o-| (not retrievable)
                        21

-------
                                SECTION V

                               FIELD TEST

       MRI personnel arrived at the refinery site on 2 June 1974, to
  assemble the sampling manifold and prepare the site for the collabora-
  tive test which was  to begin on the following day.  The sampling sys-
  tem was assembled as shown in Figure 8, and able to operate at a total
  maximum flow rate of > 100 liters/min.
Inlet Line
from Stack
Sampling
Manifold


Water
Condenser


Pump
Exhaust
           Figure 8.   Block diagram of initial sampling manifold
        On 3 June  1974,  the collaborative  test began with an orientation
  meeting at 0800.  At  the meeting each collaborator received a copy of
  the collaborator  instructions  (see Appendix C).  At the meeting all
  collaborators except  one reported that  all equipment had arrived and
  they  were ready to  test.  One  collaborator's equipment had been de-
  layed in transit.

        The collaborators  then proceeded to  the refinery test site and,
  except for the one without equipment, began setting up equipment to
  begin sampling the check gases supplied by the National Bureau of Stan-
  dards.  Each collaborator was  to analyze  three of the gases on 3 June
  and the other three gases on 14 June.   The collaborators began setting
  up their equipment on tables supplied at  the test site, except for
                                    22

-------
Collaborator No. 5* who had his own sampling van at the site with his
equipment set up inside the van.  As the sampling of the check gases
proceeded, light intermittent rain began falling, and the collaborators
moved their equipment under shelter.  Since most of the instruments
had to be kept plugged in round-the-clock for proper stability, the
field sampling was finally modified as follows:  The Tedlar bags for
two tests were filled according to the method at the field site.  Then
the bags were taken for analysis to the motel where the instruments
were kept in the rooms.**  Collaborators 2 and 5 kept their instru-
ments in the van parked at the test site.  In this manner two samples
were taken in the morning and analyzed during the lunch break.  Then
two more samples were taken in the afternoon and analyzed at the end
of the day.  To accomplish this, some of the collaborators had to
borrow a second bag and sample box from MRI due to lack of equipment.

     Figures 9 to 11 show the test site and photographs of the collab-
orators at work.

     Run No. l--the first sampling run from the CO-boiler emissions—
at the A level (~ 250 ppm) began at 1018 on 4 June 1974.  All seven
collaborators were ready for the test.  The date and time for each
run is given in Table 2.

     Due to water condensing out in the two rotameters of the mani-
fold, all collaborators sampled at a constant 400-cc/min rate during
Runs Nos. 1 and 2.  Heavy rain during the afternoon of 4 June forced
the postponement of Tests- 3 and 4 until the following day.  To elim-
inate the water condensation in the rotameters the ice-cooled con-
denser was moved to a point upstream from the rotameters as shown in
Figure 12.

     During the first three tests it became apparent that the card-
board drums--which most of the collaborators had—could not withstand
the negative pressure of about 50 mm Hg at the sample ports with a
flow rate of 20 liters/min through each branch of the manifold.
*   Hereafter the collaborators will be referred to by randomly assigned
      designations:  Collaborator 1, Collaborator 2, etc.
**  Since the refinery had no protected area of sufficient size where
      the collaborators' instruments could be set up for the duration
      of the test schedule, and there was inclement weather, this pre-
      cautionary step was necessary.
                                  23

-------
to
                               'r
               Figure 9.  Photographs of the test site - CO collaborative test, El Dorado, Kansas

-------
                      A.  Roger Johnson (Interpoll)
N>
Ul
 B.   Mike Hartman

     (TRW)
                                                                                     C.   Maynard Johnson (Scott)
                                              Figure 10.   Collaborators  at work

-------
A.  Bill McClarence (Environmental
    Triple S)
B.  Joe Schiappa (Entropy Envi-
    ronmentalists).  Dan Briggs
    (Coors) in background
          No photograph available of Sam Humphries (Ecology Audits)
                     Figure 11.  Collaborators at work
                                      26

-------
Table 2.  CO EMISSIONS SAMPLING SCHEDULE
Run no.
1A
2A
3A


4A
5A
6A
7A
8A
9A

10A
11A
12A
13A
14A
15A
16A
IB
2B
3B
4B
5B
6B
7B
8B
9B
10B
11B
12 B
13B
14B
15B
16B
17B
Date
6/4/74
6/4/74
6/5/74


6/5/74
6/5/74
6/5/74
6/6/74
6/6/74
6/6/74

6/6/74
6/7/74
6/7/74
6/7/74
6/7/74
6/14/74
6/14/74
6/10/74
6/10/74
6/10/74
6/10/74
6/11/74
6/11/74
6/11/74
6/11/74
6/12/74
6/12/74
6/12 /74
6/12/74
6/12/74
6/13/74
6/13/74
6/13/74
6/13/74
Start
1018
1146
0939


1139
1458
1616
0851
1005
1315

1430
0856
1015
1336
1450
0840
0957
0903
1019
1327
1448
0906
1024
1317
1436
0848
1010
1133
1439
1552
0842
1002
1256
1411
Stop
1118
1246
1039


1239
1558
1716
0951
1105
1415

1530
0956
1115
1436
1550
0940
1057
1003
1119
1427
1548
1006
1124
1417
1536
0948
1110
1233
1539
1652
0942
1102
1356
1511
Comments
Sampling flow constant at 400 cm^/min.
Sampling flow constant at 400 cm^/min.
Approximately 400 cm^/min sampling rates
proportional to total flow, t^O con-
denser now ahead of manifold.
Pump now between condenser and manifold.
Manifold flowrate decreasing during run.
Cloudy — no rain.
Manifold flowrate still decreasing.
Manifold flowrate still decreasing.
Change to ~ 600 cm^/min proportional sam-
pling.
Manifold flowrate now stable.
Variable weather conditions 6/5-7.
Little rainfall.




Fair weather during second week of test.



Power loss after first attempt to start run



Run deleted - CO concentration too high.








                   27

-------
Inlet Line
from Stack
Wafer
Condenser


Sampling
Manifold


Pump
Exhaust
             Figure  12.   Block diagram of sampling manifold
                             used for Test 3A
                                     28

-------
      The collaborators also had difficulty maintaining air-tight sys-
 tems under these conditions.   Any leaks  that appeared in one  collabo-
 rator's sampling lines would then allow  ambient air to enter  the mani-
 fold and affect other collaborators'  results as well.   To alleviate
 the problem,  the manifold system pump was  moved to a point upstream of
 the manifold  as shown in Figure 13.   This  change was carried  out be-
 fore starting Run 4A.  All runs from this  point onward used this mani-
 fold system with a slight positive pressure maintained at the sampling
 ports.
Inlet Line
from Stack
Water
Condenser


Pump


Sampling
Manifold
Exhaust
         Figure 13.  Block diagram of sampling manifold used
                    for all tests after 3A.
      The condenser protected the pump from water and the carbon vane
 centrifugal pump was well sealed and contained no oil or other sub-
 stances which might contaminate the sample stream.   Thus, the sampling
 ports of the manifold could be maintained at positive pressure without
 causing any bias in the results or unreliability of the sampling sys-
 tem components.   All collaborators could then sample a uniform gas
 stream with no possibility that a leak or other malfunction in one
 collaborator's system could affect anyone else's results.

      By the end of the day of 6 June, the high winds and heavy rains
 which hampered operations earlier in the week ended.  During the week-
 end of 8 to 9 June, very high winds and heavy rains overturned the
 tables supporting the manifold but caused only minor damage to the
 equipment which did not delay testing.  Hot, fair weather existed
 throughout the second week of the test.

      As the first sets of preliminary results were reported in the
 field to MRI's test supervisor, potentially serious errors appeared in
 the results of the CO- analysis by the Ascarite weighing method.  The
 weight changes of the Ascarite traps were varying widely.  The weight
 of the impinger with its charge of Ascarite was simply too great com-
 pared to the slight change in weight due to the C02 absorbed.
                                   29

-------
Furthermore, a serious design fault in the Ascarite impinger system
also appeared.  As the glass inlet tube was inserted into the bed of
Ascarite in the impinger, it became plugged with Ascarite.  Carbon
dioxide from the sample gas then converted the Ascarite in and around
the end of the glass tube to a rock-hard plug after a period of time
which varied from a few minutes to about 2 hr of operation.  The inter-
ruptions in the gas flow could be alleviated by one of two methods.
If a long, flexible tube packed with Ascarite was used instead of the
impinger, solid plugs did not form if the tube had an I.D. of £ 25 mm.
Instead, the Ascarite was progressively exhausted along its length.
The second method of preventing Ascarite fouling was to place the sil-
ica gel and Ascarite as separate layers in a single impinger.  With
the Ascarite layer above the silica gel the glass tube could penetrate
the bed without plugging and the gas stream then contacted the Ascarite
over an area sufficient to prevent flow interruption.

     By the beginning of the second week of testing, all collaborators
had adopted one of the two methods of C02 removal and no further prob-
lems were reported with plugged C02 traps.  Also, all collaborators
used only Orsat-type CC^ analysis during the second week of testing
after the decision was made, with the approval of the EPA project mon-
itor, to abandon the Ascarite weighing method for CC^ determination.

     During the first 3 days of testing the sample stream flow rate
repeatedly decreased by as much as 50% over the 1-hr period of a run.
Tests made between runs showed no decrease in the maximum flow rate
when the control valve was opened fully.  However, a heavy buildup of
rust and fly ash particles was found in the valve.  By 7 June, the flow
had stabilized and remained reasonably constant for all subsequent tests,
The flow changes were probably caused by partial blockage of the con-
trol valve by the rust and fly ash which had accumulated in the pipe
running down the stack during the period before the collaborative test
began.

     Beginning with Run 8A the collaborators were allowed to increase
their proportioned sampling rate to ~ 600 car/tain after it was deter-
mined that all collaborators had sufficiently large Tedlar bags to ob-
tain a larger sample volume.

     To regain the two runs lost due to rain on 4 June, the test sched-
ule was modified slightly by having the collaborators sample the N3S
check gases whenever they had time during the testing so that the morn-
ing of 14 June, the last scheduled day of testing, could be used to ob-
tain two additional runs at the A level of CO for a total of 16 runs at
each level.  By 13 June, all collaborators had sampled and analyzed all
six cylinders of check gases in triplicate.

                                  30

-------
     Testing at level B (•« 500 ppm) was carried out during 10 to 13
June.  Run 5B was started at 0848 on 11 June, but a power loss occurred
3 min after the test started on one of the circuits used for the test
equipment.

     The power failure was caused when refinery personnel accidentally
tripped a circuit breaker.  After power was restored,  the run was re-
started after all collaborators had reevacuated their  sample bags.

     During the first half of Run 9B the MRI CO monitor showed > 1,000
ppm CO.  When the refinery control room personnel attempted to correct
the CO boiler excess air, the CO boiler went briefly into a state of
incomplete combustion.  The control room instruments showed combustible
gases in the CO boiler exhaust for about 2 min before  the process was
brought back under control.  When Collaborator 5 analyzed his sample
immediately after the end of the run, he reported the  CO level was far
above 1,000 ppm.  The collaborators were then instructed to delete
Sample 9B and, if necessary, pump out the sample bag for that run so
that two samples could still be taken before breaking  for lunch.

     Runs 15A and 16A were made on the morning of 14 June.  All equip-
ment was then dismantled and the site cleaned.  After  a final meeting
the site was vacated by 1500 on 14 June.
                                 31

-------
                             SECTION VI

                         RESULTS OF ANALYSES

     This section discusses the results which the collaborators sub-
mitted to MRI after the field test.  Significant variations from
Method 10 are also noted.  The last part of this section contains the
measurements obtained by the MRI monitoring device.  Results from col-
laborators are contained in Volume II of this report.

COLLABORATORS' RESULTS

     A summary of the results which the collaborators submitted to
MRI is shown in Tables 3 to 5 and Figures 14 to 16.  Table 3 and
Figure 14 show results for Level A (200 to 300 ppm) and Table 4 and
Figure 15 show results for Level B (400 to 600 ppm).  The two sets of
data overlap on some runs due to the difficulty in maintaining a con-
stant level.  Table 5 and Figure 16 show the collaborators' results
from their analyses of the NBS-certified standard gases, and the values
MRI obtained from reading the collaborators' recorder charts.

     The large errors found in Collaborator 7's results for the NBS
standard gases were traced to inaccurate span gases.  The consistently
high  results on the NBS gases were noted during the test.  In an
effort to identify the cause, another collaborator's span gases were
analyzed on Collaborator 7's instrument.  Using the other collaborator's
span gases, the NBS gas results agreed with the predicted values.  From
the NBS gas data, the span gases used by Collaborator 7 were approxi-
mately 30% higher than the certified value.  Since such an error would
not have been detectable if all collaborators were operating indepen-
dently, Collaborator 7 could make no correction in his results.
                                  32

-------
                                                 Table 3.  COLLABORATORS' RESULTS FOR LEVEL A (200-300 ppm CO)


(I)*/



(2)



(3)



(4)



(5)



(6)



(7)





Instrument reading (ppm CO)
MRI readings0/
Percent C02 measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readings0./
Percent C02 measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readings0/
Percent C&2. measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readings0./
Percent CC? measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readings0-/
Percent CC>2 measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readings0/
Percent COj measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readings0./
Percent CO2 measured
Stack CO level (ppm)

\t&>
235
(245)
12.2
207
342
(346)
13.6
295
335
(323)
Neg.
-
71
(53)
2.8l/
69
416
(415)
13. 6l/
359
380
(380)
16.0
319
430
(448)
26.3d/
317

2*a/
885
(885)
15.5
748
324
(328)
9.0
295
418
(404)
Neg.
-
212
(216)
8.4l'
194
406
(405)
e.s!'
378
379
(379)
16.2
318
430
(456)
29. ll'
305

3A£/
640
(650)
14.0
550
540
(541)
12.2
474
_
-
-
-
247
(251)
' 5.1-
234
_
-
1
-
820
(820)
15.4
694
1,184
(1,185)
' sl/
1,125

4A
330
(335)
15.0
281
295
(297)
12.7
258
325
(335)
12.6
284
286
(289)
14. Ol/
246
273
(273)
14.3d/
234
319
(319)
13.6
276
320
(380)
3l/
311

5A
300
(305)
13.5
260
302
(298)
12.2
265
300
(305)
13.2
260
249
(260)
12. 7l/
228
272
(270)
14.3d/
233
280
(280)
13.0
244
_
-
-


6A
350
(350)
15.5
296
345
(350)
12.5
302
330
(335)
13.9
284
291
(296)
12 .9d/
253
311
(315)
20. 5l/
247
319
(319)
14.2
274
_
-
-

Run
7A
295
(320)
13.5
255
345
(342)
13.5
298
340
(332)
14.9
283
244
(251)
7.5l/
226
315
(315)
15.81'
265
300
(300)
14.6
256
370
(390)
0.6l/
347
Number
8A
263
(270)
13.5
228
280
(257)
12.5
245
290
(292)
14.2
249
210
(212)
4.51/
181
257
(255)
5.9d/
242
250
(250)
14.8
213
240
(253)
0.61/
225

9A
298
(305)
13.0
259
335
(333)
13.6
289
357
(359)
14.2
307
177
(184)
7.2l/
164
281
(285)
12 .Sl/
246
295
(295)
14.5
252
350
(380)
0.6l/
328

IDA
355
(363)
15.0
302
365
(367)
12.3
320
370
(374)
14.8
315
204
(210)
8. a!/
186
315
(315)
7.ol/
293
320
(320)
14.7
273
400
(428)
0.6l/
375

11A
325
(335)
14.5
278
310
(307)
13.7
268
290
(285)
14.2
249
194
(198)
8.3d/
178
270
(270)
12. Ol/
238
265
(265)
14.7
226
40
(40)
ol/
40

12 A
290
(290)
13.0
252
330
(333)
13.2
286
323
(320)
15.1
284
207
(213)
10. ol/
185
280
(280)
0
280
285
(285)
15.2
242
50
(50)
ol/
50

13A
295
(300)
14.0
254
325
(324)
14.4
278
310
(304)
13.0
270
125
(129)
6.2l/
117
286
(285)
7.6l/
264
260
(260)
14.6
222
450
(472)
12 .4l/
394

14A
305
(310)
14.0
262
315
(315)
13 6
272
318
(314)
13.5
275
119
(123)
6.8l/
111
283
(285)
13. 7l/
244
266
(266)
14.4
227
290
(305)
8.7l/
265

15A
295
(295)
15.0
251
335
(333)
14.6
286
309
(294)
15 1
262
308
(314)
13.7
266
300
(300)
14.4
257
250
(250)
14.1
215
340
(355)
14.0
292

16A
270
(275)
14.0
232
341
C341)
15.2
289
313
(304)
15.0
266
332
(333)
14.8
283
300
(300)
14.9
253
256
(275)
14.7
218
360
(400)
15.0
306
at  These runs were made under negative pressure.
b/  Collaborator.
c/  Readings MRI obtained from collaborators' recorder charts.
d_/  Value obtained by Ascarite weight gain.

-------
                                                  Table 4.   COLLABORATORS'  RESULTS  FOR  LEVEL B (400-600 ppm CO)
Run Number

(1)^



(2)



(3)



(4)



(5)



(6)



(7)




Instrument reading (ppm CO)
MRI readings^/
Percent C02 measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readingsS/
Percent C02 measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readings£/
Percent C02 measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readings^/
Percent C02 measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readings':/
Percent CC^ measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readings^
Percent C02 measured
Stack CO level (ppm)
Instrument reading (ppm CO)
MRI readingsE/
Percent CC? measured
Stack CO level (ppm)
15
400
(405)
14.0
344
425
(427)
13.6
367
430
(420)
13.0
374
307
(313)
13.1
267
372
(370)
13.6
321
360
(360)
13.4
312
360
(385)
13.5
311
2B
170
(175)
7.0
158
425
(422)
12.5
372
365
(355)
13.5
316
293
(279)
13.5
248
362
(360)
12.0
319
380
(380)
15.2
322
330
(355)
13.5
285
3B
450
(460)
14.0
387
510
(505)
14.4
437
545
(535)
13.5
471
456
(475)
12.4
399
478
(460)
13.6
413
479
(479)
14.7
409
620
(632)
14.1
533
4B
460
(470)
14.0
396
615
(617)
14.4
526
600
(600)
14.0
516
474
(484)
7.8
437
526
(530)
13.4
456
580
(580)
14.6
495
780
(795)
14.0
671
SB
495
(500)
15.0
421
495
(496)
13.6
428
538
(535)
14.4
461
455
(464)
13.6
393
441
(440)
14.3
378
445
(445)
14.8
379
610
(615)
14.6
521
6B
420
(420)
14.0
361
470
(475)
15.2
399
455
(450)
13.8
391
404
(443)
12.8
352
397
(400)
14.4
34C
404
(404)
14.7
345
540
(561)
14.5
462
7B
435
(440)
15.0
370
450
(453)
15.4
381
443
(437)
14.5
379
447
(454)
12.1
393
410
(410)
15.0
349
509
(509)
15.0
434
540
(556)
14.5
462
8B
510
(510)
15.0
434
580
(582)
15.6
490
565
(561)
14.2
485
546
(554)
10.6
488
510
(515)
14.6
436
507
(507)
14.6
431
710
(671)
14.2
609
10B2/
745
(745)
14.0
461
770
(737)
14.1
661
745
(742)
14.0
641
515
(541)
13.8
444
660
(660)
14.1
567
685
(685)
14.9
583
_
-
-

11B
655
(665)
14.0
563
640
(643)
14.8
545
695
(692)
14.0
598
513
(540)
13.8
442
606
(608)
14.8
516
640
(640)
14.5
547
840
(844)
13.6
726
12 B
492
(490)
15.0
418
535
(490)
14.2
459
505
(505)
13.5
437
498
(507)
13.6
430
445
(450)
15.0
378
440
(440)
14.6
J76
580
(590)
13.5
502
13B
390
(400)
14.0
335
400
(495)
14.6
342
440
(440)
13.5
381
256
(265)
7.6
241
408
(412)
14.4
349
400
(400)
14.3
343
520
(538)
13 0
452
14B
576
(580)
15 0
490
550
(548)
13.2
477
611
(609)
14.2
524
596
(605)
13.8
514
540
(535)
14.0
464
575
(575)
14.5
492
710
(7351
13 8
612
156
390
(395)
14.0
335
445
(445;
15.2
377
428
(418)
15.2
363
424
(435)
13.2
368
385
(385)
14.6
329
385
(3851
14.3
328
510
(5311
14 0
439
16S
515
(530)
13 0
443
640
'639)
14 7
546
625
(629)
13.7
539
647
(6631
13.7
588
603
(594)
14."
5U
619
(6191
15.0
523
S30
(S301
13 I
721
ill
580
(590,
14 0
i99
650
(C-S,
li 9
553
633
(624)
13.5
545
629
(642)
12 4
551
594
(5941
14 9
506
590
(5901
1- 0
50-
SiO

14 0
'"-
a/  Run No. 9B was deleted - CO level > 1,000 ppm.
b/  Collaborator
£/  Readings MRI obtained from collaborators'  recorder  charts.

-------
                                                    Table 5.  COLLABORATOR RESULTS OF NBS STANDARD CASES
l/i
Gas cylinder no.



(1)b/



(2)



(3)



(4)



(5)



(6)



(7)






Run 1
2
3
Average
Run 1
2
3
Average
Run 1
2
3
Average
Run 1
2
3
Average
Run 1
2
3
Average
Run 1
2
3
Average
Run 1
2
3
Average
1 (517

Reading
522
522
522
522
540
540
540
540
537
537
536
537
542
542
538
541
494
489
489
491
510
510
-
510
730
730
730
730
ppm)
MRI's
value-'
535
535
535

538
538
538

518
518
517

520
520
520

493
490
490

510
510
-

708
708
703

2 (734

Reading
730
734
735
733
740
750
750
747
760
760
760
760
740
756
758
751
686
695
675
685
740
745
-
742
1,010
1,015
1,015
1,013
ppm)
MRI's
value 2/
735
740
745

716
738
738

768
768
768

770
770
770

695
700
680

740
745
-

1,010
1,015
1,020

3 (903

Reading
900
900
900
900
930
920
915
922
903
902
902
902
871
875
872
873
800
790
790
793
910
910
-
910
1,200
1,200
1,200
1,200
ppm)
MRI's
value-'
900
900
895

930
920
915

912
911
911

895
895
895

815
800
800

910
910
-

1,200
1,200
1,200

4 (480

Reading
490
490
492
491
510
520
523
518
510
510
510
510
506
508
520
511
450
464
464
466
490
485
-
488
685
685
685
685
ppm)
MRI's
value^
495
495
500

506
513
513

507
507
507

528
528
533

470
465
465

490
485
-

659
659
659

5 (258

Reading
275
275
275
275
295
300
295
297
268
267
268
268
289
285
287
287
252
251
264
256
250
250
.
250
370
370
370
370
ppm)
MRI's
value-'
275
275
275

294
298
294

278
278
278

294
290
295

245
245
250

250
250
-

344
339
339

6 (239

Reading
270
270
270
270
290
280
275
282
270
270
270
270
265
265
264
265
241
245
248
245
250
245
-
248
332
332
332
332
ppm)
MRI's
value
265
260
260

286
281
277

264
264
264

269
271
271

245
245
250

250
245
.

305
305
305

                                                                                                                                                 a/
       a/  Readings MRI obcained  from collaborators' recorder  charts.
       b/  Collaborator.

-------
    12




    11




    10




     9




     8





 E    7

 a


S    6
o
u
              C2
6
                                                                10
12
                                   8

                                 RUNS


Figure 14.   Collaborators' results for Block A (200-300 ppm CO)
14
16

-------
O
(J
10



 9



 8



 7



 6



 5



 4



 3



 2



 1



 0
                       I
J	1
I
I	I
1	I
I
J
           IB    2B    3B    4B    5B    6B
7B    8B    10B

    RUNS
     11B    12B    13B    14B   15B    16B    17B
                     Figure 15.   Collaborators'  results for Block B (400-600 ppm CO)

-------
00
           12


           11


           10


           9


           8


           7

        Q.
        PL
        8  6
        o
        u
           5


           4


           3


           2


            1


           0
I
j
                                     54123
                                        NBS Standard Cylinder Number

                              Figure 16.  Collaborators' results  of NBS  standard gases
                                                               NBS Values
                                                       Cylinder           ppm
                                                          1
                                                          2
                                                          3
                                                          4
                                                          5
                                                          6
                        517
                        734
                        903
                        480
                        258
                        239

-------
COLLABORATORS' INSTRUMENTATION AND DEVIATIONS FROM METHOD 10

     The instrumentation used by each collaborator is noted.  Devia-
tions from Method 10 are also recorded.  Comments with regard to the
methods of calibrating and reading the instrument charts are based
upon an analysis by MRI of the strip chart recordings which each col-
laborator supplied after completion of the field testing.  Where the
procedure used was unclear, MRI requested further information from the
collaborator.

     Collaborator No. 1 - Gas sample went from inlet to rotameter to
water trap and then into a Universal Electric diaphragm pump.  The
pump forced a sample into a 3-ft^ Tedlar bag.  One bag was contained
within its enclosure, which was a large cardboard shipping barrel.  A
second bag and enclosure was borrowed from MRI.  The enclosure was a
1-ft x 3-ft x 4-ft aluminum case.  Since the cardboard barrel leaked,
a sample could not be pulled into bag as per Method 10.  A Beckman 3ISA
analyzer was used for analysis.  The calibration gases used were sup-
plied by Scott and certified as 807 ppm, 515 ppm, and 236 ppm CO.  C02
was analyzed by the Fyrite analyzer.  Impingers were used for C02 and
IUO removal traps.

     Only high span (807 ppm CO) and zero gases were generally used
before and after each run.  Manufacturers' calibration data were used
to correct nonlinearity.

     Collaborator No. 2 - Sampling was done by Method 10.  A 96-liter
Saran bag enclosed in a 55-gal. steel drum was used by this collabo-
rator.  He borrowed a second bag from MRI—same construction as that
borrowed by Collaborator 1.  An MSA Lira 303 analyzer was used for CO
analysis.  Calibration gases of 591 ppm and 324 ppm CO supplied by
Air Products were used.  C02 was analyzed by Orsat.  C02 and 1^0 fil-
ters were clear plastic cartridges 5 cm in diameter and 10 cm long.

     This collaborator did all analyses on-site in another collabora-
tor's truck, ran both span gases and zero after each sample, and
assumed a straight line between calibration points.

     Collaborator No. 3 - Sampling was done by Method 10.  This col-
laborator used 2.5 ft^ Tedlar bags.  One bag was used with a 2-ft x
3-ft x 2-ft fiberglass shipping case and the other was a similar rigid
wooden packing case.  An MSA Lira 200 CO Analyzer was used.  Calibra-
tion gases used were supplied by Air Products and were certified as
258 ppm, 609 ppm and 965 ppm CO.  Gas traps were made from 8-oz wide-
mouth bottles.  C02 was analyzed by the Fyrite analyzer.
                                  39

-------
     A  linear response was assumed.  The 965- and 609-ppm standards
were usually used with each set of  two samples.  Usually only the 965-
ppm gas reading was used  to determine results.

     Collaborator Mo. 4 - After Run 3A, all sampling was done by Method
10.  This collaborator used 1.5-ft3 Tedlar bags in a 23-gal. cardboard
drum.  The analyses were  done using an MSA Lira 300 Analyzer.  Calibra-
tion gases used were supplied by Linde and were analyzed as 310 ppm,
520 ppm, and 690 ppm CO.  Large impingers were used for CO- and H-O
filters, but finally a single impinger with separate beds of silica gel
and Ascarite was used.  A Fyrite Analyzer was used for C0~.

     Zero and 690-ppm gases were used with each sample.  A linear re-
sponse was assumed.  The apparent CO concentration from a least-squares
fit of calibration on five different days was used rather than the
manufacturer-supplied value.

     Collaborator No. 5 - Sampling was done by Method 10 with a 50-ft
length of polyethylene tubing connected between the water condenser
and the 36-liter Tedlar bag, which was enclosed in a Plexiglass case.
A Beckman 315 AL CO Analyzer was used.  Calibration gases were supplied
by Liquid Air, analyzed at 827 ppm, 594 ppm,  and 83 ppm CO.  Large im-
pingers were used initially for the C02 and 1^0 traps.   This was changed
to a plastic bottle with a hole in the bottom for the exit tube after
Test 14A.  The Ascarite weighing method for C02 was used for the first
14 runs.  The remaining runs were by Orsat.

     This collaborator ran calibrations for each run and plotted a
smooth curve through the points.

     Collaborator No.  6 - Sampling was done  by Method 10.   One hundred-
liter Tedlar bags were used with a 2-ft high cardboard drum.   All bags
for each day were analyzed together each evening.   An Intertech Ana-
lyzer was used for CO analysis.  Calibration gases were supplied by
Matheson.  Concentrations of 315,  660, and 1,050 ppm CO were used.
An impinger was used for the silica gel and a length of plastic pipe
for the Ascarite.  An Orsat was used for C02  analysis.

     This collaborator had the only CO analyzer with a linear response.
The instrument had special linearizing circuits.  Response was very
linear over the entire range.   All three standards were run once for
each set of bags analyzed.
                                  40

-------
     Collaborator No. 7 - Sampling was done by pumping the gas from
     «_^«___ o
the manifold into a 2-ft  Tedlar bag with a Universal Electric dia-
phragm pump.  An MSA Lira 300 CO Analyzer was used.  Calibration gases
of 285, 600, and 1,000 ppm were supplied by Linde.  A Fyrite Analyzer
was used for CO?.  Testing began with separate small drying tubes for
t^O and C02 absorption.  This was later changed to a single impinger
with separate layers of silica gel and Ascarite.  All three span gases
were measured with each set of samples but only the zero and 1,000-ppm
gases were used in calculating results.  Samples were calculated using
a manufacturer-supplied calibration curve but the standards were done
by assuming a linear response.

     General Comments - As can be seen from the preceding pages, the
equipment and procedures used in Method 10 are far from being stan-
dardized at this time.  A wide variety of sampling bags and enclosures
were used by the collaborators.  Due to the unexpected difficulty with
the Ascarite, C02 traps, many different methods were used to allevi-
ate the problem.  Also, only one of the collaborators had a CO analyzer
which had a linear output.  The linearizing circuits increase the
price of a CO analyzer significantly and have only recently been
available from commercial sources.  Thus most of the analyzers now in
use will have a nonlinear output.  However, many of the deviations
from Method 10 had a small effect on the results of this collaborative
test.  While the Fyrite Analyzer is not capable of as high a precision
as an Orsat Analyzer under controlled conditions, the Fyrite's simplic-
ity and superior ruggedness make it more suitable for field work.  The
results by Orsat analysis were slightly more precise during this test
but difference was small  (~0.5%).

     Most of the variations in sample bags, enclosures, and pumping
arrangements would be expected to function as well as that specified
by Method 10.  Since the sampling lines must operate at ambient or
slightly lower pressure,  leaks are a severe problem in Method 10 and
in the various modified methods used.

     Some of the methods used in reading the recorder charts and cal-
culating the CO levels leave much to be desired.  Where the instrument
output is nonlinear, a smooth curve drawn through several calibration
points is probably the best method, although it is subject to errors
in drawing the curved line.  Use of a manufacturer-supplied curve can
lead to trouble, since the shape of the curve does change with time.
Assuming a straight-line relationship between calibration points can
lead to very good or very bad results, depending on how far the sample
reading is from the nearest calibration point.
                                  41

-------
     A further problem was that the method does not state limits of
accuracy for the rate meter used to monitor the sampling rate.  The
collaborators used a wide variety of meters for this function with
accuracies of calibration and readability of from < 1% to + 50%.  Since
the CO concentration of the gas stream did change very rapidly, impre-
cise control of sampling rate may have been a major contributor to the
poor precision of the results.

MRI'S TEST RESULTS

     The results from MRI's continuous monitor are given in Table 6.
These results were obtained by assuming a linear response and measur-
ing the areas under the curves which comprised the analog results of
each run with a planimeter.  The instrument's response is linear to
about 400 ppm.  Above this concentration response becomes increasingly
nonlinear.

     The results are in general agreement with those of the collabora-
tors.  No exact comparison is possible, however, because the analyzer
went off scale frequently and because a leak was later discovered in
the sampling pump which caused dilution of the sample gas to occur to
some extent.  Also the continuous method is simply a time average,
while the integrated method is a weighted average.  The pump leak error
was partially cancelled, since the flow rate was held constant through-
out the test, and the calibration gases were run using the same ar-
rangement and flow rate.  However, the true flow rate of the sample
was so low that a significant delay time appeared in the instrument
response.  Due to temperature changes of the exposed instrument, the
instrument drift was sometimes very high (about 50 ppm over 3 hr).
                                  42

-------
      Table 6.  SUMMARY OF RESULTS, MRI'S CONTINUOUS CO MONITOR
Run 1A - 330 ppm

Run 2A - 314 ppm

Run 3A - 222 ppm     Ascarite problems

Run 4A - 282 ppm

Run 5A - 292+ ppm    Off scale 4 min

Run 6A - 262 ppm     Ascarite problems

Run 7A - 320 ppm

Run 8A - 279 ppm

Run 9A - 290 ppm


Run IDA - 329 ppm

Run 11A r 309 ppm

Run 12A - 321 ppm

Run 13A - 275 ppm

Run 14A - 266 ppm

Run 15A - 286 ppm

Run 16A - 236 ppm
Run IB - 451 ppm

Run 2B - 398 ppm

Run 3B - 489+ ppm  Off scale 7 min

Run 4B - 540 ppm

Run 5B - 569+ ppm  Off scale 5 min

Run 6B - 527 ppm

Run 7B - 476 ppm

Run 8B - 520 ppm

Run 9B - off scale
  25 min

Run 10B - 507+ ppm Off scale  8 min

Run 11B - 653 ppm

Run 12B - 484 ppm

Run 13B - 463 ppm

Run 14B - 664+ ppm Off scale  4 min

Run 15B - 429 ppm

Run 16B - 681 ppm

Run 17B - 615 ppm
                                   43

-------
                             SECTION VII

           STATISTICAL ANALYSIS OF COLLABORATORS' RESULTS

SAMPLING MTA

     Although the basic design was not altered during the field test
(see Section IV - Experimental Design), some of the data were neces-
sarily discarded as discussed below.

     Collaborator 7 demonstrated much less stable results than all
other collaborators.  This was not due to one or a few outliers, but
instead to a genuinely more erratic performance than the other collab-
orators.  Therefore, this collaborator was eliminated from the data
analysis* after it was shown that the variance of his readings was
significantly greater than the variance of other collaborators
(F28>31 = 2.43).

     The first three runs (Block 1) were under negative pressure, and
the results reflect this undesirable fact.  So the main analysis of
variance deletes these three runs (they were analyzed separately); i.e.,
there are now 13 levels of L within Block 1, and 16 levels of L within
Block 2.

     Finally, on Levels 4 to 14 (Block 1), Collaborators 2 and 5 used
a C0£ correction method that was subsequently abandoned.  Therefore,
these 22 observations of corrected CO were calculated using the aver-
age C02 readings of the collaborators who made an Orsat-type analysis
for C02-  (In the uncorrected data set, this was, of course, not nec-
essary.)

     The analyses of variance (corrected and uncorrected readings) are
shown in Tables 7 and 8.
   For completeness, the analyses of variance with Collaborator 7 in-
     cluded are shown in Appendix D.
                                  44

-------
              Table 7.  AOV UNCORRECTED CO READINGS (ppm)

Source
C
B
CB
L
LC
df
5
1
5
27
135
SS
142 ,487 .49
1,893,348.15
17,652.38
970,660.48
196,295.11
MS
28,497.50
1,893,348.15
3,530.48
35,950.39
1,454.04
F
19.60
49.79*
2.40
24.76

*  These are pse'udo F-tests, since no direct F-ratio is available for
     testing the significance of B.
               Table 8.  AOV CORRECTED CO READINGS (ppm)

Source
C
B
CB
L
LC
df
5
1
5
27
113
SS
96,909.06
1,400,344.43
16,010.33
702,166.37
141,128.11
MS
19,381.00
1,400,344.43
3,202.07
26,006.16
1,248.92
F
15.52
50.091
2.56
20.82

  These are pseudo F-tests,  since  no  direct F-ratio  is  available for
     testing the significance of  B.
                                  45

-------
     The results are quite similar whether uncorrected or corrected
readings are used.  There is a significant collaborator effect, and
the CB interaction is also significant but small in magnitude.  The
"nuisance" variables, block and level, are, of course, highly signif-
icant.

     The components of variance are shown in Tables 9 and 10.  Thus,
we see that (with + 2 
-------
       Table 10.  COMPONENTS OF VARIANCE (ppm), CORRECTED DATA
                  Source
                        OLC                35.34
                  ac                       25.00
                                           43.29
                                                  2
     As mentioned previously, the error variance o& and LC interaction
variance are inextricable.  The Kendall W Method was compared at each level
for the uncorrected and corrected data sets (see Table 11).
       Table 11.   KENDALL W METHOD (collaborators versus level)


          Data set                _W_            Significant?

     Uncorrected, Level 1        0.656        Yes [X2(5) = 42.64]

     Uncorrected, Level 2        0.458        Yes [X2(5) = 36.67]

     Corrected, Level 1          0.658        Yes [x2(5) = 42.7?]

     Corrected, Level 2          0.293        Yes [X2(5) = 23.45]
     All the concordance values are highly significant, i.e., the rank
order of the collaborators is significantly preserved from level to
level.  However, the W values are not very close to 1, especially at
the higher CO level.  Thus, a significant LC interaction may very well
exist.
                                        2    2
     An indirect method of decomposing ae + CTLC and achieving an esti-
mate of cre alone is shown on pages 50-51.
                                  47

-------
STANDARD ANALYSIS

     Six standard samples were measured three times each by all collab-
orators.*  Thus, the straightforward factorial model
                 xijk = » + Li + cj
was executed, where:

         L4 = ith (standard) level, i = 1 ..... 6;

         C. = jth collaborator, j = 1, . . .,7;

       LCji = level-collaborator interaction;

     e. x..x = measurement error of k   observation in ijt*1 cell,
                k = 1, 2, 3, for every i j ;

          u = overall mean;

                    bias (collaborator reading - true).
     Collaborator 7 produced results quite different from those of any
other collaborator.  In this case, unlike the field results, Collab-
orator 7 did not generate data with an anomalously large dispersion;
in fact, with one exception Collaborator 7 produced identical readings
at all levels of CO.  However, the magnitude of this collaborator's
average bias is very much larger than anyone else's; the average
(overall CO levels) bias of Collaborators 1 to 6 is + 7.2 ppm, but
the average bias of Collaborator 7 is + 200.9 ppm.

     Therefore, Collaborator 7 was deleted from the main analysis and
results are discussed in terms of Collaborators 1 through 6 only.**

     The analysis of variance and components of variance estimates for
the standards data are shown in Tables 12 and 13.
*   For some reason, Collaborator 6 only measured the samples twice.
      Thus six "missing values" were replaced in his results.
**  For completeness, the standards analysis of variance including
      Collaborator 7 is given in Appendix D.
                                  48

-------
                    Table 12.  AOV STANDARDS DATA
Source          df       S£           MS          F               EMS




Level            5    20,797.27    4,159.45      3.86     ae2  + 3aLC2 + 18(TL2





Collaborator     5    43,128.82    8,625.76   422.12     a&2  + 18crc2




LC              25    21,630.45       865.22    42.34     o-&2  + 3aL(,2




Error           66     1,348.67       20.43              a£2
       Table 13.   COMPONENTS OF VARIANCE (ppm), STANDARDS DATA










                       Source                        _£_




                       Error                         4.52




                       Collaborator                21.86




                      >/CT_2  + CT 2                    22.33
                                  49

-------
Cl
31
17
11
5
-1
-3
C2
43
39
38
23
13
19
C3
31
10
30
20
26
-1
C4
26
29
31
24
17
-30
C5
6
-2
-21
-26
-49
-110
C6
8
-8
8
-7
8
7
All
24
14
16
6
3
-20
     All  the F-values  in  Table  7  are highly  significant.   Thus,  the
collaborators differ in the bias  exhibited,  and  the  (average)  bias
does depend upon  the CO level  (see  Table  14).  In  general,  a sizeable
positive  bias is  shown at the  lower CO  levels, but a negative  bias
exists at the highest  CO  level.   However, not all  collaborators  have
parallel  bias versus concentration  curves  (see Table 14).
             Table 14.  AVERAGE BIAS VERSUS CO CONCENTRATION
 CO level                       Collaborator
  (ppm)
    239
    258
    480
    517
    734
    903
    All           10       29       19       16     -34
     The measurement standard error (ag) is only 4.5 ppm; i.e., a col-
laborator produces readings within about ± 9 ppm of his nominal value.
However, the standard error of collaborator averages is 21.9 ppm; i.e.,
a set of collaborator averages will be about ± 44 ppm about their cen-
ter.  Thus, most of the imprecision in CO readings is due to collaborator-
to-collaborator variability, very little attributable to lack of repeat-
ability.

     Although the average bias is quite low, five of the six collabora-
tors showed positive bias (in general), and the bias is definitely var-
iable according to CO level.

COMPARISON FIELD DATA VERSUS STANDARDS DATA

     In general, the standards data are more precise than the field
data (see Tables 9 and 13).  The "total" standard error (>/o| + o2^ + oj:)
is about 1-1/2 times as great in the field results as in the standards
data (43.29 ppm versus 27.93 ppm).  However, the standard error of col-
laborator means (ac) is about the same size in both cases (25.00 ppm,
field, versus 21.86 ppm, standards).   Thus, almost all of the "loss" in
                                  50

-------
precision when going from the standards data to the field data is due
to increases in o~ and/or increases in OLC •  Unfortunately, the field
data only allow the estimation of the sum of of and afr  . In the stan-
dards data, of is very much smaller than O^Q (20.4 ppnr versus 281.6
ppm2); that is, collaborators reproduce their own readings quite well
at a given  CO concentration, but their (average) values depend heav-
ily on CO concentration.

     A working rule of experimental design will allow us to roughly
estimate o£ from the field data even though no replicates exist.  If
two runs, r^ and re, say, apparently exist at the same CO level, then
the variance of their difference is theoretically 2o~ .  In practice,
many pairs of runs in the field experiment do have virtually the same
CO value, because the average reading of all collaborators was nearly
the same.  Thus, o-e can be estimated from the field data from analyz-
ing these paired results.  Logically, of course, it is circular to
simultaneously "believe" the collaborator results in order to con-
struct pairs and then use the pairs to evaluate the reliability of the
collaborators.  Statistically, however, this method has produced sat-
factory results in many instances and has been applied to the CO data.

     The result is that a& = 13.06 ppm (field data); i.e., the o~ +
    term is 73% LC interaction.

     In summary, then, the best available estimates of components of
variance are shown in Table 15.
     Table  15.  FIELD DATA VERSUS STANDARDS:  COMPONENTS OF  VARIANCE
          Standard deviation
          	(ppm)	            Field         S tandards

                  ov,                     13.06           4.52
                 o-c                     30.54          21.86

                o-LC                     30.13          16.78
              Te2 + ac2                  38.13          22.33
               + o-LC2 + o-c2             48.85          27.93
                                 51

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                            SECTION VIII

                             CONCLUSIONS

     This collaborative test comprised 16 1-hr runs at a high level
nominally 500 ppm of CO, and 16 1-hr runs at a lower level nominally
300 ppm of CO, where seven different collaborative organizations sam-
pled simultaneously according to the integrated sampling procedure
given in Method 10 of the Friday, 8 March 1974 (Vol. 39, No. 47) issue
of the Federal Register.  These samples (two to four daily) were ob-
tained from a manifold apparatus that was located at ground level and
connected via piping to the CO boiler stack at an elevation of approx-
imately 60 ft.  In addition each collaborator took three samples from
each of six cylinders of CO in nitrogen that had been supplied by the
National Bureau of Standards.  Several of the collaborators did not
come adequately prepared to sample from the test setup.  Moreover, the
first few days of testing were done under extremely adverse weather
conditions where heavy rains were experienced, with tornadoes in neigh-
boring areas.

     The major conclusions that can be drawn from the results of this
collaborative test are:

     1.  Method 10 as executed in this collaborative test will produce
results with only moderate accuracy of ± 87 ppm (2a) on the average.

     2.  The procedures as written in Method 10 are not adequate be-
cause :

          a.  The Ascarite weight gain method for measuring C02 content
on the sample is subject to large errors due to the difficulty of mea-
suring the small weight change obtained compared to the weight of the
impinger plus the Ascarite;
                                 52

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          b.  The use of an impinger or bottle for the Ascarite trap
causes great difficulties because the Ascarite tends to form a dense,
solid plug in and around the glass inlet tube which, in turn, blocks
the flow of the gas after a period of time;

          c.  Most commercial NDIR instruments have a significant amount
of curvature in the calibration curves and many of the collaborators
did not adequately correct for this nonlinearity of response; and

          d.  Some calibration gas suppliers provide certificates of
analysis that show errors of as much as 30% when compared with standard
gases.
                                 53

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                             SECTION IX

                           RECOMMENDATIONS

     Based upon the conclusions that have been drawn from the results
of this collaborative test, it is recommended that Method 10 be revised
to cover the following points:

     1.  All mention of the C02 determination by weight gain of the
Ascarite gas scrubber should be deleted.  C02 analysis should be done
by Method 3 (Orsat-type analysis) of the Federal Register.

     2.  The use of an impinger or bottle type of silica gel and
Ascarite gas scrubber should be deleted.  Sections of a flexible plas-
tic pipe, capped at the ends, should be used instead.  A minimum inter-
nal diameter of 2.5 cm is recommended to prevent blockage.

     3.  More explicit instructions on correcting for nonlinear re-
sponse of the instruments is desirable.

     4.  Analysis procedures of some calibration gas suppliers are
clearly inadequate.  Reliable calibration gases might require NBS cer-
tification or a requirement that gas suppliers follow specific guide-
lines in their analysis of calibration gases.
                                  54

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                 APPENDIX A
METHOD 10 - DETERMINATION OF CARBON MONOXIDE
      EMISSIONS FROM STATIONARY SOURCES
                     55

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                                             RUIES AND  REGULATIONS
                                                                                                                  •1M !
nv\ed representative grab s-imp'e ul the
-Incige can be obtained.
  'I he general rationale (or the change
in  the  opacity standard is presented
m  the  discussion  ot  opacit?  above
The three  factors  winch  led  to  Uus
. lii-nge are  (1)  the data,  summarized
in Volume 3 ol the background informa-
tion document, which. In the judgment
of the Administrator, show that the pro-
posed opacity standard was too restric-
tive ind that the promulgated standard
is  not more restrictive than the mass
standard. (2) the separately promulgated
irgulauons  which provide  exemptions
from opacity standards during periods of
startup, shutdown, and malfunction  (see
FEDERAL REGISTER of October 15 1973. 38'
FR 28584). and (3) reevaluatlon of data
and collection of  new data and Informa-
tion which, show that there Is ro basis
for additional time exemptions
  Minor changes to the proposed version
of the  regulation  have been  made to
clarify meanings and  to exclude repeti-
tive provisions and definitions which are
now Included In subpart A. General Pro-
visions, and. are applicable to all  new
iource performance standards
            TEST METHODS
  Test Methods 10 and 11  as proposed
contained typographical errors that are
now corrected in both text and equations.
Some  wording is changed to  clarify
meanings and procedures as well
  In Method 10. which Is for determina-
tion of CO  emissions, the  term "grab
sampling" Is  changed  to  "continuous
sampling" to  prevent confusion.   The
Orsat analyzer Is deleted from the  list
of analytical equipment because a  less
complex method  of analysis was judged
sufficiently sensitive. For clarification, a
sentence Is added to the section on re-
agents requiring  calibration gases to be
certified by the manufacturer Tempera-
ture rf the  silica gel Is changed from
177'C (350'P) to 175'C  (347T) to be
consistent with the emphasis on metric
units as the  primary units. A technique
for determining the CO, content of the
gas has been  added  to both  the  con-
tinuous and  Integrated sampling proce-
dures This technique may be used rather
than  the  technique described in Method
3  Use of the latter technique was  re-
quired In the proposed Method 10
  Method 11, which Is lor determination
ot US emissions. Is modified to require
five midget  Impmgers rather  than  the
proposed  four. The fifth Implnger con-
tains hydrogen peroxide to remove  sul-
fur dioxide as an interferant.  A para-
graph Is added specifying the  mdrogen
peroxide  solution to  be  used,  and- the
procedure description  Is. altered to  la-
elude procedures specific to the fifth Im-
plnger. The term "iodine number flask" is
changed'to "Iodine flask" to prevent con-
fusion
  Dated  February 22. 1974
                  RUSSELL E TRAM.
                       Administrator.
  Part 60. Chapter I. Title 40. Code of
Federal Regulations,  Is amended by re-
\ laing subpart A, by adding new subparts
IJ.K.L.M.N.  and  O, and  by  adding
Methods 10 and 11 to the Appendix, as
follows
       Subpirt A—Central Provision*
See
en 2    Definitions
003    Abbreviations
CO 4    Address
6ns    Keviewofpians
oO 7    Notification and recurclkeepmg
o08    Performance testa
6012   Circumvention
Subpirt I—Standards of Performance lor Asphalt
             Concrete Flints
6090   Applicability and designation of af-
         fected facility
0091   Definitions
6092   Standard  for participate matter
60 D3   Test methods and  procedures
   Subpart ]—Standard! of Performance for
           Petroleum Refine*lam
60100  Applicability and designation of af-
         fected facility
60101  Definitions
60102  Standard for putlculate matter
60103  Standard for carbon monoxide
60 104  Standard for sulfur dioxide
50105  Etnlasioa monitoring
HO 106  Tnt methods and procedures

Subpart K—Standards of Performance for Storage
        Vessels for Petroleum Liquids
60110  Applicability  and   designation  or
         affected facility
60111  Definitions
60 113  Standard for hydrocarbons
60113  Monitoring ot operations.
   Subpirt L—Standards ol Performance for
          Secondary Lead Smelters
60130  Applicability  and   designation  of
         affected facility
60131  Definitions
60122  Standard for paniculate matter
60123  Test metaoda and procedures.
Subpart M—Standard! of Performance for Sec-
ondary Brass and Brorue Info* Production plants
60130  Applicability and   designation  of
         affected facility
60131  Definitions
60132  Standard for paniculate matter
60 133  Teat methods and procedures
  Subpirt N—Standards of Performance for Iron
             and Steel Plants
60140  Applicability and   destination  of
         affected, facility
60141  Definitions
60112  Standard for paniculate matter
60143  I Reserved |
60144  Test methods and procedures
   Subpart O— Stanilardl of Performance lor
          Sewage Treatment Plants
60190  Applicability and   designation  of
         affected facility
60151  Definitions
60 152  Standard for paniculate matter
60 15?  Monitoring of operations
60154  Test methods and procedures
        AFPC.NDIX—TEST METHODS

Method 10—Determination or carbon  mon-
             oxide  emlsslona  from  sta-
             tionary sources.
Method 11—Determination of hydrogen sul-
             flde emissions from auttoaary
             source!

  AUTUOUIT-  Sees.  111. 114. Pub L. 91-«04
(42 USC. 1857(C)(S) and (9)).
      Subpart A—General Provis ons
  1  Section  60 2 Is amended by revising
p.ii:ieinphs d) and (1 > and nddmo, paia-
Rraplis  (s),  (I), (u), (v).  and  (w)  as
follows

S Ad 2  IMmiiiDii.
     •      •      •       •      •
  in "Commenced" means, with respect
to the definition of "new source" In sec-
tion 111 (a) (2) of the  Act, that an owner
or opeiruor has undertaken a continuous
progiam of construction or modification
or that an owner 01 operator hai entered
into a contractual  obligation to under-
take and complete, within a reasonable
time, a continuous piogram of construc-
tion or modification
     •      •      •       •      •
  (l) 'Standard conditions" means  a
temperature  of 20"C (68'F) and a  pres-
sure of 760 mm of Hg  (29 92 in of Hg)
     •      •      e       •      •
  (s) "Reference  method" means any
method of sampling and analyzing for an
air pollutant  as described In the appendix
totnlspart
  it) ' Equivalent method" means any
method ol sampling and analyzing foi  un
air pollutant which have been demon-
strated  to  the Admimstartor's satisfac-
tion to have  a consistent and quantita-
tively known relationship to the refer-
ence method, under specified conditions
  (u) "Alternative method" means any
method of sampling and analyzing for an
air pollutant which Is not a reference or
equivalent  method but which has  been
demonstrated to the Administrator's sat-
isfaction to.  In specific  cases,  produce
results adequate for his determination of
compliance
  (v) "Portreulate  matter" means any
finely divided solid or liquid  material,
other than uncomblned water, as meas-
ured by method 5 of the appendix.
  (w) "Run" means  the net period of
time during  which an emission sample
is collected  Unless otherwise specified,
a run may  be either Intermittent or con-
tinuous within the limits of good  engi-
neering practice
  2. Section  603 is levlsed to  rend  as
follows

§ 60.1  Ablirrtialiniis.
  The abbreviations  used In this part
have the following meanings'
A S T M —American Society  for Testing and
           Materials
Btu—British thermal unit
•C—degree Celsius (centigrade)
cal—calorie
CdS—cadmium bulflde
cfra—tublc feet per minute
CO—carbon monoxule
CO —carbon dioxide
dftcm—
-------
                                            RULES AND REGULATIONS
romoliancc n ith the standaids prescribed
in 5 60 92 as follows
  (1) Method S for the concenliatlon of
paniculate  matter and the associated
moisture content.
  (2) Method 1 for sample and velocity
traverses.
  (3) Method 2 for velocity and volu-
metric flow rate, and
  (4) Method 3 foreasanalysis.
  'b> For Method 5. the sampling tune
for each run shall be at least 60 minutes
and the sampling rate shall be at least 0 9
dscm/hr  (0 53  dscf/nun)   except  that
shorter sampling times, when  necessi-
tated by process variables  or other fac-
tors, may be approved by  the Adminis-
trator

Subpart J—Standards of Performance for
          Petroleum  Refineries
§60.100  Applicability  and dnignalion
    of affected facility.

  The provisions of this subpart are ap-
plicable to the following- affected facil-
ities In. petroleum refineries. Fluid cata-
lytic cracking unit catalyst regenerators,
fluid catalytic cracking: unit tncinerator-
v.aste neat boilers, and fuel gas combus-
tion devices.

§ 60.101  Definitions.
  As used In this subpart.  all terms not
defined herein shall have  the  meaning
given them  In the Act and  In subpart A
  (a) "Petroleum refinery" means any
facility engaged In producing  gasoline.
kerosene, distillate fuel oils, residual fuel
oils,  lubricants,  or  other   products
through distillation  of petroleum  or
through redistillation, cracking  or  re-
forming  of    unfinished   petroleum
derivatives
  (b) "Petroleum" means  the crude on
removed from the earth and the oils de-
rived from tar sands, shale, and coal
  (c)  "Process gas" means any gas gen-
crated by a petroleum refinery process
unit, except fuel gas and process upset
gas as defined In this section
  (d) "Fuel gas" means any gas nhlch
Is generated by a  petroleum refinery
process unit and which Is combusted, In-
cluding any gaseous mixture of natural
gas and fuel gas which Is combusted.
  (e)  "Process upset gas" means any gas
generated by a petroleum refinery process
unit as  a result  of start-up, shut-down,
upset or malfunction.
  (f)  "Refinery process unit" means any
segment of the petroleum refinery  In
which a specific processing operation Is
conducted. •
  (g)  "Fuel gas  combustion   device"
means any  equipment, such as process
heaters, boilers and flares used to com-
bust fuel gas. but does not Include fluid
coking unit  and fluid catalytic  cracking
unit Incinerator-waste- heat boilers or fa-
cilities In which gases are combusted to
produce sulfur or sulfurle add.
  (h> "Coke burn-off" means the coke
removed from the surface  of the fluid
catalytic cracking unit catalyst by com-
bustion In the catalyst regenerator The
rate of coke bum-off Is calculated by the
formula specified In i 60106.
S 60.102   Standard
    mutter.
                      fur   piirlirulul.-
   (a)  On and after tlie date on nhich
 the performance test required to be con-
 ducted by 1 60 8 Is completed, no owner
 or operator subject to the provisions of
 this- subpart shall discharge or cause tlic
 discharge Into the atmosphere from any
 fluid catalytic cracking unit catalyst i e-
 generator or  from any fluid catalytic
 cracking  unit  incinerator-waste  he-it
 boiler
   (1)  Partlculate  matter  In  excess  of
 1 0 kg/1000 kg  (1 0 Ib/lOOD Ib) of  coke
 burn-off In the catalyst regenerate!
   (2)  Gases exhibiting 30 percent opac-
 ity or  greater, except for  3 minutes In
 any 1  hour  Where the presence of un-
 comblned water Is the only reason for
 failure to meet the requirements of this
 subparagraph. such failure shall not be a
 violation of this section
   (b)  In those Instances In which  aux-
 iliary  liquid  or solid  fossil  fuels are
 bumed In  the  fluid  catalytic cracking
 unit incinerator-waste heat boiler,  par-
 ticular matter In excess of that permit-
 ted by paragraph  (a) (I) of this section
 may be emitted to the atmosphere, ex-
 cept that the Incremental rate of panic-
 ulate emissions shall not exceed 0 18 g/
 million cal (0 10 Ib/mllllon Btul of heat
 Input attributable  to such liquid or  solid
 fuel
 § 60.103  Standard for enrhon  monoxide.
   (a)  On and after the date on which
 the performance test required  to be con-
 ducted by i 60.8 Is completed, no owner
 or operator subject to the provisions of
 this subpart shall discharge or cause the
 discharge Into the atmosphere from the
 fluid  catalytic  cracking  unit catalyst
 regenerator any gases which contain car-
 bon monoxide In excess of  0 050 percent
 by volume.
 8 60 104  Standard for .ulfur dioxide.
   (a)  On and  after the date  on which
 the performance test required to be  con-
 ducted by 1 60 8 Is completed, no own-
 er or operator subject to the provisions of
 this subpart shall  burn In any fuel gas
 combustion device  any fuel  gas which
 contains ttS In excess of 230 mg/dscm
 (010  gr/dscf),  except as provided In
 paragraph (b) of this section.  The com-
 bustion. of process  upset gas In a flare.
 or the combustion  in a flare of process
 gas or fuel gas which Is released to the
 flare as a result of relief valve leakage, Is
 exempt from this paragraph.
  (b) The owner or operator  may elect
 to treat the gases resulting from the com-
 bustion of fuel ens In a manner which
 limits  the release of SO, to. the atmos-
phere If It Is shown to thj satisfaction
 of the  Administrator that this prevents
BO, emissions as effectively as compli-
 ance with the requirements of paragir-'i
 (a) of this section.  -
 S 60.105  Emission monitoring.
  (a) The owner or operator of any pe-
 troleum refinery subject to the provisions
of this subpart shall Install,  calibrate.
maintain, and operate monitoring Instru-
ments as follows*
   (1)  A  photoelectric  or  other  tyiie
 smoke detector and recorder to continu-
 ously monitor and rerord the opacity of
 cases  discharged  Into  the atmosphere
 from the fluid  catalytic  cracking  ujut
 catalyst regenerator
   (2>  An instrument  for continuously
 momtonng and recording the concentra-
 tion of CO> In eases discharged into the
 atmospnerc from  fluid catalytic  Track-
 ing  unit  catalyst  regenerators,  except
 where the requirements of paragraph (a)
 (3) of this section are met
   (3) Instruments  for   continuously
 monitoring and recording firebox tcm-
 peiature  and Oj  concentration  in  the
 exhaust gases  from   any  Incinerator-
 waste  heut  boiler  which  combusts  the
 e-chanst gases  from  a  fluid  catalytic
 cracking  unit catalyst regenerator  ex-
 cept where the requirements of para-
 graph (a>(2) of this section are met
   (4)  An Instrument  for continuously
 monitoring and recording concentrations
 of H-S  In fuel gases burned In any fuel
 gas combustion device, except where the
 requirements of 9 60 104(b) ate met Fuel
 sas combustion devlres having a common
 source of fuei cas mav be morrtorrd .it
 one  location  If  sampling at this loca-
 tion produces results  representative of
 the  H.S concentration In the  fuel  gas
 burned
   (5)  An instrument  for continuously
 monitoring and recording concentrations
 of SO,  In the gases discharged Into the
 atmosphere from the combustion of fuel
 gases except  where the lequirements of
 § 60 104 (a) are met
   (b) Instruments and sampling systems
 Installed and used pursuant to this sec-
 tion shall meet specifications prescribed
 by the Administrator  and each instru-
 ment shall be calibrated  In accordance
 with the method prescribed by the manu-
 facturer of such instrument The instru-
 ments shall be subjected to the  manu-
 facturer's recommended zeio adjustment
 and calibration procedures at least once
 per 24-hour operating  period unless the
 manufacturer specifies or  recommends
 calibration at shorter Intervals, in. which
 case such specifications or recommenda-
 tions shall be followed.
   (c)  The average coke  bum-off  rate
 (thousands of kilogram/hr)  and houis of
 operation for  any  fluid catalytic  ciack-
 Ing unit catalyst regenerator subject to
 i 60 102 01 GO 103 shall be recorded daily
   (d) For any fluid catalytic cracking
 unit catalyst regenerator which Is subject
 to i 60 102 and which utilizes an Inclnei-
 ator-n-aste heat boiler to combust  the
 exhaust gases from the catalist  regen-
 erator, the owner  or operator shall le-
 cord daily the  rate of  combustion  of
 liquid or solid fossa fuels (Uteis/hr or
 kllograms/hr> and the hours of opera-
 tion during which  liquid  or solid fossil
 fuels are combusted In the  Incinerator-
waste heat boiler
  (e) For the purpose of  reports pur-
 suant  to  S607(c>, periods of  excess
emissions  that shall be reported are  de-
fined as follows:
  (1)  Opacity  All hourly peilods  In
which there are four or more 1-minute
periods during which the average opacity
     No 47—Pt n-
                                FEOMAL lEGIfltl, VOL 19, NO  47—FRIDAY. MAICH t. 1974
                                                       57

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 n;ifi
                                                 RULES AND  REGULATIONS
o' the Ra^es discharged Into the atmos-
phere front any Quid catalytic cracking
trvii catalyst  regenerator  subject  to
: 60 102 esceeds 30 percent.
   i2>  Carbon monoxide  All hourly pe-
riods during which the average carbon
r?no\ide concentration In  the gases dis-
charged ur.o the  atmosphere from any
i\iid catahtic cracking unit catalyst re-
"T.eraior  subject to  960103  exret-ds
o 350 perent by volume, or any hourly
period  in which  O,  concentration  and
firebox temperature measurements Indi-
cate that the average concentration  of
CO in the gases discharged Into the at-
mosphere  exceeds   OOSO   percent  by
lolume for sources which  combust the
exhaust gases Iron  any fluid  catalytic
cracking  unit catalyst regenerator sub-
ject to } 60.103 In an Incinerator-Taste
heat boiler and for which  the owner  or
operator elects to monitor In accordance
with !60105(a>(3>
   (3>  Hydrogen tulfide. All  hourly pe-
r.ods during which the average hydrogen
sulflde content of any fuel gas combusted
in any fuel gas combustion device sub-
ject to  i 50 104 exceeds 230 mi? 'd. except where the
requirements of 3 60 104fa) are met
§ 60.106   Tnl imthwfe and  promliirr*.
   (a)  For the purpose of determining
compliance with 5 60 102'ai (l).  the fol-
lowing  reference methods  and calcula-
tion procedures shall be used
   U i For gases released to the  atmos-
phere  from the fluid catalytic cracking
unit catalyst regenerator.
    Method 5 for the concentration of
participate matter and moisture  con-
tent.
   i il i Method 1 lor sample and  velocity
traverses, and
   (ul) Method 2 for velocity and volu-
metric flow rate.
   '2) For Method 5. the sampling time
for each run .shall  be at least 60 minutes
and the sampling  rate shall  be  at least
0015 dscm/mln  (053 dscf/min). except
that shorter sampling times may be ap-
proved by the Administrator Then proc-
ess variables or other factors preclude
sampling for at least 60 minutes
   <3> For exhaust gases from the fluid
catalytic cracking unit: catalyst regenera-
tor prior to the emission control ssstem-
the  integrated  sample  techniques  of
Method 3 and Method 4 for gas analysis
and  moisture   content,   respectively:
Method  1  for  velocity traverses: and
Method 2 for velocity and volumetric flow
rate
   (4) Coke burn-off rate shall be deter-
mined by the following formula-
R -OOIs8Q»,(r-;cOH-%CO)+01My».-Or..,:Qr,("r"|  f HH-7i
                                                           (MiMc I'nlu)
                                                            v 10" U,  ilnV-m»
    On.-A-Fiiiil.Hh indMniat^n.lbibiirt LvbirdiMil f^ntrat'ir em i I--L i •.< HUM ruin l-rnn rnl«iliu tli« 0
          rontrol ->v5t«ni u dHemnnwl li> ii>rttiii>l _'. i« m\*\ rut ••! !•> v ipml I
   % ( n»p>»rr*iil carbon iii(.no«i.vi^  inl> [-1 iumfEnu by volume Jrylnoi < udcttrrnn M l>> M^tluxl 3
    .•ftv*»metric units innlrrfal bsl.tnw fnrior i.iMilc.1 by |i» IL n in -ir m1
   0 l3u3«Fnt(Udh units malcrinl bnl«m»> f.w l«r i.nl-Ul \>y in) llt-miii l>r li>
    WHt*alr r,.t« to fluid CDLiI^ tk rnutinic utntritalvjt r u.n. r*lnr. L* >teii>riiiniHl from fluul (.nUly.icr
          inilteoninilrooinlnalninipntdtioii il^nLnuii (hm-'i li unit* (lotf nun)
   n (Fm<*rn.)ti1c iiiilt« m&ti>riiil hjtoure f* tor ilivi'ltvl hv lm k? nun hr-in1
   0 uurt-.'-tDRUsh units matfrinl balance f-icu>r rUTiitfJ by i»i .l>nnn,hr (ii

   (5)  Particulate emissions shall be determined by the following equation.

                            RB-(UX10-*)QKvC. (Mftni. UiilU
                                         ivinn nU- kjllr fFnt:ll^n unil» Ib/hr)
    6UXIO-*"metrie uulul eoiiverilon laelor. inliiAulir-riiii
   S.»Xlir<"Eniiltohuiill9coiiTCnionL>ctor mln-lbi1ir«T
      Wkv-iTotumalrlc Row rnu of a.i»cs di^rbnnErd Into tbp Um<>.[tlirrr Fmrn lh» (liild canlj tit rrncklne unit
            CAUllyst tfff nt r»lor rollowinit the rml^ioa runtrol ^y^trnj. Da tlvlarnilofd by .Melhoil J. tl
                                               iall be clettimineil by the  lollowir.*
                                     " (Vlriru or Fniili.h Unib)
    R.-ninlrulnlr f mission ralr. Lvfimu kt (Cni.l»h unlu IL lini II.) ,,l ,-,.l« l,iirn-oH In lilt nul.1 ul il>lu « « V-
         ing ilnll cntiil>it rmrnarjlor
   inw.ronTrr.lon factor. KR to IdU k« (Entliih uniu 111 u> l>ui II. I
    R K-pnrtlculiila emission nilc.kKlir (EnKli^li ilinla Ib lirj
    K,-u>kg buriwiS ratr. tK.1ir (En|U»h uullo ll> lir)

   (7>  In those Instances in which auxiliary liquid  or  solid fossil fuels are  burned
In an  Incinerator-waste heat boiler, the rate of particulate matter emissions pei -
nutted under i 60 102(b) must be determined  Auxlliaiy fuel heat Input, cxpiessed
In millions of cal/hr (English units  Millions  of Btu/hn  shall be calculated  for1
each run by fuel flow rate measurement and analysis of the liquid or solid auxiliaiy
fossil  fuels  For  each run. the rate of  particulate  emissions permitted  under
I 80 102 (b) shall be calculated from the follow ing equntion
                              R.-IOV- •l^rufnf. I in i.)
    Jl.-iillo\>iiM< rmrtknlolr rmlvdon rolo tc/ICA) kn ,in» Ib)  of cuko burn-oft in tho
        llulfl mtal>llc crnrUng unit caul>st mifn^rator
    1 0«emii»lon slAmlluil. 10 kvMUUU b8 (English uniu I 0 Ibiinro Ib) ul coke hum-cff in tli* RiiM (nlUvtif
        crurldng unit cntitl)!! rnt-nprntor
   0 H-m'trlc unlu minimum nllowsbli Incrrinrnl il rate ol n irliLiil itr- anik>linn. K/mllllnn L il
   0 10- !• nKllbh unlu maximum allowable mcrifiiir-iilal r.ih) of p.irucuLite rinl^mni. Ib/milllon lllu
    Tl— ht^»l Input from «Mii! nr HnnM fftrd.ll fnM million t il V
    Ki-coko burn-oil rab, kK,lir i bnitluh uiutd Ih lir)
                                                    h nniL-i million Rru/llr)
   (b)  For  the purpose of determining
compliance with i 60 103. the Integrated
sample technique of Method 10 shall be
used  The sample shall  be extracted at a
rate proportional to the gas velocity at a
sampling point near the centroid of the
duct  The sampling time shall not be less
than 60 minutes
   (c)  For  the purpose of determining
compliance with 160 104 (a). Method 11
shall be  used  When  refinery  fuel  gas
lines are operating at pressures substan-
tially above atmospheric, the gases sam-
                                          pled must be  introduced into the sam-
                                          pling tram at approximately atmosphei ic
                                          pressiue This  may be accomplished with
                                          a flow control  valve If the line piessuie
                                          is  high eiiouoh to opeiale the s.implim
                                          tram wllhuut a vacuum pump, the pump
                                          may be eliminated  from  the sampling
                                          tram. The sample shall be drawn from a
                                          point near the centroid of the fuel gns
                                          line The minimum sampling time shall
                                          be  10  minutes  and the minimum sam-
                                          pling volume 001 dscm (035 dscf) for
                                          each sample The arithmetic aveiage of
                                   FfOBIAl tECISTII, VOL 3*. NO 47—FBIOAY, MAICH I, 1974
                                                          58

-------
     RULES  AND  REGULATIONS
»in ii nrrrsMiatrd hj  process- uriaoles
 i- u '.cr tutors. ma> b>: .upro.Kt tiy the
 \i>-  litralor A c c!e v*ia;i -.tart :.'. t.''e
lu'jmniiiE  of nthor the  scrap pr-heat
ci- t'le o\vgen bio* and shall tcrni.n.uc
i nmediatel> pnor to taupirs
Suopart O—Standards of Performance for
         Sewage Treatment Plants
 , dO 1 ID   Vpplii iihihlv  nnil  ilf-Mgn ilniii
     nf .llln let! f.n ililv.
   t.-r ...tecled taiilily to -\i:ch Ire pro-
 > talons  of  this  suopart apph  is  each
ircinirnuir which burns tne slLcge pro-
duced by  municipal  se»ige  treatment
lucJmes
S, 60 I>1   l><-r,nition<.
  As used  in this subpart  all terms not
denned  herein  shall have the meaning
p.en them in the  Act and in subpart A
of this part
§ M 152   SlundarJ for pjrlimldir  ni.it-

   (ai On and after the date on nhich the
performance test  required to  be  con-
uucted by  i 60 8 is completed, no owner
or ooerator of any sewage sludge incin-
ff-au>r subject to the provii.ons of tnu
subpart  shall discharge or cause the dis-
charge into the atmosphere of.
   ' 1 > Partlculate matter at a rate in ex-
cess of  0 65  g/kg dry sludge input  ' 1 30
Ib/ion dry sludge input)
   (2) Any gases which evilubii 20 per-
cent opacity or greater. Where the pres-
ence  of  uncombuied  water is the only
reason  for failure to meet the require-
ments of  this  paragraph,  such failure
shall not be a violation of this section
5 fiO. 113  Monitoring of operation-*.
   i a) The owner  or  operator  of any
sludge incinerator subject to the provi-
sions of this subpart shall
   (1) Install, calibrate, maintain  and
operate  a  flow measuring deviro which
 can be used to determine either the mass
 or volume of sludge charged to the incin-
 erator  The  flow measunng device shall
 have an accuracy of ±5 percent over its
 operating  range
   (2) Provide   access  to  the  sludge
 charged so that a well-mixed represen-
 tative grab sample of the sludge can be
 obtained.
§ 60 154  Teat  Mrthnd* anJ Proralurr-.
   'ji The reference methods nappnded
 to this  part, except as provided lor in
 !608'b>.  shall be  used  to determine
 compliance  with  the  standards  pre-
 scribed In  3 60 152 as follows.
   (D Method  5 for  concentration  of
 uurf.culate matter and a&socia.cd  mo»-
 ture content
   121 Method 1 for sample and \elocity
 traverses.
   (31  Method 2 for volumetric Ron rate.
 and
   (4i  Method 3 for gas analysis.
   (b)  For Method 5. the sampling time
 for  each run shall be at least 60  min-
 utes and  the sampling rate shall be at
 least 0015  dscm/nun  (053  dscf/mm).
 except   that shorter  sampling  times,
 when necessitated  by process variables
 or other factois. may be appioved bv the
 Administrator
  fc) Dry sludge charging rate .lull be
ilolei mined ris fnllons
  (1) Drleimme  the mau> (S,,)  ui  vol-
ume i S>)  of sludge  cliarKCd to the m-
cineratoi  during each run using a flow
measuring device meeting the  require-
ment;; of  !60153ia)(l)   If  total input
din me a run is measured by a flow PIIMS-
ui ins device, sm h readings shall tie used
Othera ise. i ecoi d the How me.iMii in,! de-
uce i endings at 5-mmute mterv ils din-
i r;  a  run   Dr-termine  tne  nuiuitay
charged during each interval bv avpias-
IIIK the flow  lates at the beginning and
end of the interval and then multiplying
the average for each  interval  by the lime
for each interval  Then add the quantity
for each interval  to  determine the total
quantity charged during the entire run.
IS.) or(Sv)
  '2> Collect  samples   of  the  sludge
charged to the Incinerator In  non-porous
collecting Jars at the beginning of each
tun ar.d  at  approximately  1-hour in-
ternals thereafter until the test ends  and
drlprmmc for r:u h sample the (In  sluoVa-
cimMit (tutal  sbluN residue)  in .vioiid-
uitii null ".KM Ci  Method  for Solid .ni'l
Si mi .ond  Simples' btaniltirtl MetliiHl
far  the  k, lamination  ol  Witter  unit
\Va leicaliT. Tliirle-'iith rditiim. Amen-
r m Public Health ^ssoiialirm. Iiic , NLW
Ynr* H Y . 1071. pp 019-41. CXI l'|)l III it
  MI  l'\ ipiM.mnc dishes  hall lie iRiuti ii
to .it l".t,t id.i'C  rnihPr than the S.riO C
int'ifieti m ',tcn3  Uett iiiiination ol xulallle iniidui*.
Moi^'bi  nn> be Deleted
  inn The qimnlity of  div  slurtse  per
unit slud;;p charBed shall be (Ipterinmcd
in terms of eithrr R... 'metlic units  m>;
dry sludyc/litei sludge chaigecl or Eng-
lish units  Ib'fi)  or Rnn tmetrir umb>
mg dry sliidge/mg  sludge charged  01
English units  Ib/lb)
  13)  Determine  the  quantity  of  dry
sludgp per unit sludge chaigcd In terms
of either Rn. or Ri»
  (i)  If the volume of sludge charged U
used
                                      —: Olnrie 111114
      Si.»'\rcrDi!i>dr> -.Iml^p pi arvlnR rilp iliiiii< j Mn- run tchr |p,vl<.li iiiuu Ilih')
     H[iv«.Bveiiu.Iaf|uaiitll> ol dry blurtue i«r uiut vutuiiir of '•Ill-Is^ cliaiijeil tn the inrnipr ilnr. me I (Kngli Ii
           unlu ll>'lt>)
      St -sludge elinrpert to lh« Ineiurntor ilunnR the nin. ILI trnuli^li ui.it* i;.il)
       T -duration of rim. mlri IFmlKli units  mini
      rr^-melilc umuronvenilon bi.tar. l-krf'infn/m1 mK-lir
     b OM - Enall^h unlu ranrenluo lM.\or. fl«-niiii'R3l hr
  (ii)  If the mass of sludge charged is used
  "in  .irr«edry9lii'l|»irliin,nni;nu> iliinnelht run Lchr (Fnululi milts IMirl
   KI>M  IVITIRU rilinnltiuuillly olrio sludge lit i|lllinlltl nf -lil'L'i-ili inlril In tllA m< Inrnlor. in*, i i (I I
         units lb/ll>)
    E>M«Mliilp« charged duniiR thii run LR (Em.li*h uiuu H>)
     T -dnrjliun nl inn niln iMnni or Kncu-h nuns)
     60 'Conversion (lUor, niln nr (Mrlnc or Entli-li uuits)

  (d) Partlculate emission rate shall be determined bv
                          e1* Bcstjs (Metric or Lucnsh UiJl*)
    •• -nnitliul.»t«innllcr mass tmlsrinns. ms/hr (Eiwli'h nnlfo Ihli
    t« -nnnliiiUteinUiei conci nlriuon. nw in1 (himll'lniniw Inils
      •piirttiuUte miliai concintritlon. nw in1	—	- -.
       »nlilitlflrtc>larki!a,llo«rniKi.a-cni|7lrlEnBiif^li>ii ( iCUir i  nj
   juuu 'Eiislbh iniivri^ion fjni>r ll> 'nn
  9  Methods 10 and 11 aie added to the
appendix as follows
METHOD 10— DirrntMimiTioM or CARBON ilov-
 oxmE EMISSION! moil STtTlONjuT Souncrb
  1  Pnnciflt and Apfli
  1 1  Principle An Integrated or continuous
gas sample li extracted from n nampllng point.
and analyzed for carbon monoxide ICO) con-
tent using a Luft-ljrpe noncllsprrslvg liifrn-
red analyzer (NDIR)  or equivalent
  1 2 Applicability This  method  la appli-
cable for the determination of carbon mon-
o«ldc emlislona from stationary sources only
when specified by the test  procedures (or
determining compliance  with new source
                                               Ilillli Pi ton III)
pfr-3-mu'ce «-l tndards The tut pibcccluie
»til  nd'.nte uhether  u  continuous  or un
Integrated sumple Is to be user!
  2  Pange and stnsifiLicy
  21  Jlnnn* 0 to l.OnOpprn
  9^ Sensitivity  Minimum dptcclnblr ruii-
c<>ntr.aloM 1» JO  ppm  for n 0 to 1.000 ppin
span
  3  Intfr/frentPt  Any substance having a
strong abwipllnn  of  tnfrnrcd  oiierfty  will
Interfere to  some extent  Vat pxnmple  clla-
crtmlnitlon ratios far  water (H O) and  cnr-
bon  dioxide  (CO ) are 3 5 percent  K O per
7 ppm CO And  10 percent CO^  per 10 ppm
CO. respectively,  for devices mensiu Ing In the
1 SOU to 3 nno ppm range  For devices mcns-
IEGISTEI. VOl  39. NO  47—fRIDAY.  MARCH  8. 1574
                59

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                                                    RULES  AND REGULATIONS
!•••!•-..; In the 0 to IfHi ppm r.in^". Intn foronn1
-.•:<•-. .-i*a  be as lilijh R.s  3.6 pt-rcenL H O per
j> v-pm CC> iuid  10 percent CO per 5n  ppm
*-u. The tii»e of si.Ira RK! »nd a^-arlwt  traps
 ^;:i  nllevi.kte tbe  maj.tr Intertcrenre nrob-
!f:r.A. The  mviinurcU [,-aa  vulumc  must be
iL.iii-cte(l If th*.«« ira(«i at« used.
  4.  r.'fct.r.on find accuracy.
  4 1  Pr^rtMO'i. The precision of mo.-.t NDIR
;-.:i.xl~rr^  Is approximately  -^ 2 percent of
s*>i::.
 ' ; ?  Accuracy. The arcuracy of most NDin
..•  •.'. /rrs  li approximately  ••- S perrent of
 i-sn Mfcer calibra'-tcn.
  ."•  .-I ipur.if!/,»,
  i 1  CkJniinuotu sum;]/** il-'i^ure !<>-!).
  j 1.1 Probe.  Stamles*  steel   or  sheathed
P- rex  ','liis, equipped with, a Qiter to remove
p:ir::c«late matter.
  .M 2 Air-cooled  condenser or ecitiirn'.tnt.
T,t remove any excess moisture.
  32 /ntegrored sample (Figure 10-2).
  5.2.1 Probe.  Stainless  steel   or  sheathed
Pyr« glasa. equipped with a filter to remove
pariicuiate matter.
  522 Air-cooltd  condenser or equicalent.
To remove any excess moisture.
  5 2 J  Va.'re. Needle valve, or equlvn^nt. to
to adjust flow race.
  52-4 Pump.  Leak-free  diaphragm type, or
equivalent, to transport gas.
  j 2.5 Rate meter. Rotameter. or equivalent.
 10 ir.ea.sure a flow rarge from 0 to 1.0 liter
 ;ier mm. 10.0^5 ffm).
  .> C.J F.Vxib^c ^att. Tfliar.  or equivalent,
 \M:A a capacity of  60 to 'JO  liters (2 to 3  ftJ).
Leak-test  the  bag  In the  laboratory before
using  by evacuating bag with  a  pump fol-
lowed by a dry gas  meter. When evacuation
 U complete, there  should be no flow through
 the meter.
Mvt-  lnfr;ircrt  pprctromcter.  or  equivalent.
This liihtrumt-nt  ^houlrt  b?  demons) rated.
preferably by the manufacturer. to meet or
I'xcecd  manufacturer's  specification*  and
thus** desert bed in this method.
  5 J.M  l>rying  tube. To contain  apjirnxi-
mauiy 200 n of silica gel.
  5 ..< 3 Cultbi'atinn  yax. Refer  to p;u,i;.;r:vpu
C I.
  5.3 4  Filter  As  i>rt  '. M  up   ' it"
                                                                                           c(|-npin( MI. it:, i.liown In H'lure u>-i Ni.ii.ri-.
                                                                                           -.nr-1 :iit ciitun i lions  nre v,ik fn-r. I'l-i--*-  '.i--
                                                                                           jiriih- in the :,tfl*-k ;it ft ::implm» (n-n'. nr..i
                                                                                           HUI'£P  Hi*"  .'.umpliny  liiif.  rr.mi'-'-t  ' -"f ru it-
                                                                                           ly/fr  iurl  hc>;in  drawing  sa:npli*  Info  t:i"
                                                                                           ;ui;il;.vrr.  Allow  5 mlnilt*"? J'nr  tll«  s\.,f- IM
                                                                                           to .'itrihltlxt1.  (linn rprord the oiinl'.'Z'T r-'.ni
                                                                                           hit! as required by tn«  trjt prrw.,-Uiirf  r ••<•
                                                                                           f 7.2 and 0). CO.-  content of lh«  ;;ns nuty ti-
                                                                                           drti-rnilufU  bv  >i .n,;;  the Me'hud  :i  lii*f-
                                                                                           (•1-j.ied sample pi-o;-ctlure  (:iH  J-'H 'JlHfl'i). "'
                                                                                           |jv  •Ac:>:iilii£ IU^  n.oc.irii*  CO.  v»:nov,»l l'ib»-
                                                                                           o:irt computing CO.  c.jnrenlr:\ritin  irorn  tn •
                                                                                           x:i:-  VO!MIV.P  Mimplpd an-J  i!:«  v-u'l'c t: u'.
                                                                                           of thelubp.
                                                                                             7.1 .'J  lutetfr^tf.tl miinttttng.   Lvaciitt'.iS  th--
                                                                                           Jexiblt* hi-,-  Sft up the  equipm-nt an shi-A i
                                                                                           in  Ft'turo  10-2 with' the  bng  dlneonnerml
                                                                                           PI are 111 u prune  In the  sufck  and purge  tti"
                                                                                           j,aniplin- lino. Connect the bnu', mitkinR i^ui.-
                                                                                           that all r.mnertlons  are leak free. Sample .(;.
                                                                                           a  rate  proportional  to the stack  vflorltv
                                                                                           cn. conient of the  gas may  b«  detfrnilnfd
                                                                                           by  using the  Method 3  integrated  sample
                                                                                           procedures  (3ti FR 24886), or by  weighing
                                                                                           tin; aticarltc  CO  removal  mbe and comput-
                                                                                           ing CO. concpnti-atton from the gas volume
                                                                                           sampled and the weight gain of the tuhc.
                                                                                             7.2 CO Analysis. Assemble the apparatus as
                                                                                           sho*n  in Figure  10-3. calibrate  the Instru-
                                                                                           ment., and perform other required operations
                                                                                           :is  described In paragraph  B. Piir^e analyrpr
                                                                                           w>'r«.  >f *jr'rtr *o lnrroduc;ion  >t' —*rh 5Arir:'»
                                                                                           D.rftct itie .iftinple strffim chr-ni-isi the ii-irri,.
                                                                                           meiic for the te^t period, recording the read-
                                                                                           ings.'Check the zero and span  »i!ain after the
                                                                                           test to assure  that any drift or malfunction
                                                                                           is detected. Record th« sajnple data on Tab I a
                                                                                           10-1.
                                                                                             8. Calibration. Assemble the apparatus ac-
                                                                                           cording in Figure 10-3. Generally an ln>tru-
                                                                                           ment requires a warm-up  period brfore r.ta-
                                                                                           billty 1« obtained Follow the manufacturer's
                                                                                           Instructions for specific procedure. Allow  a
                                                                                           minimum  time  of on« hour  for warm-tip.
                                                                                           During  this time check the  sample  condi-
                                                                                           tioning apparatus. I.e., filter, condenser, dry-
                                                                                           ing tube, and CO' removal tube, to cnnttre
                                                                                           that  each component la  tn, good  operating
                                                                                           condition. Zero and calibrate the Instrument
                                                                                           according  to the manufacturer's procedures
                                                                                           using, respectively, nitrogen and  the calibra-
                                                                                           tion pases.
                                                                               TABLE 10-1.—Field data.




p
Clock tim.-

	 Comments:




Rotameter setting. Htrrs per minute
(cubic /(**:( per minute)

                                                 9. Calculation— Concentration of carbon monoxide. Calculate the concentration of carbon
                                               monoxide in the stack using equation 10-1.
                                „         ,-,            ,,   .
                                Cea.iMt"*tco,i.n|E(i-fcf*)
                                                                                                                          l!t(Ufttion 10
  52.7 Pilot t-ibe. Type 6. or equivalent, at-
tached  10 th» probe so that  the sampling
rate can be regulawd  proportional to  the   \\hcn1:

                                    i Is con-        Cco.,,,k = coucclltr;lt'"n °' CO in stack, )>|)in liy volume (dry ha.*!?).

                                                   (7COumii = concentration of  CO miw.urcil by Nil in analyzer, ppin by volume (dry
                                                              ' basis).
            is (Figure 10-3).
 ^SSStt&SSSIZS&ff&Sl           reo,- volume fraction of CO, In  wm.-lc. I,-., p, rccut CO, from Or«l unu.y,,
 EnTlromnental Protection Agency.                              divided by 100.
                                      FEDERAL MOISIEK, VOL 39, NO.  47—FRIDAY, MASCH «, 1974
                                                                 60

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                                                   RULES  AND  REGULATIONS
   )1! iVjrapl V
   ;  MiElroj VTiuV. T-c Iii-i-r erS s iMT-CO
     \na'v tr  P >-i IXHJ  at II *i  Vr:ln-I-
     Cnnfrrerce on  Mr Pol'.ut *-n T. u  er^i* '
     of  Cill.'orn i  D*.-1 eley  La1.'   \p-II  1
     1HT3
     J icoba M D .  ft il  CoiUlniioiii IV »• r-
     m n^lian n' ("ft*non ^aincciile < 'd H -
     (I  ocirtxms In  .\*r by -. McJ!'<-»d Infri-
     rexl AiiMv?-"  J  *.r  Polh ' uii Coi -rol
     V-f* Lilian  !/-:i  I'D-1.4  \U« .3'  I°j9
   '  Mot  LLKA  In'rarM  G t»  .u rt 'jqj *l
                                                  \n  1,/pr Instruction Book. Mine *-aU*t t
                                                  Appl  HUM Co, liThnlial Prrxhic'.- I* -
                                                  vi.ion I'ntsburgh I'i
                                              I'M M(*lol!) 2)J\, 31CA  AIU)  4151 rnfrirr-l
                                                  Miil>7er3  BcckmMi  Instruments  Tnc,
                                                  Hcc^man  In .iructionn 163S-D.  Kuller-
                                                  UMI C illf October 19b7
                                              10 *• t'ontiii'ioiis  CO  Moultorlpp  Sy->n-*ni(?iit i urn is
  Output—LlPC-rlLil Jvnal wbici is propor-
tional to ihe me*»urf-nent.  Intended for con-
nection to readout cr data processing device?.
Usually expressed as millivolt* or mil'nmps
full scale at a given Inuxdnnc*
  full seal*—The maximum measuring limit
for a given range
  .Minimum    detectable    jrnjitn *(v—The
smallest amount of input concentration that
cin be detected as  the concentration  ap-
proaches zero
  Ac-curacy—The  degree of  agreement  be-
tween a measured \ilue and the true vilue
usually expressed AS  * percent of full scale
  Time to 99 pprr»nt re*ponae—The time »r-
tertal from a step change In the Inp-it con-
rfntratlon at the instrument tn'rt to a read-
ing of 90 percent of the  ultimate recorded
cnncenrmiOD
  £•«• rime  (90 p^rc*if)—The Inte-vnl *w-
tvtren initlM renoor^ Lime and tlrnr to 90
perrent response after n step IncreaM In the
mletconcentrat'on
  Fa'l Tim? (90 percent)—The Inter* nl he-
f-.een JrltUl response time and time to 90
percent mponw after a step dec-rue  in the
1'ilet concentration
  Vert* Dn/t—Tht rhdi 3f In in-,fument out-
put o^er a  stai*>d  time pp-iod  usuMl? 24
hours of unadjus'ed comim.om opera' on
\ hPn tire input conce-Tniioi Is /ero usual!?
expressed as PTC^T,  full vnle
  •?j-in Drt'^—The -*!*•!•:» i" lps.-*im?nw' nur.
PUG o.er a  aiai«d  tm e ptfiu>l  UMUH/ -4
hours, of unadjusted crm'inuou^ operniion
*»!ien tbe input concentration Is a stated
unsettle value,  luualiy expressed \s percent
full scale
  p-ecit-on—The d?eree  of p*-s»m"n-  b»--
t*fI3E L MISSIONS PTOM bT&TTOVAAT SOtnCCS
  1  Principle and  arolurabilir*/
  I i  Principle  Hydrogen  sulftde (HS)  b
collected from the source in a aeries or midget
                                              impiivurs and rencted  with alkaline end
                                              mium  hvdroTido  |Cd(OH)j|  to form c.id-
                                              n.ii'n  >uintie  (CJSi  The pr*cipir trcii  LfIS
                                              ij rheii (UbMiliect  In  hydroohmnr  n. •!   .HI
                                              abs^ro«d in a  known volume ot iodine solu-
                                              tion  Ihe Iodine consumed ti a meajii*« of
                                              tbft H 5 rontfnt of the gas An implnger rnn.
                                              talning hydrogen peroxide Is Included to rp-
                                              mo <• SO. us an Interfering- species
                                                l 3 Applicability  This method Is applica-
                                              ble for the determination of hydrogtn  fciil-
                                              nde emissloos  from stationary  sources only
                                              urtni itpecined by the  test procedifes  for
                                              determining compliance with the new source
                                              perfoi mince standards
                                                2 Apparatus
                                                2 1 Sampling train
                                                2 1 1  Sampling line—6- to 7-mm (<4->nc-lt)
                                              leQon  ' tubing to connect sampling tram to
                                              sampling  \ilve, with provisions for  heitlng
                                              u> present condensation  A pressure reduc-
                                              ing  vilve prior to the Teflon snmplinf*  li.ie
                                              may  be   required  depending  on  sampling
                                              stream pressure
                                                2 I 2   /nj»mj«rs—Five  midget  Implngers
                                              each wnh 30-inl capacli.)  or equivalent
                                                '2. 1 3  'cr bath container—To maintain  ub-
                                              snrblnfi solution at a constant temperntvire
                                                2 14  Silica  gel  dn/tng  tubf~To  proter:
                                              pump and dry gas incur
                                                2 1 5  ffcrdle  lalue  or equivalent—Stiinlp<-s
                                              11 eel or other Tirroston resistant mnterhil to
                                              adjiid*  t'.'Ui How rare
                                                2 l 6  Pump—lAtik free  dlnphrn^m  t>pe ur
                                              equivatrnt to  transport  gns  (Nut  retjuired
                                              if n.impllns stream under positive pre**ure l
                                                .'1 7  /)?'/ nfi Tipfsr—Sifllctentl/  -uturi'i1
                                              in 'Ticiiiirv  trnp e volume ro within 1  per-
                                              cent
                                                2 1 BRatc meter—Rotameter or e'liuvilrnt
                                              to muasurp  n  now rate  of 0 to 3  it. era  per
                                              minute (0 1  ft'/min)
                                                2 I 9  CrTtiiluntrd ry/mrfT—°5  ml
                                                £ 1 10 Barttmtter—To ine^&ure atmospheric
                                              pr^sinre  vmhln ^-25 mm (01  In )  Hj;
                                                2 2 Sum pi? Retotery
                                                22 1  Sample container— 5i)0-nl g'a-s-vop-
                                              percd iodine Rask
                                                222 Pipttte—50-ml vul time trie npt
                                                a 2 3  Bealffrs—?50 ml
                                                224  Wash bottle—Dittos
                                                23 Analvsn
                                                231  Flask—500-ml glass-stoppered lodins
                                                1 Mention of trade names or specific prod-
                                              ucts does not constitute endorsement by the
                                              Environmental Protection Agency
   '  I  c.y * :<
   ' 1   ii> v'1 '''
  3 I I  \ty.' rn-rv;   sni if . *l  f  (Milum   liy-
M-..VU e (CdifJlf l 1- Mi   1 i r i.uiiiii'iiii ' ul
'•\'e I  ,»lr-tc  la Li'iO.ttHOj  «>"!  »'I r o!
•ntl-u n li il-rt Iilr iNiOM)  in  I  I '>r i-f ill.-
l ll-rl tn.'riilUl  Mlx'VLM
  4\i'•'   I'it  culimuni hytlnnlfle r>rmftl li
I'M* i  \'U:P vMI jir-t.TUrt'f HI  i w'u't J»u.-
p   j'on   Tii  r* K-r»  1'iu  -»liii  rut'*  li"
   •i01  ,lv MI*-I !«'"'rt  Msiiii' '•>   >>»r   in
r ^ i O'a rihiiiuin -if tne cadi IUIIM 'i,flio\nli
  J I " H i Irmi n /icronrff 1 p '• ff— Hilnl •
30  pun it hjflrfi^'ii  p^roxu'i1  '.•»  i JHT-« nt
p . ii t>LL(l  I'ropart  fresh d.ul>
  3 n M.mii/i1 rrroi rry
  "21 Hwlrtrnlctnr ccitl ,f»'ii(if»Ti (HCI\  lit
pvr*>n( by  xcwht— Mix 210 ml ol  rtmc' n-
wiiied I1C1 fspfCit c ^wlt> I 10) and 770 ml
oi tlKti.'pd H O
  32^ Icxiine solution  0 t .V—l>i--».lv^ 24 •
polonium lodirte  (KI) m 3D i il of  dl.lillc'i
FTO In i 1-liter Rradiiikteri (.jltiuler WLI/II
1J 7 r nf rcbuhlimcd ir^inc (I ) Into a wl-h-
i-j botilu and add to the pota  Mim indide
•>niutton bh ike the m•>•  Oi'ir O •  i II N   i>l-
lti'«  t el low Add n few
dropi  of  the starch solution uui  conLinue
turaitpg  until  th«  hluo rolop just flisip-
pfan*  Prom thn r^ull* of this lnr it ion  c ti-
culare  the ex.ict  normnlity of the li»rllii»
solution f-.ce p irn^rnph 5 11
  324  niSflU'd r!« U'H^fft tiuUr
  30 Analysts
  331  Sodiitrn  thiont*fatf snlurmii -.'nnrin.it
01 .\—For each  liter of  lolniu-'.  duinhp
218 po' jodlmn thiosnirue ( MA S O. ill O)
 in disitlied v-.iter and add 001 <;nf uih>diou-«
-odium carbnnttp  (NiCO)  nnrl  04 ml  ol
t lilorr.fo m (CIICl)  to rtahih'f  Mix ihnr-
oimhly bv tn»Kinc <»r  b; npntnu. with nitro-
gen 'or approximately 15 n-'lnutej. and a1 fire
in n glass-stoppered R!L»S., hut11?
  biindardize  frctj\iently ^ folio ^-> Wi.lgh
Into n f.OO-ml  i*olurr"irlc flask  HhruiL ?  [• of
potai&ium  dirhrom tt.e   (K *.rO }   \\t-\rrheil
to  t.hi  ML irrs.  .mill. r.\m and diln^i* to  th-
 •PO-'-nl  n"»r»:  »n*i  cll-tilkU  LI O  Uw   rli-
chronuae \vhifn hiUi  utii\ cr  '.vll Til  (run
dMltlCd  AUKT  P I'I ulPll-rlriPd  tl  IH'J r  10
 ].|Q»C 'Jhit P to  'tO'*"*!   DLsiol ^  'ii»oml-
   tU I r i  ' i>i put i k-iii u i«.>"nn   vli   11 l^-i*up|ii rid jid'i-nil
ronirnl "a, k  then adJ 5  ml <»( .'ft-ppf-onL
h><1rocrlurLc held solulioii IMpifie  r>0 ml of
 the di< hromate -.oluti&n  into  il.ii  mxtuu
Gently snlrl  the soltiinn 01 r<  n id ullo'v it
to  stand  m  Ihe f'.irk 'or S mmiiifs P'lule
 , n.' u v.uh  mi to 'Jii)  n,i i.: in.ruled
 w iu?r  va'ihirfr down i1 P sides m 'he n i  K
 v.';h p.irt of the  u IUT Sivirl  the  Ln'tiiinn
Mrtwly and iiirnle  v.r,i me  thoitMlfiic Mrin-
tinn until the oolu'ioi Ls  lipht j.-l'o-v  Add
4 ml or sianh •uiluiion and continue with A
s'ow tun Lion with the  rhUisttlfittf tuiLiI  the
bright blue color r"is dlsnpptnrrd  *\iitl only
the pale  green  color of tMe chromic Ion f-
ninins F>-nm this tltrarlon rvlculito the «>x-
a< t normality of the fiouium thiOiiiiiKte solu-
tion (see paragraph 521
   333  Sottium  th ingulf at? snlutMii starttlnnl
001 iV—P'peue 10J ml of the stniidiiJ u l 'V
thio4ulrito solution  Into  a i*nluin»irli. I n .
-------
                     APPENDIX B
REQUEST FOR PROPOSAL SENT TO CANDIDATE COLLABORATORS
        FOR THE METHOD 10 COLLABORATIVE TEST
                          63

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                             SCOPE OF WORK
1.   Purpose

          Tlic purpose of this task is to provide the Environmental
Protect ion Agency (EPA) with data on the reliability and bias of "Method 10,
Determination of Carbon Monoxide Emissions from Stationary Sources."  (A
copy of a write-up of this method, pages 9319-9321 of the Federal Register.
Vol. 39, No. 47—Monday, March 8, 1974 is attached.)
II.  Statement of Work

          A collaborative test program will be undertaken to achieve the
purpose given in Section I above.  Midwest Research Institute (MRI), as
prime contractor under Contract No. 68-02-1098, will coordinate the test-
ing, analyze the results of the collaborators, and report findings to EPA.
Testing will be done simultaneously by all collaborators at the same sampling
location at a specific test site.  This testing will be done according to a
specific experimental design made by MRI.
Til.  Collaborators

     A.  Qualifications

          Each collaborator is required to provide MRI with it qualifi-
cations to do the required testing and reporting.   These qualifications
include:

          1.  Capabilities and experience of personnel who do the work;

          2.  Management's interest in the work;

          3.  Field equipment that will be used in the field on this pro-
ject; and

          4.  Past and current programs or jobs of your company in which
Carbon Monoxide (CO) was measured from stationary-source emissions and
in the ambient air.

     B.  Project Personnel

          The people who will be assigned to do this work should be iden-
tified by name.  A biographical sketch of each should be given that

                                 .   64

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includes capabilities and experience th.-it is directly rclntcd to tlic work
task.  F..icli person's function on the project should also be given, as well
.ns his position on your staff.

     C.  Managements Interest

          This should include a statement by management on its ability
to furnish all the equipment that is required and that it can meet the
work requirements.

     D.  Equipment

          Each collaborator is to furnish all equipment (Figures 10-2 and
10-3 on page 9320 of the above-referred Federal Register) that is required
to perform the field testing in accordance with Method 10, using the
integrated gas-sampling procedure.  The type (manufacture and model) and
amount of this equipment that will be taken to the field for use there on
this test should be identified.  The recorder (Section 5.3.9 on page 9320
of above-referred Federal Register) will be_ required to provide permanent
records of NDIR readings.  Preconditioning equipment requirements specified
by the NDIR instrument manufacturer must be met.

     E.  Company's Experience in CO Measurement

          Information given should be that which is directly related to
the work task of the program (current and past programs).  The summary
of each program cited should include the names of those project personnel
(Section III.B of this RFP) who worked on it.
IV.  Plan of Test

     A.  Number of Collaborators

          Ten collaborators will be needed for this test--five  to use  the
continuous—sampling techniques (Section  7.1.1 on page 9320 of  the  above-
referred Federal Register), and five to use the integrated-sampling
technique (Section 7.1.2 also on page 9320).  However, each collaborator
should be prepared to sample according to the integrated, gas-sampling
procedure.  The recorder (Section 5.3.9 also on page 9320) will be_  required
to provide permanent records of NDIR readings.

     B.  Test Site

          The test site will be the El Dorado Refinery of the American
Petrofina of Texas, which  is located in El Dorado, Kansas.

                                     65

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      C.   Test  Location

           The  test  will  be  conducted  at  ground  level  from  a  sampling mani-
 fold  that is connected  to the  CO boiler  emissions  stack.   A  representative
 system is shown  in  schematic form in  Figure IV-1,  which is attached.

      D.   Experimental Design

           The  goals of  the  test  are to determine:   (1)  accuracy—the devia-
 tion  of  an individual measured value  from an accepted reference  level; and
 (2) precision--tho  spread between individual measured values, specified by
 repeatability  and reproducibility.  It is desirable to  execute Method 10
 in according to  each of  the two  procedures  stated  in the Method  write-up--
 the continuous sampling  procedure and the integrated sampling procedure,
 and to have a  design so  that occasional missing data will  not affect the
 results  significantly.   The design in summary is:

           1.   Five  block of tests;

           2.  Two blocks in which each collaborator samples  from the sam-
 pling  manifold for  two different  levels of  CO—L,and Lo;

           3.  Three blocks  in  which each collaborator samples from
 "standard  tanks" (Prepared  by  the National  Bureau of Standards)  for three
 different  levels of CO—LJ, L2 and LT;

           A.  Sampling times:   60 minutes per run.  The experimental pro-
 cedure will be for  each  of  the ten collaborators to determine the CO con-
 centration at LI four times a  day; five collaborators using  the  continuous-
 sampling  procedure, and  five using the integrated, gas-sampling  procedure.
 After  four days of  testing,  a  second level  of CO will be generated, and
 four days  of observations at L2 will be collected.

           Three observations will be made by each collaborator from each
 of the three levels (L^ L2 and L.J) from the "standard  tanks" both before
 and after  the CO observations  of  levels Lj  and L2 of CO from the CO boiler
 emissions.

     E.  Test Schedule

          The test period in the  field is to be ten, 8-hr days,  assuming
no delays due to process operation, weather or other possible contingencies,
The general tentative schedule is:
                                    66

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Pressure
gauge
Sampling
ports
                       Flowmeter
                           Pressure
                        y gouge
                                              Stack port
                                                               Intake located
                                                               in CO stack
                                                              t
                                                        Direction of
                                                     ,i  stack gas flow
                                       Moisture
                                       drain valve
                                  Moisture
                                  collector
                                                      •Ground level
                          Sampling
                          ports
                                        Flow meter
                                         Pump
                                                   •Exhaust
                 Figure  B-l.   On site general test setup
                                     67

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Day
Monday


Tuesday

Wednesday

Thursday

Friday

Monday


Tuesday

Wednesday

Thursday

Friday



Date
06-03-74


06-04-74

06-05-74

06-06-74

06-07-74

06-10-74


06-11-74

06-12-74

06-13-74

06-14-74


F. Field
Activities
Orientation of collaborators, collaborator
preparation for test, "standard tank" ob-
servations at levels L^, L^ and I/j .
Runs 1-4: sampling from manifold with CO
boiler at L, .
Runs 5-8: sampling from manifold with CO
boiler at L^.
Runs 9-12: sampling from manifold with CO
boiler at L, .
Runs 13-16: sampling from manifold with CO
boiler at L, .
Runs 17-20: sampling from manifold with CO
boiler at L0.
2
Runs 21-24: sampling from manifold with CO
boiler at L..
Runs 25-28: sampling from manifold with CO
boiler at L .
Runs 29-32: Sampling from manifold with CO
boiler at I*,.
"Standard tank" observations at levels, L^,
1*2, and Lo; dismantling of test set-up.
Test completed.
Data Sheets
          These forms will be furnished by MRI for recording all pertinent
field data.  A copy of each completed data sheet of a collaborator is to
be given to MRI after the completion of a day's testing.
V.  Summary Report

          Eight copies of a summary report are to be submitted to MRI
attention Paul C. Constant, Jr., within 3 weeks  from the completion
                             68

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of field testing.  This report should not be elaborate in any way,  hut
should include:  (1) field data, (2) calculated results,  (3) a discussion
on how these results were obtained, (4) a discussion covering problem arms
encountered in testing, explanations of data and procedures that you be-
lieve -ire germane to a reader's understanding of your work, and pros and
rons on the write-up of Method 10, (5) a description of the field equip-
ment you used in field sampling, giving type, manufacturer, model etc.;  and
(6) identification of the project team, including each person's responsi-
bility and areas of participation.
                                    69

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          APPENDIX C
INSTRUCTIONS FOR COLIABORATORS
     CO COLLABORATIVE TEST
       EL DORADO, KANSAS
              71

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 GENERAL INFORMATION

      1.  Calibration, sampling, analysis, etc., should be done explic-
 j±ly  as  stated  in  the 8 March 1974 version of Method 10 analysis for
 Performance Standards for Petroleum Refineries.  A permanent recorder
 output  is required for this test.  The probe and Pitot tubes will not
 be  used.  Connection of the sampling lines shall be made directly to
 the sampling manifold.

      2.  Each collaborator will be assigned a port number.

      3.  Code numbers for each sample will be assigned by the test
 supervisor.  The code numbers will consist of a run number (1-2), fol-
 lowed by port number (1-10), followed by level designation (A or B),
 terminated by a collaborator number (1-7).  These code numbers should
 appear  on the recorder charts for each sample.
               Collaborator

               Scott Research

               Interpoll, Inc.

               TRW

               Environmental Triple S

               Ecology Audits

               Coors

               Entropy Environmentalists, Inc.
     4.  The results for each day's runs should be given to the test
supervisor at the end of each day.

     5.  Each collaborator should work independently of each other
collaborator.

     6.  The morning of 3 June will be spent setting up equipment and
during the afternoon a series of check gases supplied by the National
Bureau of Standards will be analyzed by all collaborators.   For these
tests only the continuous mode test will be used.
*  Omitted on purpose for this report.

                                  72

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     7.  Within 1 month of the end of test a report containing the fol-
lowing items shall be submitted to MRI:  (a) original recorder charts,
(b) calculated results, (c) a discussion on how these results were ob-
tained, (d) a discussion covering problem areas encountered in testing,
explanations of data and procedures that you believe are germane to a
reader's understanding of your work, and pros and cons on the write-up
of Method 10, (e) a description of the field equipment you used in
field sampling, giving type, manufacturer, model, etc., and (f) iden-
tification of the project team, including'each person's responsibility
and areas of participation.

TEST INSTRUCTIONS

     1.  Prepare your equipment.  The Tedlar bag with the other com-
ponents of the assembly shown in Figure C-l of Method 10  may be placed
on the ground beside the sampling port.  The NDIR and other equipment
in Figure C-2 may be set up on the tables provided.  Power outlets for
both areas will be available.

     2.  Obtain a code number for the run.

     3.  Upon notification of "Start testing" from the test supervisor,
connect your integrated gas train to your port and sample according
to the March 1974 version of Method 10.

     4.  Test duration for each run will be 60 min.

     5.  At the signal to "Stop testing" terminate sampling and pro-
ceed immediately to analyze the sample obtained according to the method.

     6.  The initial flow rate with the integrated gas train shall be
identical for all collaborators and will be determined by the capacity
of the smallest bag.  During each test you will be required to sample
at a rate proportional to the flow reading from the rotameter connected
to your side of the sampling manifold.  A calibration curve for these
meters is supplied at the end of these instructions.

     7.  During sample analysis the sample stream should be connected
to the NDIR until a straight line of zero slope is obtained, usually
no more than 10 min.
*  See Appendix A for Method 10 write-up.
                                  73

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     8.  Data for each test should be recorded as shown in Table 10-1
of Method 10.  All pertinent analytical data should appear on the re-
corder chart for each run.

     9.  When analysis is completed, the next run will be started after
everyone is ready.

     10.  The tentative schedule of testing is for four runs to be made
on each day.  Measurements at Level A will be made 4 to 7 June, and
Level B will be measured  10 to 13 June.

     11.  After the first day, the initial run for each day should
begin at 9:00 a.m.
                                  74

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   FISCHER & PORTER CO.
                TEK CO.  I

                'ft-lT'' '.-'}  '•'
TUPE -fi-j4 -.40 -& - I _ i
FLOAT - 1/4-CA




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      APPENDIX D
EFFECTS OF DELETED DATA
           77

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     From the field data, one collaborator (Collaborator 7) and three
levels  (Runs 1 to 3, run under negative pressure) were deleted from
analysis.  Collaborator 7 was also deleted from the standard data.
This appendix examines the reasons for these deletions and presents
the analyses including the deleted data.

FIELD DATA

     The pertinent changes in results arising from inclusion of Levels
1 to 3 and Collaborator 7 are shown in Table D-l.  (The complete AOV's
are shown in Table D-2.)
            Table D-l.  EFFECTS OF INCLUDING RUNS 1 TO 3 AND
                     COLLABORATOR 7 (FIELD DATA)
                          w/o Runs 1-3 (w/o
                           Collaborator/ 7)          WR 1-3

I-A.  Level mean square        26,006                38,473
      Error mean square         1,249                 3,549

                          w/o Collaborator 7
                            (w/o Runs 1-3)             WC7

II-B. Collaborator mean
        square                 26,006                57,270
      Error mean square         1,249                 6,058
                                  78

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             Table D-2.  FIELD DATA ANALYSES OF  VARIANCE
 II-A.  w/o Collaborator  7, w/o  Runs  1-3

            Source     df         ss           IDS
II-B.
II-C.
c
B
CB
L
LC
With Runs
C
B
CB
L
LC
5
1
5
27
113
1-3 added
5
1
5
30
122
With Collaborator 7
C
B
CB
L
LC
6
1
6
30
133
96,909
1,400,344
16,010
702 , 166
141,128

146,244
1,170,001
61,013
1,154,186
433,019
added
343,619
1,524,765
84,579
1,745,452
805,732
                                              19,381       15.52
                                           1,400,344     437.32
                                              3,202       2.56
                                              26,006       20.82
                                              1,249
                                             29,249       8.24
                                           1,170,001       95.88
                                             12,203       3.44
                                             38,473       10.84
                                              3,549
                                             57,270       9.45
                                           1,524,765      26.21
                                             14,096       2.33
                                             58,182       9.60
                                              6,058
     As seen in Table D-l, the inclusion of either Levels 1 to 3 or
Collaborator 7 significantly increases the residual variation and the
pertinent components of variance.  In fact, the variance within Col-
laborator 7 is about three times greater than any other within collab-
orator variance.  Also, 12 of the 21 observations taken on the first
three runs could be labeled outliers, and two values are missing.

STANDARDS DATA

     Collaborator 7 was eliminated from the standards analysis simply
because Collaborator 7's bias was so great.  Collaborator 7's average
                                  79

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bias was 30 times as great as the average bias of the other six collab-
orators, and an order of magnitude greater than the bias of the next
most biased collaborator (see Table D-3).
          Table D-3.  ANALYSES OF  VARIANCE  (STANDARDS DATA)


 III-A.  w/o  Collaborator  7

             Source        df        ss         ms
                C
                L
               CL
                e
 III-B.  With  Collaborator  7  added
5
5
25
66
43,129
20,979
21,630
1,349
8,626
4,159
865
20.4
422 . 12
4.81
42.34
-
C
L
CL
e
6
5
30
78
621,749
5,047
146,236
1,365
103,625
1,009
4,875
17.5
5,921.4
< 1
278.57
-
                                  80

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                                   TECHNICAL REPORT DATA
                            (Please read {mmctiuns on the rnrm- bejorc completing)
 1 REPORT NO
  EPA-650/4-75-001
                                      3. RFCIPIFNT-S ACCESSION-NO.
4. TITLE AND SUBTITLE
 "Collaborative Study of Method  10  -  Reference Method for
 Determination of Carbon Monoxide Emissions from
 Sources - Report of Testing."	
                                      5. REPORT DATE
                                       January 1975
                            Stationar 9- PERFORMING ORGANIZATION
                                  CODE
 7 AUTHORIS)
 Paul  C. Constant, Jr., George  Scheil,  and Michael C.
 Sharp	
                                      B. PERFORMING ORGANIZATION REPORT NO


                                        3814-C
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 Midwest Research Institute
 425 Volker Boulevard
 Kansas City, Missouri 64110
                                      10. PRC'GRAM ELEMENT NO.

                                        1HA327
                                      11. CONTRACT/GRANT NO
                                                             68-02-1098
 12. SPONSORING AGENCY NAME ANO ADDRESS
 Environmental Protection  Agency
 Office of Research and  Development
 Washington, D. C.  20460
                                      13. TYPE OF REPORT AND PERIOD COVERED
                                      14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
 16 ABSTRACT
           A collaborative test was conducted by MRI at the  El  Dorado  Refinery of Armen-
ian Petrofina of Tex.  during 3 to 14 June 1974.  Seven organizations participated in the
;est of "Method 10."   All  collaborators sampled simultaneously  using the integrated bag
lethod.  The sampling  manifold was connected to the CO boiler stack of the fluid catalyt-
 c cracking unit.  All  runs were of 60 min duration.  Each collaborator obtained 4 sample
jer day—two in the morning and 2 in the afternoon.  Sixteen runs were made at each of 2
:0 levels.  MRI had an NDIR operating in the continuous mode during each run to monitor
the CO concentration. ' Each collaborator analyzed 6 cylinders of CO in nitrogen which had
)een certified by the  NBS.
      The collaborators  submitted tentative readings after each test and later sent MRI
their final results, which included the original recorder charts.  MRI checked the colla-
xjrators' results and  then statistically analyzed the collaborators' results.
      The collaborators'  results from sampling the1 CO boiler stack were analyzed to
tetermine the precision  of the method and the standard gas results were used to deter-
nine the accuracy of the method.
 7.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
 Air pollution
 Carbon monoxide
 Data
 Emissions
 Refineries
 Field tests
 Tests
Infrared spectrometer
                        KlDrNTIFIERS/OPEN ENDED TERMS
EPA Method 10
CO boiler stack
Collaborative tests
Stationary sources
                                                                         L. COSATI I ii.lil/(.rimp
13B
 7B
14B
 3 DISTRIBUTION STATEMENT
 Release Unlimited
                                              19 StCURITV CLASS (Illtl Hfport/
                                               Unclassified
                                                                         21 NO or
                                                                         32 PRICE
EPA Form 2220-1 (9-7J)
                                            81'

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