EPA Project Report No. 73-SFA-3B
  CD
AIR  POLLUTION
EMISSION  TEST
O
    ifi,
                          FINAL REPORT
    MISSISSIPPI CHEMICAL CORPORATION
                       PASCAGOULA, MISSISSIPPI
         UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
                Office of Air and Waste Management
              Office of Air Quality Planning and Standards
                 Emission Measurement Branch
           f    Research Triangle Park, North Carolina

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                                     FINAL REPORT

                               CONTINUOUS MEASUREMENT OF
                               SULFUR DIOXIDE  EMISSIONS
                            EPA Project Report No. 73-SFA-3

                           MISSISSIPPI CHEMICAL CORPORATION
                                PASCAGOULA, MISSISSIPPI
                   Prepared  For

        The Environmental  Protection Agency
             United States Government

              Contract No. 68-02-0232
                    Task  No. 26
            ESE Project No.  73-011-026
environmental science and engineering, inc.

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                         FINAL  REPORT
REPORT NO:   .    73-SFA-3
PLANT TESTED:    Mississippi  Chemical Corporation
                Pascagoula,  Mississippi
EMISSIONS  FROM:  No. 2 Sulfuric Acid Plant
TESTOR:
Environmental Science and Engineering, Inc.
Post Office  Box 13454
University Station
Gainesville, Florida  32604
CONTRACT NO:     68-02-0232,  Task Order No. 26
      environmental science and engineering, inc

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                     TABLE OF CONTENTS
                                                         Page Number
1.0  INTRODUCTION                                              1

2.0  PERFORMANCE AND MAINTENANCE OF THE  CONTINUOUS
     MONITORING SYSTEM                                         4

     2.1   PERFORMANCE CHARACTERISTICS  OF THE CON-
          TINUOUS MONITOR                                      4

     2.2   LONG-TERM PERFORMANCE AND MAINTENANCE OF THE
          CONTINUOUS MONITORING SYSTEM                         7

3.0  PROCESS OPERATION                                        10

4.0  OPERATIONAL COSTS                                        11

     APPENDICES

          APPENDIX A - PROCEDURES FOR  DETERMINING ACTUAL
                      PERFORMANCE OF  THE MONITORING SYSTEM
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                        LIST OF TABLES
                                                       Page Number
Table 1.   Determination of Factor to Convert Monitoring
          Units Into Units of the Applicable Emission
          Standard.                                          5

Table 2.   Performance of the Sulfur Dioxide Continuous
          Monitor.                                           6

Table 3.   Cost and Level of Effort Based Upon Procurement,
          Installation, and Operation by a Service
          Organization (e.g., an  Engineering Consultant
          Firm)9                                            12
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1.0  INTRODUCTION
     As part of the  Continuous Monitoring Project directed by the Emission
     Measurement Branch, Office of Air Programs, U.S. Environmental  Protec-
     tion Agency (EPA), an evaluation of sulfur dioxide emissions from a
     sulfuric acid plant and of a continuous sulfur dioxide monitor for
     stationary sources was conducted by Environmental Science and Engineer-
     ing, Inc.  (ESE).  The evaluations included conducting performance tests
     on the continuous monitor and analyzing the long-term performance of
     the plant over  a six-month period.

     The continuous  sulfur dioxide measurement system evaluated was in oper-
     ation at the No. 2 sulfuric acid plant of the Mississippi Chemical
     Corporation (MCC) in Pascagoula, Mississippi.  The system continuously
     measures and records the sulfur dioxide concentration in the effluent
     gases of the plant.

     The purpose of  the performance tests was to evaluate the operation of
     the continuous  sulfur dioxide measurement system in regard to certain
     "performance specifications."  General requirements for continuous
     monitoring and  recording of sulfur dioxide emissions from sulfuric
     acid plants were initially published by the EPA in the Federal  Register
     (Vol. 36, No. 247, Subpart H, Section 60.84, December 23, 1971, Wash-
     ington, D.C.).  More recently, specific monitoring requirements, per-
     formance specifications and procedures for determining whether a
     continuous monitoring system meets the performance specifications
     have been proposed by the EPA for monitors of sulfur dioxide emissions
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from stationary sources (Federal  Register,  Vol. 39, No. 177, Part II,
September 11, 1974, Washington,  D.C.).   The required performance tests
were conducted during the period from September 10-14, 1973, and as
such occurred before the suggested  methods  were published by EPA.  The
testing procedure adhered to  in  the operational testing period was
very similar to that specified  in the above Federal Register.  However,
the performance specifications  by which  the sulfur dioxide monitor was
evaluated in the interim report  have been significantly modified.  To
determine the effects of these  changes on the performance evaluation
of the continuous monitor, the monitor was  re-evaluated according to
the new specifications, using the data contained in the interim report.
The re-evaluation is presented  in this report.

A continuous sampling program utilizing  the continuous sulfur dioxide
monitor was conducted for a 6-month period.  The purpose of the con-
tinuous monitoring was to evaluate  the long-term emission performance
of the MCC sulfuric acid plant  and  long-term performance and maintenance
requirements of the continuous monitor.  The 6-month period extended
from September, 1973 through  March, 1974.

Procedures, results and discussion  of the performance testing are con-
tained in the interim report  under  this  contract, entitled "Source
Test Report, Measurement of Sulfur  Dioxide  Emissions, Mississippi
Chemical Corporation, Pascagoula, Mississippi, Report No. 73-SFA-3."
The long-term performance of  the sulfuric acid plant in regard to its
sulfur dioxide emissions will be presented  in the "Data Summary Report"
for this project task order.  Statistical and analytical data summaries
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will also be contained  in this report.  The long-term  performance
characteristics  and  operational problems associated  with  the continuous
sulfur dioxide monitor  are discussed herein.

The continuous sulfur dioxide monitor evaluation  project, of which this
report is part,  was  in  general a marked success.   A  wealth of knowledge
was gained concerning the instrument performance  and maintenance, over
both the short-  and  long-term.  The sulfur dioxide monitor proved to
be a reliable, low maintenance, easy to operate system and complied
with most of the new, more stringent, EPA performance  guidelines.
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2.0  PERFORMANCE AND MAINTENANCE  OF THE CONTINUOUS MONITORING SYSTEM
2.1  PERFORMANCE CHARACTERISTICS  OF THE CONTINUOUS MONITOR
     The interim report under  this contract task order evaluated the con-
     tinuous sulfur dioxide  monitoring system in different terms than those
     proposed in the  aforementioned September 11, 1974 issue of the Federal
     Register.   Since these  new specifications for the performance of con-
     tinuous monitoring systems seem to be more stringent than the former
     guidelines, it is of interest to compare and re-evaluate the system
     in regards to the proposed guidelines.

     The data contained in the interim report was used to determine the
     actual  performance of the sulfur dioxide monitor in terms of the pro-
     posed EPA specifications.  Since a portion of the specifications is
     expressed as a percentage of the relevant emission standard, it was
     first necessary to formulate a conversion factor relating output of
     the continuous monitor, in parts per million (ppm), to emission rate,
     expressed as pounds of  sulfur dioxide per ton of sulfuric acid produced
     (Ib/ton ^SO^).  The pertinent parameters necessary for the conversion
     and the conversion factor for each test period are listed in Table 1.
     Averaging of all the testing period factors resulted in a conversion
     factor of 0.01482 Ib/ton  H^SO./ppm - ppm as read from the sulfur dioxide
     analyzer.   This factor  was used in converting the monitoring data units
     to units of the applicable standard.

     Table 2 summarizes the  actual performance of the sulfur dioxide analyzer.
     The table also lists the  proposed Federal EPA performance specifications,
     and the pertinent parameters used in obtaining the performance figures.
     The methods used in determining the performance specifications, including

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                              Table 1.   Determination  of Factor to Convert Monitoring Units
                                         Into  Units of  the Applicable  Emission  Standard.
en
i
Date
9/11/73
9/12/73
9/13/73
ppm = parts
Average '
Manual Measured S02
Test Emissions
No. (ppm)
1
2
3
4
5
6
7
8
9
per million
317.0
342.5
303.0
358.5
338.5
310.0
392.5
402.5
362.5

Average
Flow Rate
(SCFM)
91252
86226
87933
81049
91445
88121
88442
88450
88469

Average S02
Emission Rate
(Ib/hr)
284
290
262
285
304
268
341
349
315

H2S04
Production
Rate
(tons/day)
1505
1505
1505
1507
1507
1507
1509
1509
1509

S02
Emission
Rate
(Ibs/ton H.S04)
4.53
4.62
4.17
4.54
4.84
4.27
5.42
5.56
5.01

Average
Continuous
Monitor
Reading
(ppm)
307
300
250
325
320
290
390
395
340

Adjusted0
S0? Emission
Rate
(Ib/ton H2S04
per ppm)
0.01475
0.01541
0.01668
0.01398
0.01512
0.01473
0.01390
0.01407
0.01473
,,_, 'b/ton HoSO,
        SCFM = standard cubic feet per minute
        a EPA Reference Method No.  8
          Average of two simultaneous tests
        c ppm as read from the continuous sulfur dioxide monitor
ppm

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                          Table 2.    Performance  of the  Sulfur Dioxide  Continuous  Monitor.
en
Mean
Difference

1.

2.


3.
4.
5.
6.
7.
Parameter
Accuracy Train "A"
Accuracy Train "B"
Calibration Error (45
(245
(446
Zero Drift (2 hours)
Zero Drift (24 hours)
Calibration Drift (2
Calibration Drift (24
Response Time
(ppm)


ppm)
ppm)
ppm)


hrs)
hrs)

-19.
-28.
- 3.
-22.
2.
- 0.
- 4.
- 0.
- 6.
NA
2
3
2
5
5
4
0
9
0

95%
Confidence
Interval
(ppm)
23.
22.
6.
7.
8.
5.
—
16.
—
NA
7
7
0
7
4
0

4


12.
14.
20.
12.
2.
2.

6.

1.7
Actual
Performance
5%
5%
4%
3%
4%
0%

4%

of RMV
of RMV
(of each cali-
bration gas
(mixture value
of ES
—
of ES
--
minutes (max)
Proposed
Federal EPA
Performance
Specifications
<20% of
<20% of
fof
RMV
RMV
each cali-
< 5%-
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     the major portions  of the applicable Federal Register, are contained
     in Appendix A.

     As shown, the sulfur  dioxide monitor performed within the EPA guidelines
     for the majority  of categories.  Of major importance, the relative
     accuracy of the instrument was well within the performance specifications.
     The mid-range and low-range calibration error and 2-hour calibration
     drift did not meet  the EPA guidelines.  Sufficient data was not avail-
     able from the interim report to evaluate 24-hour zero and calibration
     drift of the instrument.  The available data do indicate the analyzer
     system may have some  inherent problems associated with it.

     Although the accuracy of the monitor is more than adequate, the high
     values for calibration error at the low and mid-ranges indicate a
     possible scale problem.  Thus, if plant S02 output dropped to these
     lower concentration levels, the accuracy of the instrument might de-
     crease.  Further, the 24-hour zero and calibration drift could not
     be quantified from  the available data, but should be determined in
     order to properly schedule routine calibration requirements of the instrument.

2.2  LONG-TERM PERFORMANCE AND MAINTENANCE OF THE CONTINUOUS MONITORING SYSTEM
     The DuPont 460 continuous S02 monitoring system has proven to be an
     adequate system,as  was borne out by the one-week operational testing
     and the 6-month monitoring period.  Results of the one week operational
     testing period are  presented in the First Interim Report under this
     contract, and also  in this report, but in different terms.  The results
     are favorable and show the DuPont system performs within most of the
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guidelines prescribed by the  EPA.  The  system performed exceptionally
during the 6-month monitoring period.   The DuPont analyzer proved to
be an accurate,  reliable instrument, with low maintenance requirements
during this time.

Normal maintenance performed  for the monitoring system consisted of:
     1)  Daily calibration  by manual injection of standard gases.
     2)  Cleaning  of probe  filter.
     3)  Routine replacement  of spent system components.
                   f-
Daily calibrations normally involved injection of a zero gas into the
analyzer system followed by a calibration gas of 250 ppm.  These daily
operations were sufficient  to minimize  the effects of drift of the in-
strument, which usually occurred 16 to  18 hours after calibration.
Thus, less than daily calibration of the DuPont system may be insuf-
ficient to maintain proper  instrument performance.

The monitoring system probe is equipped with a screen filter to remove
large particulate  matter before it enters the sample line.  During
the 6-month study  period, this filter plugged about once a week, causing
a reduction in flow rate to the analyzer.  This would in turn necessitate
switching to a second probe,  while the  filter was being cleaned, in
order to avoid a lengthy interruption of monitoring.  This second probe
was not equipped with a particulate filter, but the instrument operated
normally while sampling with  the secondary line.  This indicates the
filter may be unnecessary for short periods of time; however, over
longer periods, entrainment of sulfuric acid mist in the sampling line,
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due to the absence  of a  probe filter, may cause major problems in ana-
lyzer operation.  The probe  filter idea should probably be retained,
but a more practical  filter  should be employed to remove particulate
and ^564 mist from the  sample gases.

Overall, the DuPont 460  continuous S02 monitoring system displayed ade-
quate performance characteristics, has a high degree of accuracy and
reliability, required a  minimum amount of maintenance, and is easily
operated.  The principal  improvement that could be made in the present
monitoring system,  besides those mentioned above, would be in providing
an automatic calibration system wherein no manual operations need be
performed, except for the turning of a switch.  A system of this nature
can easily be devised with the use of a valve-timing system.  The imple-
mentation of an automatic calibration system would free operator personnel
for other duties, and be more practical for performing calibrations on
a daily, routine basis.
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3.0  PROCESS OPERATION
     Plant shutdowns  and  process upsets occur frequently at sulfuric  acid
     plants and  are normally due to equipment failure, breakdown or normal
     maintenance of the plant.  MCC's sulfuric acid plant No.  2 recorded
     frequent plant down  times during the 6-month continuous monitoring
     period.  SOp emissions exceeding 1000 ppm were recorded a total  of
     eight times during the study period.  Six of these occurrences were
     during periods of plant start-up, the other two being associated with
     plant upsets.  Since the range of the DuPont analyzer and of the strip
     chart recorder were  both set at 1000 ppm, no visual output greater than
     this concentration could be obtained.  However, electrical output of
     the analyzer was recorded on the Westinghouse magnetic tape.   This data
     indicated the highest 15-minute average S02 concentration during the
     study period to  be approximately 1500 ppm.  The reliability of the DuPont
     instrument  is unknown for "off-scale" readings, therefore, it is ques-
     tionable whether or  not the readings over 1000 ppm are accurate. The
     S02 analyzer displayed no noticeable effects of going off-scale.
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4.0  OPERATIONAL  COSTS
     Table 3  lists  the  level of effort and costs associated with  the  complete
     continuous monitoring project.  This table assumes that a consultant
     obtains,  installs,  and operates the monitoring system under a turn-key
     contract.  The  specifics of each category are listed under the "comments"
     section.  Note  that under the given contractor situation, the source
     plant personnel  retain an active role in operating and maintaining  the
     monitoring system.

     Cost estimates  based on the source plant obtaining, installing, and
     operating the continuous monitoring system were not available at  the
     time of this report.  The estimates will hopefully be forthcoming
     shortly after this  report is submitted.  However, the man-hours asso-
     ciated with  the monitoring task would probably not be significantly
     different than  those listed in the attached table, excluding  travel
     time.  Dollar amounts might be quite different.
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                                                                             TABLE 3.
ro
 i
        Source  H?SO/t Plant,  Miss.  Chem.  Corp.
        lnstrument(5) DuPont 406 SO,  Analyzer                  Attachment  #1~COHTINUOUS MONITORING

             Cost and Level of Effort Based Upon Procurement,  Installation,  and Operation by a Service Organization (e.g., an Engineering Consultant Firm)
1. Site Selection and
     Preparation^

2. Instrument Selection
     and Purchase
   a. Monitoring Instrument
   b. Data Recorder6

3. System Design
   a. Monitor—Recorder
        Interface
   b. Calibration Systeitr
   c. Enclosures (Shelters)
   d. Other

4. Installation, Setup,
     and Calibration

5. Check-out and Certification
    (Manual  Testing  & Report)
6. Maintenance (one year)

7. Data Handling, Reduction
     and Report Preparation
     (one year)

8. Direct Administrative Cost
                                           Level  of Effort

                                        Man-Hours  Total  Cost
                                           24
                                           NA
                                           24
65Q.
 NA
550
10
NA
NA
250
290
320
' 200
75
270
NA
NA
3750
3000
3100
3000
1150
                                                             Rental
                                                             Cost or
                                                           Service Charqe
                                                            (per year)
                                                                       NA
                                                                       $5300
                                                                (Semi-Automatic)
                                                                       $1750
   Travel
 Number of
Round Trips

     1
    NA
                                                                                           NA
                                     NA
Other                       Comments

	     (Gainesville, Fla. to Pasragonla,
          (Performed by Source Personnel	
          (Instrument  installed prior  to EPA
          (evaluations	
          (Westinghouse Adviser Tape Recorder	
            §onitor & Probe Supplied by DuPont
            ecorder supplied  by Westinghouse
            ample Line supplied by Samuel Norse  Co.
                                                          (Someone in.iects calibration gases daily
                                                          (Included in original purchase	
                                                                                                                                  NA
                                                          (Gainesville, Fla. to Pascagoula. Miss.

                                                          /      ii       M    ii      n        ii


                                                          (Personnel at plant maintain Instrument
                          ( Westinghouse evaluates tapes on computer
                                                                                                                                  NA
        Assuming tue consultant obtains, installs and operates  the  monitoring  system, under a turn-key contract.

         Include all fees  and overhead; assume one year on-line operation.
        clndicate origin and destination under "Comment"; e.g.,  plant  to vendor.
         Additional costs not included in items 1  through 7.

        eSpecify type.

         Specify whether manual or automatic.
        ^Assu:ne scaffolding and other facilities for manual  testing  already  exist.

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                   APPENDIX A
   PROCEDURES FOR DETERMINING ACTUAL PERFORMANCE
            OF THE MONITORING SYSTEM
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              Procedure for Determining Mean Values
                  and  95% Confidence Intervals
MEAN VALUE
               X  =  i=l
           Where  X  = Mean Value
               X.j  = Individual Values
                 n  = Number of Data Points
                 z  = Sum of the Individual Values
95% CONFIDENCE  INTERVAL
               CI95 =          ,/n (= *i2) - (l X.)2
           Where  CIg5 = 95% Confidence Level
                   X.,- = Individual Values
                    T} = Number of Data Points
                    z = Sum of the Individual Values
                t Q7t. = t, a    for n samples from a table of
                 • •/ / o     i ~"y  t
                       percentages of the "t" distribution
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 32861
                               PROPOSED  RULE*
. Date of Test _.
Span Filter
Analyzer Span Setting
1
Upscale 2
3
_ 1 Opacity
2 Opacity
seconds
seconds
seconds .
      Downs cale
1
2
3
seconds
seconds
seconds
                     Average response
                                   seconds
                           Figure 1-2.   Response Tire Test
 Zero Setting.
 Sp*n Setting,
,(See paragraph 6.2.1)
 Cite    Zero Reading
 end    (Before cleaning
 line   end adjustment)
                       Span Reading                Calibration
 Zero Drift   (After cleaning and zero adjustment         Drift
   (iZero)       but before span Adjustment)           (iSpan)
 Zero Drift • [Mean Zero Drift*	+ Cl (Zero)	
             « Emission Standard] x TOO »	.

 Calibration Drift - [Kean Span Drift*	+ CI (Span).
                   » Enlsslon Standard] x TOO ».
  Absolute value
                        Figure 1-3.  Zero and Calibration Crlft Test
PERFORMANCE SPECIFICATION  S—PERFORMANCE
  SPECIFICATIONS AND SPrciPICATION TTST PRO-
  CEDURES FOB MONITORS Or SO, AND NO, FROM
  STATIONARY SOURCES

  1. Principle and Applicability.
  1.1 Principle. Oases are continuously sam-
pled In the stock emissions und analyzed for
either sulfur dioxide or oxides of  nitrogen
by a continuously operating  emission meas-
urement system. Sampling may Include either
the extractive or non-extractive (In aitu) ap-
proach.
  1.2 Applicability. This method  Is  appli-
cable to the Instrument systems specified by
                    subparts for continuously monitoring oxides
                    of  nitrogen and  sulfur  dioxide  emissions.
                    Specifications for continuous measurement of
                    nitrogen oxides or sulfur dioxide nro given
                    In  terms of performance specifications. Test
                    procedures are given to determine the capa-
                    bility of the measurement systems to conform
                    to  the performance speculations prior to
                    approving the systems Installed by an atlccted
                    faculty.
                     2. Apparatus.
                     2.1 Calibration Oas Mixture. Mixture of a
                    known concentration of pollutant gas in
                   oxygen-free nitrogen. Nominal concentrations
 of SO percent  and 00  percent  of  *paa are
 recommended. The 00 percent pas mixture Is
 to be used to set and to check the  span and
 Is referred to as the span gas. The gas mix-
 tures shall be analysed  by the Applicable
 reference method  (See 5.1.1) within 2 weex.s
 prior to use. or demonstrated to bo accurate
 and  stable by an alternate method subject
 to approval of the Administrator.
   2.2 Zero Oas. A gas containing less than 1
 ppm of the pollutant gas.
   2.3 Equipment  for rr.exsurerr.ent  of  the
 pollutant gas concentration using the ref-
 erence method  specified  In the applicable
 standard.
   2.4 Chart necorder. Analog chart recorder,
 Input voltage range compatible with analyzer
 system output.
   2.5 Continuous  measurement  system lor
 SO, or XOi pollutants as applicable.    -
   3.  Definition*.
   3.1 Measurement System, The total equip-
 ment required  for the determination of  a
 pollutant gas concentration In a given source
 effluent. The system  consists ol three  major
 subsystems:
 •  3.1.1  Sampling Interface — That portion of
 the measurement system  that performs one
 or more of  the following operations: delinea-
 tion, acquisition,  transportation, and con-
 ditioning of a sample of the source eQuent
 or protection of the analyzer from the hostile
 Aspects of the sample or source environment.
   3.1.2 Analyzer — That portion of the  meas-
 urement system which  senses the pollutant
 gas and generates a  signal output  that Is a
 Junction ol the pollutant concentration.
   3.13 Data  Recorder— That portion of the
 measurement system that provides  a per-
 manent record of the output signal In terms
 of concentration units.
   32 Span. The value of pollutant concen-
 tration at which the measurement system Is
 set to  produce the maximum data display
 output. For  the  purposes of this method,
 the span shall be set at a sulfur dioxide or
 nitrogen  dioxide concentration equivalent to
 1.5 times the relevant emission standard.
   3.3 Accuracy (Relative). The degree of cor-
 rectness with which the measurement system
 yields the  value of gas  concentration of  a
 sample relative to the value  given  by a de-
 fined reference method. This  accuracy  Is ex-
 pressed In  terms of error, which Is the dif-
 ference  between  the paired  concentration
 measurements expressed as a percentage  of
 the mean reference value.
   3.4 Calibration Error.  The  difference, be-
 tween the pollutant concentration Indicated
 by the  measurement system and the known
 concentration of  the test  gas mixture.
   3.5 Zero Drift. The change In measurement
 system output over a stated period of time of
 normal continuous operation when the pol-
 lutant  concentration at the  time for the
 measurements Is zero.
   3.6 Calibration Drift. The chanse In meas-
 urement system output  over a stated period
 time  of  normal continuous operation  when
 the pollutant concentration at the time of
 the measurements Is the^ame known upscale
 value.
   3.7. Response Tl.T.e. The time Interval from
 a  step change In pollutant concentration at
 the Input to the measurement system to the
.time  at which 95 percent of the  correspond-
 ing Qr.al value Is reached as displayed on the
 measurement system data  presentation de-
 vice.
   3.8 Operational Period. A minimum period
 of time  over  which a measurement system
 |j expected to operate within  certain per-
 formance specifications without unscheduled
 maintenance, repair or adjustment.
   4. Measurement    System   Performance
  A measurement system must meet the per-
formance specifications In Tablo 2-1 to be
considered acceptable  under this method.
                               HDERAl REGISTER. VOL 39, NO.  177—WEDNESDAY. SEPTEMBER  11,  1974

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                                                       PROPOSED  RULES
                                                                                32805
                        TABU 2-1.—PinronMANci SPZCOICATIOHS

  '   .            Parameter                                gpedflcatlon
 1. Accuracy*  	..."	.	......—  :£20% of reference mean Talue.
 3. Calibration error*	—  «£«%  of each  (60%.  80%)  calibration gaa
                        •                      mixture, value.
 3. Zero drift (2 hours) •	  ^£2% of emission standard,
 4. Zero drift  (21-hour)*	——  —* 7c of emission standard.
 6. Calibration drift (2  hours)*	._—  £"2% of emission standard.
 6. Calibration drift (24-hour)*	  ??67c of emission standard.
 7. Response time		  16 minutes maximum.
 B. Operational period...		  168 Lours minimum,
   •Expressed as  turn of absolute mean value plus 95 percent confidence Interval of a series
 of tests.
                                               6.12 The  6} percent confidence Interval
                                             (two tided)  is calculated according to equa-
                                             tion 3-2.
   6. Performance  Specification  Te.it  Pro-
 cedures. Trie following test procedures Bhnll
 be used to determine coiilormance  with the
 requirements of paragraph 4:
   6.1 Calibration test.
   5.1.1 Analyze each calibration pas mixture
 (50';t, SO1;})  using reference methods  C  for
 sulfur dioxide and 7 for oxides of  nitrogen.
 and record the results on the example  sheet
 shown in Figure 2-1. This step may be omit-
 ted for non-extractive monitors where dy-
 namic calibration gas mixtures are  not xiscd
 (See 5.1.2).
   6.1.2 Set tip and  calibrate the  complete
 measurement system according to the  man-
 ufacturer's written Instructions. This may
 be accomplished either In the  laboratory  or
' In the field. Make a scries of five non-contec-
 utlve readings with span gas  mixtures alter-
 nately at each concentration (e.g., 50','. W.i,
 6071. 90%,  50',c,  etc.).  For  non-extractive
 measurement systems, this test may be per-
 formed using procedures and  two  or  more
 calibration gas  concentrations differing   by
 a factor of two or more, certified by the  man-
 ufacturer. Convert the measurement system
 output readings to ppm  and record the  re-
 cults on the example  sheet shown In Figure
 2-2.
   62 Field Test for Accuracy (Relative). Zero
 Drift. Calibration, and Drift—Install and op-
 erate the measurement system in accordance
 with the manufacturer's written instructions
 and drawings as  fo)lo\vs:
   6.2.1 Conditioning Period—Offset  the zero
 setting at least 10 percent of  span so tbat
 negative zero drift can be quantified. Operate
 the system for au Initial 163-hour condition-
 Ing period In a normal operational manner.
   622  Operational  Test Period—Operate
 the. system  for  an  additional   168-hour
 period! The system shall  monitor the source
 effluent at  all  times except  when  being
 eeroed, calibrated, or backpurged. For meas-
 urement    systems  employing  extractive
 campling. It Is recommended  that the meas-
 urement  system  and the-   probe  tips   be
 placed adjacent to each  other  in  the  duct.
 Record the reference methods test data and
 measurement system  concentrations on the
 example dato sheet shown In Figure 2-3 for
 the  tests given  as follows:
 •  55.2.1   NO, Monitoring  Systems.  Make
 twenty seven NO, concentration  measure-
 ments  using   the  applicable  reference
 method. No more than three measurements
 shall be  performed In  any  one hour, and
 any set  of  three measurements  shall   be
 performed  concurrently  or   within  a   3-
 mlnute Interval and the results averaged.
   62.2.2  SO.  Monitoring Systems.  Make
 nine SO. concentration measurements using
 the  applicable reference  method. No  more
 than one measurement shall be performed
 In nny one hour.
   6.2.3 Field Test for  Zero  Drift and  Cali-
 bration Drill. Determine  the  values given  by
 rero nnd span  (."as pollutant concentrations
 at 2-hour Intervals until  15 sets of data are
 obtained. Alternatively,  for  non-extrnctlve
. measurement systems, determine the values
 given by an electrically or mechanically pro-
 duced zero condition and by  Inserting  a
 certified    calibration   gas   concentration
 equivalent to not less than 300 ppm Into the
 measurement system. Record these readings
 on  the example Eheet shown in Figure 2—4.
 These 2-hour periods need not  be consecu-
 tive but may cot overlap. The zero and span
 determinations to be made under  this para-
 graph may be  made  concurrent  with  the
 tests  under 5.2.2.  Zero and calibration cor-
 rections  and adjustments  are  allowed only
 at 24-hour  Intervals or at such shorter In-
 tervals as the  manufacturer's  written  In-
 structions  specify.  Automatic  corrections
 made by  the measurement system without
 operator  intervention  or Initiation are al-
 lowable at any time. During the entire 168-
 hour  operational  test period,  record  the
 values given by zero and span gas pollutant
 concentrations  before and  after adjustment
 at 24-hour  intervals In  the  example  sheet
 shown in Figure 2-5.
   6.3  Field  Test for Response Time.
   5.31 This test shall be accomplished using
 the entire measurement system  as Installed,
 including sample  transport  lines U  used,
 Flow  rates, line diameters, pumping  rates,
 pressures  (do not allow the pressurized cali-
 bration gas to change  the normal  operating
 pressure  in the sample line), etc., shall bo
 at the nominal  values for normal  operation
 as specified in  the  manufacturer's written
 instructions. If  the analyzer  is  used to
 sample  more  than one pollutant  source
 (stack), this test shall be repeated for each
 sampling  point.
   5.3.2  Introduce zero gas into the measure-
 ment system sampling Interface or as close
 to the sampling interface as possible. When
 the system output  reading has stabilized.
. switch quickly  to a kno-.vn concentration of
 pollutant  gas at 70 to 90  percent of span.
 Record the time from concentration switch-
 ing to final stable response.  After the sys-
 tem response  has stabilized at the  upper
 level,  switch quickly to a zero concentration
 of pollutant cos. Record the time from con-
 centration switching to final stable response.
 Alternatively, for  nonextractive  monitors,
 the highest available  calibration  pas con-
 centration shall be  switched  into and out
 of  the  sample  path  and  response   times
 recorded.  Perform this test sequence  three
 (3) times. For  each test record the results
 on the example sheet shown in Figure 2-6.
   6.   Calculation}, Data Analysis and Report-
 ing.
   6.1  Procedure for determination of  mean
 values and  confidence intervals.
   C.I.I The mean value of a data  set Is cal-
 culated according  to equation 2-1.
               '   .  " <•>»    Equation 2-1
 where:
   x, = Individual values.
    l' = sum of the individual values,
    x = mean valvie. and
    n = number of data points.
                                                         f»Vn— 1
                                                                          Equation 2-2
                                             where:
                                               IX. = Bum of all data polnta,
                                                   ='l— o/2. and
                                                  W=95 percent confidence Interval esti-
                                                       mate of the average mean value,
                                                          VAXUTB ron '.876
  2  ....... r.. ......... - ............. 12.706
  3  ................. - ...............  4.303
  4  -. ...... . ........................  3.182
  6  .................... - ............  2.776
  6  _________________________________  2.571
  7  ............ - ................... .  2.447
  8  .......... ______ .................  2.365
  9  .................................  2.30S
 10  - ............ - .......... _ ........  2262
 11  .................. _____ ..........  2.228
 12  _____ . ............ - ....... - ......  2.201
 13  ........... ------------ ..........  2.179
 14  _____________________ ............  2.160
 15  ........ . ........... - ............  2.145
 16  ........................ --- ......  2.131
 The  values In this table are already cor-
 rected for n-1 degrees of freedom. Use n equal
 to the number of samples as data points.
  62 Data Analysis and Reporting.
  62.1 Accuracy  (Relative) For each of the
 nine reference method testing periods, de-
 termine the average pollutant concentration
 reported by  the continuous  measurement
 system. These average concentrations shall be
 determined  from the measurement system
 data recorded under 522 by integrating the
 pollutant concentrations over each of the
 time Intervals  concurrent with  each  refer-
 ence method test, then  dividing -by the
 cumulative time of each applicable reference
 method testing period. Before proceeding to
 the next step, determine the bases (wet or
 dry)  of the measurement system  data and
 reference  method test data concentrations.
 If the bases are not consistent, then a mois-
 ture correction shall be applied to either the
 reference  method  concentrations or  the
 measurement  system  concentrations  as Is
 appropriate. The correction  factor shall  be
 determined  by  moisture  tests  concurrent
 with the reference method testing periods.
The moisture test  method  and the correc-
 tion  procedure employed shall be reported.
 For each of the nine test runs, subtract the
 respective reference method  test concentra-
 tions (use average of each set of  3 measure-
ments for NO,) from the continuous moni-
 toring system average concentrations.  Using
 these data, compute the mean difference and
 the 95 percent  confidence  Interval  using
 equations 2-1 and 2-2. Accuracy is reported
 as the sum of the absolute value of the mean
 difference and the 95 percent confidence in-
 terval expressed as a percentage of the mean
 reference  method  value.  Use  the example
 sheet shown in Figure 2-3.
  62.2 Calibration  Error — Using  the  data
 from paragraph 5.1. subtract the measured
 pollutant  concentration determined under
 paragraph 6.1.1 (Flfure 3-1)  from the value
shown by the measurement system for each
of the 5 readings at each concentration meas-
ured under 6.1.2 (Figure 2-2). Calculate the
mean of  these difference values and the 95
percent confidence  Intervals according  to
equations 2-1 and 2-2. The calibrntion error
Is reported as the sum of the absolute value
of the mean difference nnd  the  PS percent
confidence interval  as a percentage of  each
respective calibration pas concentration. Use
example sheet shown In Figure 2-2.
  62.3 Zero Drift (2-hour) — Using the zero
concentration values measured  each 2 hours
                                FEDERAl REGISTER, VOL. 39. NO. 177—WEDNESDAY, SEPTEMBER  11. 1974

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328GG
           PROPOSED RULES
during th» Geld if at. calculate the dlfTerenccs
between coniemttvc 2-hovir rcucllngs express-
ed In  ppm. Calculate the niton dlMercnce
And  the confidence Interval using equation*
9-1  and  3-2.  Report  the yero drift M tli»
Bum of the absolute mean value  and the
confidence Interval as a percentage of the
emission standard. Use example sheet shown
In Klguro 2-4.
  6.2.4 Zero Drift (24-hour)—Using the zero
concentration   values  measured every  24
hours during the field tost,  calculate the dif-
ferences  between the rx?ro point after zero
adjustment and the zero \alue 24 hours later
Just prior to zero adjustment. Calculate tho
mean value of thcso  points and Hie confi-
dence Interval using equations 2-1  and 2-2.
Report the zero drill  (tho  sum of the abso-
lute mean and confluence Interval) as a per-
centage of the emission standard. Use exam-
ple sheet shown In Figure 2-S.
  6J2.5  Calibration Drift  (2-hour)—Using
the calibration values obtained at 2-hour In-
tervals during the  field  test,  calculate the
differences between consecutive 2-hour read-
Ings expressed as ppm- These  values should
be corrected for the corresponding zero drift
during that 2-hour  period.  Calculate the
mean and confidence  interval of these cor-
rected difference values us In;  equations 2-1
and  2-2.  Do not use the differences between,
non-consecutive readings.  Report the cali-
bration drift as the sum of the absolute mean
end  confidence  interval as a  percentage of
the emission standard. Use the example sheet
shown In Figure 2-4.
  6.2.6 Calibration Drift   (24-hour)—Using
the  calibration values measured every 24
hours  during  the  field test,  calculate the
differences between the calibration concen-
tration reading after zero and calibration ad-
justment and  the  calibration  concentration
reading 24 hours later after zero adjustment
but  before calibration adjustment. Calculate
the mean value of these differences and the
confidence Interval  using equations 2—1 and
2-3.  Report the sum  of the absolute mean
and  confidence  Interval as a  percentage of
the emission standard. Use the example sheet
shown In Figure 2-5.
  6.2.7  Response  Time—Using  the charts
from paragraph 5.3, calculate the time Inter-
val from concentration switching to 95 per-
cent to the final stable value for all upscale
and downscale tests. Report the mean of the
three upscale test  times and the mean of
the  three downscale test times. The two av-
erage times should not differ  by more than
15 percent of .the  slower  time. Report the
Blower tune as the system response  time.
Use the exafnple ihret shown In Figure 3-8.
  8.3.8 Operational Test Period—During the
168-hour performance and operational  test
period,  the  measurement nystem shall not
require any corrective maintenance or repair
or replacement or  adjustment  other  than
that clearly  specified  as required In the op-
eration and maintenance manuals aa routine
and expected during a 1-week period. If the
measurement  nystcm  operates  within  the
specified performance parameters and docs
not require  corrective maintenance, repair.
replacement or adjustment other  than as
specified above durl.i" the ICO-hour test pe-
riod, the operational period will be  success-
fully concluded. Failure of the measurement
to meet this  requirement  thall call  for  a
repetition of tho  ICB-hour test period. Por-
tions  of tho test which were satisfactorily
completed need not  be repeated. Failure to
meet  any performance specifications  shall
call for a repetition of the  1-wcek  perform-
ance  test period  and that  portion  of the
testing  which U related to the failed  speci-
fication.  All  maintenance  and adjustments
required shall be recorded. Output readings
ehnll be recorded before and After all adjust-
ments.
  7. Re/erentei.
  7.1 Monitoring Instrumentation for the
Measurement of St/J/ur Die-ride in Station-
ary Source Emissions, Environmental Protec-
tion A;cncy. Research Triangle Pork, N.C.,
February  1073.
  7.2. Instrumentation  /or the Determina-
tion of Xitro*jen Oiidei Content o/ Station-
ary Source Emissions. Environmental Protec-
tion Agency. Research Triangle Park. N.C,
Volume 1. APTD-0047. October 1971; Volume
2, APTD-0042. January  1972.
  7.3 Experimental Statistics. Department of
Corrunerce. Handbook 91. 19C3, p. 3-31. par-
agraphs 3-3.1.4.
  7.4 Performance Specifications for Station-
ary-Source Monitoring  Systems  for Case*
and Visible Emissions. Environment*! Protec-
tion Agency, Research  Triangle  Park, N.C.
EPA-650/2-74-013. January 1974.
                                                  Reference Kethod Used
  Date
K1d-Ranae'Cal1brat1on Gas "Mixture1
Sample 1
Sample 2
Sample 3
Average
ppn
ppm
ppn
ppm
                 man-Ranee  (span) CaHEratlftfi GaS Hfxture

                 Sample 1             PPB  •     '  -••  '
                 Sample 2             ppa
                 Sample 3	j>pn
                 Average„	ppn
             Figure 2-1.  Analysis of Calibration Gas Mixtures
                               FEDElAl REGISTES, VOL 39, NO, 177—WEDNESDAY.  SEPTlMBEg II, 1774

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