United States
           Environmental Protection
           Agency
          Environmental Monitoring
          Systems Laboratory
          Research Triangle Park NC 27711
EPA-600/4-85-004
January 1985
           Research and Development
vvEPA
A Summary of the
1983 EPA National
Performance Audit
Program on Source
Measurements

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                                                  EPA-600/4-85-004
                                                  January  1985
A SUMMARY OF THE 1983 EPA NATIONAL PERFORMANCE AUDIT PROGRAM
                   ON SOURCE MEASUREMENTS
                             by
          E.W. Streib, T.J. Logan and M.R. Midgett
                 Quality Assurance Division
        Environmental Monitoring Systems Laboratory
            U.S. Environmental Protection Agency
       Research Triangle Park, North Carolina  27711
        ENVIRONMENTAL MONITORING SYSTEMS  LABORATORY
             OFFICE OF RESEARCH AND DEVELOPMENT
            U.S.  ENVIRONMENTAL PROTECTION AGENCY
       RESEARCH  TRIANGLE PARK, NORTH CAROLINA  27711

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                      NOTICE

This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication.  Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
                       11

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                                  FOREWORD
     Measurement and monitoring research efforts are designed to anticipate
potential environmental problems, to support regulatory actions by develop-
ing an in-depth understanding of  the nature and processes that impact health
and the environment, to  provide  innovative means of monitoring compliance
with regulations, and to evaluate the  effectiveness  of health and environ-
mental protection regulations  through  the monitoring  of  long-term trends.
The Environmental Monitoring Systems  Laboratory,  Research  Triangle  Park,
North Carolina, has responsibility for:   assessment  of environmental moni-
toring technology and systems;  implementation of agency-wide quality assur-
ance programs for air pollution measurement systems; and supplying technical
support to  other  groups in  the  Environmental  Protection  Agency, including
the Office  of  Air  and  Radiation,  and  the  Office of  Toxic  Substances.

     The major task of this study was to report the results of the national
quality assurance audit program for stationary source test methods.  Audits
were designed to estimate the minimal analytical and computational accuracy
that can be expected with EPA Method 5 (dry gas meter only), Method 6 (sul-
fur dioxide), Method  7 (nitrogen oxides),  Method 19  (coal),  and  Method  3
(carbon dioxide and oxygen).  Statistical analysis was used to characterize
the data.
                          Thomas R. Hauser, Ph.D.
                                  Director
                Environmental Monitoring Systems Laboratory
                   Research Triangle Park, North Carolina
                                    iii

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                                  ABSTRACT
     In the  spring  and fall  of  1983,  the Quality Assurance Division  con-
ducted the National Audits  for  Stationary Source Test Methods.   The audit
materials consisted of:  a  calibrated  orifice for Method 5  (dry  gas meter
only), five  simulated  liquid  samples  each for Method 6  (SC>2)  and Method 7
(NOX), two coal samples  for Method 19A, and  a disposable gas  cylinder for
Method 3  (Orsat analyzer).   Participating laboratories  sent their data to
the Source Branch and  in return received a written  report  comparing their
results to EPA's.

     In the  Method  5  spring audit,  the mean value for all  participants
differed by  5.7% from  the  true  (EPA) value.  For  the  fall  audit, the par-
ticipants' mean was 4.1% from the  true  value.  In the  two Method 6 audits,
the average  mean differed  by 3% from the true value.  The  average mean in
the two Method 7 audits was 15% of the true value.

     In the  two coal audits, the parameters measured were sulfur, moisture,
ash, and  Btu.  On the  average for  the  sulfur analysis,  85%  of the partici-
pants measured within 10% of the expected value; for Btu, 100% of the parti-
cipants measured within 10% of the expected value.

     In each of the  two Method  3  audits, each parameter had only one  con-
centration.  The means  for  C02  were  within  10%  (spring) and  6%  (fall) of
the expected value.   For both  audits,  the mean  for 02 was less than 1%.

     This report  covers the  period  from January  1983  to December 1983.
                                     iv

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                                  CONTENTS




                                                                      Page




Foreword	   iii




Abstract	    iv




Figures	    vi




Tables	   vii




Acknowledgments	viii




     1.   Introduction 	     1




     2.   Summary	     2




     3.   Method 5 Dry Gas Meter Audit	     6




     4.   Method 6 Audit	    12




     5.   Method 7 Audit	    14




     6.   Method 19A Coal Audit	    16




     7.   Method 3 Audit	    20




References	    22




Appendices




     A.   Frequency Distributions  	    23




     B.   Instructions for EPA Audit Materials 	    31

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                                  FIGURES
Number                                                                Page
  1       Cumulative accuracy for participants in the
          Method 5 audits, 0383 and 0983	    8

  2       Previous results of Method 5 audit 	 .....    9

  3       Results of the Method 5 audit 0383	   10

  4       Results of the Method 5 audit 0983	   11
                                     vi

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                                   TABLES
Number

   1      Participants' Results for Method 5 Audit
          (All Data - No Outliers Removed)	    2

   2      Participants' Results for Method 6 Audit
          (All Data - No Outliers Removed)	    3

   3      Participants' Results for Method 7 Audit
          (All Data - No Outliers Removed)	    3

   4      Participants' Results for Method 19A Coal Audit
          (All Data - No Outliers Removed)	    4

   5      Participants' Results for Method 3 Audit
          (All Data - No Outliers Removed)	    5

   6      Method 5 Audit Participants  	    6

   7      Method 6 Audit Participants  	   12

   8      Summary of Source SC>2 Audits	   13

   9      Method 7 Audit Participants  	  .   14

  10      Summary of Source NOX Audits	   15

  11      Coal Audit Participants	   17

  12      Source Coal Audit - 0383	   18

  13      Source Coal Audit - 0983	   19

  14      Method 3 Audit Participants  	   20

  15      Source Method 3 Audit - 0583	   21

  16      Source Method 3 Audit - 1183	   21
                                    vii

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                              ACKNOWLEDGMENTS
     We express our  appreciation to the laboratories  that  participated in
our audits.  Thanks also to the Standards Laboratory (EPA/EMSL/ Performance
Evaluation Branch) who  did  our  Acceptance Testing  on the audit  samples.
For providing the data systems to store and evaluate the data, we thank the
programmers of the Data Management and Analysis Division/EMSL.
                                    viii

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                                 SECTION 1

                                INTRODUCTION
     The Environmental Monitoring Systems Laboratory  (EMSL) of EPA, in 1977,
established a performance audit program to evaluate the performance of com-
panies that  conduct  compliance testing, using EPA Reference  Methods.  The
audits verify the analytical accuracy of EPA Reference Methods 3, 6, 7, and
19A and  the calibration  accuracy of  the  Method  5  control  console  (1).
Accuracy is  defined  as  the percent  difference  between  the  participant's
analytical results and  the  EPA  expected  value.   By participating  in this
(free and voluntary) program,  testing  companies  can  compare their perform-
ance to other laboratories conducting similar measurements.

     Two audits were  conducted for each of  Methods  3, 5, 6, 7  and 19A in
1983.  Every participating laboratory  received an  audit package consisting
of the audit sample,  a data card, instructions, and an envelope for return-
ing the  data to EPA.   A label  for  returning the  audit device  was also
included for the Method  5 audits.  Participants had  8 weeks to return data to
EPA.  At the end of  this period all data received were statistically ana-
lyzed to determine the precision and accuracy obtained by the participants.
Participants were given 8 weeks  to return the  data, which was then statis-
tically analyzed for precision (repeatability) and accuracy.

     The Quality Assurance Division of EMSL maintains a repository of audit
samples for  the EPA Methods  3, 6, 7 and for coal.   These (stable) samples
are available  to  any laboratory  needing  them (for  example)  to  train new
personnel or to  conduct quality  control  checks  in the  laboratory.  Since
the expected values (for these samples) are included with the analysis in-
structions, there is no requirement for the data to be returned to the EPA.
However, we  recommend that participants make use of  this sample repository
to help improve their overall analytical skills.

     This report summarizes the results obtained in the 1983 source audits.

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                                 SECTION 2

                                  SUMMARY
     In the spring  and fall  of  1983,  EPA's EMSL,  Research  Triangle Park,
North Carolina, conducted National  Quality  Assurance Audits  for Stationary
Source Test Methods 5  (dry  gas meter only), 6  (S02>,  7 (NOX),  19A (coal),
and 3 (Orsat analyzer).  Industrial laboratories, contractors, foreign lab-
oratories, as  well  as  local, state,  and  federal agencies  participated.

     Two Method 5 audits were conducted in 1983.   The  overall  results (no
outliers removed) are  summarized  in Table  1.   In the  first audit, the mean
for all participants was 5.7% from the true value  and  in  the second audit
it was 4.1%.  After  correcting for outliers, the means for the 0383 and 0983
audits were 2.6% and 2.IX,  respectively, from the true value.  The partici-
pants' performances  were not   statistically different  from previous audits
(2,3,4).
            TABLE 1.  PARTICIPANTS' RESULTS FOR METHOD 5 AUDITS
                      (ALL DATA - NO OUTLIERS REMOVED)
Type of
sample
Orifice

Audit
Parameter date
Volume 0383
0983
No. of
analyses
763
614
Mean
(% from
5.7
4.1
Median
EPA value)
2.2
1.9
Std.
dev.
32.7
21.3
     Table 2  presents  the data  (no outliers  removed)  from  the two  1983
Method 6 audits.  This  audit  procedure requires the participants to deter-
mine the sulfate content in five aqueous solutions using the titration pro-
cedure of Method 6.  For  each concentration in the 0283 audit,  the  mean of
the participants was 4% higher than the true value, in contrast, the median
differed by less than 1%.  In the 0883 audit, the means differed by 3%, and
the medians again  were less  than  1%.   In  both  audits,  50% to  68%  of the
participants achieved an accuracy within 2% for 9 out of 10 of the samples.
However, on one low  concentration  sample,  only 43% achieved this accuracy.

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            TABLE 2.   PARTICIPANTS'  RESULTS FOR METHOD 6 AUDITS
                      (ALL DATA - NO OUTLIERS REMOVED)
Type of Audit
sample date
Aqueous 0283
sulf ate



0883




No. of
analyses
113
113
113
112
113
88
90
90
90
90
EPA
true
value
343.20
762.60
1143.90
1906.50
2A78.50
396.60
594.80
633.00
1349.80
1426.10
Participant results
Mean
361.54
794.51
1188.32
1971.14
2579.04
393.57
589.35
621.39
1314.46
1384.05
Median
342.80
758.30
1140.00
1890.00
2456.00
395.50
595.15
629.35
1339.45
1416.65
Std.
dev.
109.11
233.13
349.57
580.91
778.94
50.93
67.21
89.04
168.73
192.16
     Table 3 presents the data (no outliers removed)  from the  two  Method 7
audits in 1983.  This audit procedure requires that the participants deter-
mine the nitrate content in five aqueous solutions.  For each concentration
in the 0483 audit,  the mean of the participants was 22% higher than the true
value, but in  contrast,  the  median  differed by less  than 3%.   In  the 1083
audit, the means were  12%  higher  than the  true  value, and again the median
value differed by only  3%.   In both audits, 34% to 38% of the participants
achieved an accuracy within  3%  of the true value for 8 out  of  10  samples.
However, on the  two lowest  concentration   samples  only  25%  achieved this
accuracy.
            TABLE 3.  PARTICIPANTS' RESULTS FOR METHOD 7 AUDITS
                      (ALL DATA - NO OUTLIERS REMOVED)
Type of Audit
sample date
Aqueous 0483
sulfate



1083




No. of
analyses
59
62
63
62
63
53
53
54
54
52
EPA
true
value
59.70
298.70
477.80
737.20
955.60
118.40
218.40
240.30
407.20
454.80
Participant results
Mean
71.66
348.99
581.76
892.88
1159.22
128.12
235.98
267.01
440.13
511.48
Median
58.10
302.80
480.00
750.00
975.60
121.00
221.40
245.70
407.45
469.65
Std.
dev.
68.67
280.20
579.80
720.34
1005.48
32.76
64.95
71.78
136.98
143.74

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     Table 4 summarizes  the  results of the two  coal  audits.  Participants
analyzed each coal sample in duplicate  for  percentage of sulfur, moisture,
and ash, and  for gross  calorific  value  (Btu/lb).  The  means of  the ash,
moisture, and sulfur content were  within 4% of the expected value on both
concentrations.  An  accuracy  of  IX  was  achieved   on  the  Btu  content.
         TABLE 4.  PARTICIPANTS' RESULTS FOR METHOD 19A COAL AUDIT
                   (ALL DATA - NO OUTLIERS REMOVED)
 Type
  of    Audit
sample  date
            No. of   EPA true
Parameter  analyses   value
 Participants' Results
                     Std.
Mean      Median     dev.
Coal 0383 % S
0983
0383
0983
0383 Z H20
0983
0383
0983
0383 % Ash
0983
0383
0983
0383 Btu/lb
0983
0383
0983
125
112
127
113
125
113
127
114
123
112
125
113
125
112
123
111
0.74
0.74
2.98
2.95
2.05
1.62
6.13
5.75
7.40
7.31
11.42
11.33
12719.00
12470.00
14165.00
14059.00
0.74
0.75
2.89
2.85
2.06
1.59
5.97
5.86
7.35
7.60
11.37
11.61
12643.50
12574.22
14115.97
14068.90
0.74
0.73
2.91
2.87
2.05
1.68
6.16
6.10
7.33
7.29
11.42
11.40
12684.00
12597.50
14141.00
14093.00
0.05
0.21
0.17
0.21
0.71
0.37
0.53
0.71
0.41
3.35
0.24
2.59
251.79
207.38
150.59
170.01
     The results of the Method 3 audits  are summarized in Table 5.  Partici-
pants analyzed  the  gas  sample  twice  for  percentage  of  carbon dioxide,
oxygen, and  carbon  monoxide.   The  mean  value of carbon dioxide in the 0583
audit differed  by  11%  from the expected value; whereas,  in 1183 the mean
value was  within  6%.   In  both  audits,  the  mean  values  for  oxygen were
within 1%. In contrast, the mean values  for carbon monoxide differed as much
as 21% from  the expected  value.

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             TABLE 5.  PARTICIPANTS' RESULTS FOR METHOD 3 AUDIT
                       (ALL DATA - NO OUTLIERS REMOVED)
Type of   Audit               No. of    Repli-
sample    date   Parameter   analyses   cate
                                      EPA     Participants' results
                                      true                     Std.
                                      value    Mean   Median   dev.
Small     0583
 cylinder
         Z C02


         Z 02


         Z CO


1183     Z C02


         Z 02


         Z CO
64
63

64
63

53
53

52
51

52
51

40
40
1
2

1
2

1
2

1
2

1
2

1
2
 5.00
 5.00

15.10
15.10

 1.00
 1.00

 7.10
 7.10

11.20
11.20

 0.50
 0.50
 4.49
 4.59

15.12
15.10

 0.81
 0.79

 6.72
 6.70

11.23
11.20

 0.47
 0.47
 4.70
 4.70

15.05
15.00

 0.80
 0.90

 6.80
 6.80

11.40
11.40

 0.50
 0.40
0.73
0.98

1.22
1.22

0.30
0.33

0.34
0.53

1.20
1.27

0.23
0.31

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                                 SECTION 3

                        METHOD 5 DRY GAS METER AUDIT
     In the Method 5 audit procedure, participants use a calibrated orifice
to check the calibration of the dry gas meter in their EPA Method 5 control
console (meter  box).   They insert the  orifice  in the Method  5  meter box,
allow the box to warm-up,  and  then make three 15-minute volume measurements.
The participants  convert   each  of the  three  volumes to  cubic  meters  at
standard conditions using the formula  specified in  Method  5 (Eq.  5.1  of
Appendix A 40 CFR 60) and record them on the data card.  Finally, they mail
the orifice and the data card to EPA for statistical analysis.

     In the spring audit  (0383),  71% of the 160 laboratories that received
the audit package returned data.   In the  fall  audit  (0983),  65X of the 153
laboratories returned data. These percentages are slightly lower than those
found in previous audits  (2,3,4).   Table 6  (which  classifies the partici-
pants into general categories)  compares  the number  of participants who re-
quested to participate  in the Method 5 audit with the  number who actually
returned data.
                   TABLE 6.  METHOD 5 AUDIT PARTICIPANTS
Total
                         No. requesting samples
160
153
                             No.  returning data

Contractor
University
Industry
Foreign
Federal
State
Local
0383
88
1
44
3
3
15
6
0983
80
0
43
4
3
17
6
0383
59
0
33
3
3
12
4
0983
43
0
32
4
2
15
4
114
100
     Figure  1,  a  cumulative histogram,  shows the accuracy obtained by par-
ticipants in the  0383 and  0983  Method  5  audits,  expressed  as the percent
difference from the  true (EPA)  value at  various  levels  of  accuracy.  The
Code of  Federal Regulations  (1)  requires  that the dry  gas  meter be cali-
brated with  an accuracy  of  ±2%.   Figure  1  also  shows  that 46%  of the
reporting laboratories in the  0383 audit and 53Z in the  0983 audit obtained

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this accuracy.  These results indicate a slight increase to those in previ-
ous audits (Figure 2).   Seventy-three of  the  laboratories  participated in
both audits.

     The histograms in  Figures  3 and 4  compare the individual  results of
the 0383 and 0983 audits with the mean and the median values for all parti-
cipants.  The majority  of the  laboratories  (0983)  reported  values higher
than the  EPA value.   The standard  deviation  of  the  triplicate  analysis
(precision) by each  laboratory  indicated  that  for the 0383 audit,  65% of
the standard deviations for each set were within 0.3%.  For the 0983 audit,
70% of the standard deviations were within 0.3%.  Three percent of the 0383
and 4%  of the  0983  data  were  identified as  outliers using  Chauvenet's
Criterion (5).  Before  the outliers  were  removed, the  mean  values  for the
0383 and  0983 data differed  by 5.7  and  4.1%  from the  true  value,  respec-
tively.  After deletion of outliers, these values were  reduced  to  2.6 and
2.1, respectively.

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    100
     80


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          OAUDIT0383.n = 763

          EiAUDIT0983,n = 614
                                                             8
                                                                   9
 234      667

DIFFERENCE IN MEASUREMENTS FROM EPA VALUE, percent
                                                      10
           Figure 1.  Cumulative accuracy for participants in Method 5 audits 0383 and 0983.

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     55
    50
    45
to
UJ

£


I
K
O
CD
40
     35
    30
            I         1         I         I


          DEGREE OF ACCURACY = 2 PERCENT
                     I
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        0280/622   0880/725  0381/738   0981/723   0382/827  0982/769   0383/763   0983/614




                               AUDIT/NUMBER OF SAMPLES



                     Figure 2.  Previous results of Method 5 audit.

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  20
      NUMBER OF VOLUMES = 763


                 MEDIAN = 1.4
   15
 8
co
IU

E  10
K

O
0
rt.
       OUTLIERS

       REMOVED
                           J.
   JL
            MEAN = 4.3
J_
                 OUTLIERS

                 REMOVED
       >9 -8  -6   -4-2   0    2   4   6   8


            DIFFERENCE FROM EPA VALUE, percent



          Figure 3.  Results of Method 5 audit 0383.
                   10 <10
                           10

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   20
   15
V)
IU
K
O
CD
2
   10
       NUMBER OF VOLUMES = 614

                 MEDIAN =-0.8
      OUTLIERS
      REMOVED
                 I
                                    MEAN = 1.0
                  OUTLIERS
                  REMOVED
J  1 I
        >9  -8   -6   -4   -2   0    2    4   6    <8

             DIFFERENCE FROM EPA VALUE, percent

          Figure 4.  Results of Method 5 audit 0983.
                           11

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                                 SECTION 4

                               METHOD 6 AUDIT
     This audit checks the participant's  ability  to  analyze  Method 6 sam-
ples for sulfate.   The audit set  consists  of five  dilutions of 10 N sulfuric
acid in  25  ml sealed  glass  ampoules.  The  analyst  withdraws  5.0  ml from
each ampoule, adds  30  ml of 3%  hydrogen  peroxide, and dilutes this sample
to 100 ml with distilled water.  A 20 ml aliquot is then withdrawn from the
diluted sample, 80  ml  of 100% isopropanol and  thorin  indicator are added,
and the sample is  titrated with barium perchlorate (BalClO/,^) to a pink end
point.  In calculating the results,  the  participants  assume  an original sam-
ple volume  of  100 ml, and a sample of 0.021  dry standard  cubic  meter  of
stack gas.

     Table 7  (which classifies  the  participants into  general categories)
compares the total number of participants requesting participation with the
number returning data.   In the spring audit  (0283),  71% of the 160 labora-
tories that  received  the audit  package  returned data.  In  the fall audit
(0883), 61%  of  the 147  laboratories returned  data.   Seventy-five labora-
tories participated in both  audits and returned data.
                   TABLE 7.  METHOD 6 AUDIT PARTICIPANTS


                          No. requesting samples        No. returning data
                            0283          0883            0283      0883
Contractor
Industry
Foreign
Federal
State
Local
85
46
3
1
16
9
76
44
4
1
14
8
54
35
2
1
13
8
41
28
4
0
11
6
Total                       160           147              113        90
     Table 8  shows  the percentage of laboratories  that  achieved 2% and  5%
accuracy for  each of the five different concentrations in the  1983 Method 6
audits.  It also  shows that 55% of  the  reporting laboratories in the 0283
audit achieved  an  accuracy within 2% for  the three higher concentrations.
However in  the  0883 audit,  59% of  the  laboratories  achieved an accuracy
                                      12

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within 2X for  all concentrations.  Approximately  81% of  the laboratories
were able to achieve an accuracy level of within 5% on 9 of the 10 samples.
                   TABLE 8.  SUMMARY OF SOURCE S02 AUDITS
                                        0283                    0883
Concentration	± 2%	± 5%	t 2%	± 5%

   0 -  500 mg/DSCM                43%         73%         59%         82%

 501 - 1000 mg/DSCM                50%         83%         68%         81%
                                                           68%         84%

1001 - 1500 mg/DSCM                58%         84%         61%         84%
                                                           60%         86%

1501 - 2000 mg/DSCM                55%         88%         —

2001 - 3000 mg/DSCM	55%	88%	™	—

       n                                 113                     90
                                     13

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                                 SECTION 5

                               METHOD 7 AUDIT
     This audit checks the participant's ability to analyze Method 7 sample
for nitrate.  The NOX audit  set consists of  five  dilutions of a potassium
nitrate (KN03) solution  in  25 ml glass ampoules which are autoclaved after
sealing so that bacteria which might attack the nitrate are destroyed.  The
analyst withdraws  5.0 ml  from  an  ampoule,  adds  this  with  25 ml  of  the
Method 7 absorbing solution to a flask, adjusts the  pH with sodium hydroxide,
and dilutes to 50  ml with distilled  water.   A 25 ml aliquot  is  withdrawn
from the  diluted  sample, placed in  an evaporating  dish,  and  treated as
described in  Section  4.3 of  Method 7.  After  this treatment  is completed,
the absorbance is measured  at 410 mn  with  a calibrated spectrophotometer.
In calculating  the   concentrations  present,  the  participant  assumes that
2000 ml of stack gas was sampled.

     Table 9  shows  both  the  total  number of laboratories requesting parti-
cipation and  the  number that  returned data for Method 7  audits  0483  and
1083.  In the  spring audit  (0483),  51* of the  124  laboratories  receiving
the audit package  returned  data.   In  the  fall audit  (1083), 49%  of  the
laboratories returned  data.    Forty-two  laboratories  participated  in both
audits and returned data.
                   TABLE 9.  METHOD 7 AUDIT PARTICIPANTS
                          No. requesting samples        No. returning data

Contractor
Industry
Foreign
Federal
State
Local
0483
75
32
1
1
8
7
1083
67
31
2
1
5
5
0483
30
21
1
1
5
5
1083
22
21
2
1
4
4
Total                        124            111              63         54
     The percentage of  laboratories that can achieve 5 and 10% accuracy for
each of  the  five concentrations  are  shown in Table 10.   In addition, 32%
of the reporting laboratories in  the 0483 audit achieved an  accuracy within
5X on the  lowest concentration.   In the  1083 audit, 47% of the laboratories
                                      14

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achieved an accuracy within 5%.  Sixty-six percent of the laboratories were
able to achieve 10% accuracy on 9 of 10 samples in both audits.
                  TABLE 10.  SUMMARY OF SOURCE NOV AUDITS
                                        0483                    1083
Concentration	± 5%	± 10%	± 5%	± 10%

  0 -  200 mg/DSCM                 32%         51%         47%         66%

201 -  400 mg/DSCM                 52%         74%         58%         77%
                                                           63%         83%

401 -  600 mg/DSCM                 46%         71%         63%         81%
                                                           42%         73%

601 -  800 mg/DSCM                 52%         66%         —

801 - 1000 mg/DSCM	52%	68%	•—	—

      n                                   63                      54
                                     15

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                                 SECTION 6

                           METHOD 19A COAL AUDIT
     Subpart Da of 40 CFR 60 allows  coal  sampling and analysis to serve as
an acceptable  method for  demonstrating  scrubber  inlet  flue  gas  sulfur
concentration.  The coal audit  checks  the participant's  ability to analyze
a coal sample for sulfur, ash,  moisture, and BTU content.

     Each set of coal samples  consisted of two bottles,  each containing 50
grams of 60-mesh  coal.   The participants analyzed  each  sample for sulfur,
moisture, ash, and gross calorific content.  The following American Society
for Testing  and  Materials  (ASTM) procedures  (6)  were recommended  but  not
necessarily mandated for participant's  use in analyzing the  coal samples:

     •  ASTM D-3177 (Standard Test Method  for Total  Sulfur  in the Analysis
        of Coal and Coke);

     •  ASTM D-3174 (Standard Test Method for Ash in the Analysis Sample of
        Coal and Coke);

     •  ASTM D-3173 (Test for Moisture in the Analysis Sample of Coal); and

     e  ASTM D-2015 (Standard Test Method for Gross  Calorific  Value of Solid
        Fuel by the Adiabatic Bomb Method).

     The participants measured  the parameters and  reported their results for
moisture (%) on an as-received basis, and their results for sulfur (%), ash
(%), and gross calorific value (Btu/lb) on a dry basis.

     In the  spring  audit (0383),  85% of the 130 laboratories that received
the audit package returned data.  In the  fall audit (0983), 84% of the 117
laboratories returned data.  Eighty-three laboratories participated in both
audits and  returned data.  Table  11  shows the total number  of laboratories
requesting participation versus  the  number  that  returned  data  for  coal
audits 0383 and 0983.
                                     16

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                     TABLE 11.  COAL AUDIT PARTICIPANTS
                            No. requesting samples      No. returning data

Contractor
Industry
Federal
State
Local
0383
72
41
1
11
5
0983
62
40
0
11
4
0383
60
37
0
9
5
0983
51
34
0
9
4
Total                         130           117           111        98
     Tables 12 and 13 summarize the coal audit  results.  The number of anal-
yses is greater than the number  of participants  because some companies had
more than  one laboratory  participating.   In  this  case, each  laboratory
received its  own  set of samples and was  asked to analyze  the  samples in
duplicate.  Accuracies of 5% and 10% were  chosen as the reporting criteria
for each of the four parameters (sulfur, moisture, ash, and gross calorific
content).

     In both audits, 54% of  the  laboratories  were able to analyze the sul-
fur content  of  the  low  level  samples  within  5%  of  the expected  value.
Sixty-three percent achieved 5%  accuracy  for  the high  level  sulfur concen-
trations.  Only 28% achieved 5% on the low moisture concentration; however,
65% achieved 5% on the higher concentration in the 0383 audit.  For the ash
analysis and Btu  content,  92%  to  99%  of  the reporting  laboratories were
able to  achieve  an  accuracy  within 5%  for   both  sample  concentrations.

     The participants'  accuracy  improved  with  higher  concentrations on all
parameters except ash, where there  was  a  slight decrease.  For those labo-
ratories that reported  duplicate analyses, the  intra-laboratory precision
(repeatability) showed no correlation with concentration level.
                                     17

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TABLE 12.  SOURCE COAL AUDIT - 0383
Expected
value
0.74%
2.98%
2.05%
6.13%
7.40%
11.42%
12719. Btu/lb
14165. Btu/lb
No. of
analyses
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
125
120
127
120
125
120
127
120
123
118
125
118
125
118
123
118
Laboratories
accurate within i 5%
Sulfur
64%
64%
74%
71%
Moisture
34%
40%
65%
70%
Ash
96%
97%
92%
92%
Gross Calorific
94%
95%
99%
99%
Laboratories
accurate within ± 10%
87%
83%
90%
86%
69%
68%
87%
86%
99%
99%
100%
100%
99%
99%
100%
100%
                 18

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TABLE 13.  SOURCE COAL AUDIT - 0983
Expected
value
0.74%
2.95%
1.62%
5.75%
7.31%
11.33%
12470. Btu/lb
14059. Btu/lb
No. of
analyses
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
112
109
113
110
113
110
114
111
112
109
113
110
112
109
111
108
Laboratories
accurate within ± 5%
Sulfur
54%
56%
68%
63%
Moisture
29%
28%
26%
29%
Ash
97%
96%
96%
95%
Gross Calorific
97%
98%
99%
99%
Laboratories
accurate within ± 10%
76%
77%
89%
88%
48%
53%
74%
78%
99%
99%
99%
98%
100%
100%
100%
100%
                 19

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                                 SECTION 7

                               METHOD 3 AUDIT
     This audit  checks  the participant's ability to  analyze a  gas  sample
using an Orsat analyzer.  The audit package consists of a disposable cylin-
der that  contains  a 4 liter  sample  of  oxygen,  carbon  dioxide,  and carbon
monoxide.  The analyst  expels the gas into the  Orsat  analyzer  using posi-
tive pressure of the  cylinder.   The gas sample  is  analyzed for percentage
of carbon dioxide,  oxygen, and carbon monoxide.

     In the spring  audit  (0583),  55% of the 110 laboratories receiving the
audit package  returned  data.   In the  fall  audit  (1183),   53%  of  the  94
laboratories returned data.  Thirty-seven laboratories participated in both
audits and returned data.  Table  14  shows  the total number  of laboratories
requesting participation versus the number  that returned  data for the Method
3 audits 0583 and 1183.
              TABLE 14.  METHOD 3 AUDIT PARTICIPANTS
                          No. requesting samples
Total
110
94
                            No.  returning data

Contractor
Industry
Foreign
Federal
State
Local
0583
66
29
1
2
9
3
1183
52
24
1
2
12
3
0583
30
18
1
2
8
2
1183
25
13
1
1
7
3
61
50
     Tables  15  and  16 summarize the Method  3  audits.   Each laboratory was
asked to  analyze the sample  in duplicate.  Five  and  ten percent accuracy
were chosen  for the precision  reporting  criteria for  each  of the parame-
ters.  Each  parameter had only  one concentration.

     In the  0583  audit,  only 43% of the reporting laboratories achieved an
accuracy within 5%  for  the C02.  However,  since  the C02 concentration was
higher in  the 1183 audit, 61% of the  laboratories  achieved an accuracy with-
in  5%.  In both audits,  81%  of  the laboratories achieved  an  accuracy  within
5%  of the  true  value for the ©2 analysis which was  three times better than
                                      20

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the previous audit (4).  For the CO analysis,  only 25% of the laboratories
in 0583 and  29%  in  1183 achieved an  accuracy  within 5% and  22%  of the
laboratories did not report a value for CO.
                  TABLE 15.  SOURCE METHOD 3 AUDIT - 0583
Expected
value
5.00%
15.10%
1.00%

Expected
value
7.10%
11.20%
0.50%
No. of
analyses
(1) 64
(2) 63
(1) 64
(2) 63
(1) 53
(2) 53
TABLE
No. of
analyses
(1) 52
(2) 51
(1) 52
(2) 51
(1) 40
(2) 40
Laboratories
accurate within ± 5%
O>2
44%
43%
02
84%
84%
CO
32%
21%
16. SOURCE METHOD 3 AUDIT
Laboratories
accurate within ± 5
C02
62%
61%
02
81%
84%
CO
35%
23%
Laboratories
accurate within ± 10%
73%
76%
91%
86%
42%
43%
- 1183
Laboratories
accurate within ± 10%
92%
92%
90%
90%
35%
23%
                                     21

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                                 REFERENCES
1.   U.S. Environmental Protection Agency.   Standards  of  Performance for
     New Stationary Sources - Appendix A.  Title 40, Part 60, Code  of  Fed-
     eral Regulations.

2.   Fuerst, R.G., E.W. Streib,  and M.R.  Midgett.   A Summary  of  the  EPA
     National Source Performance Audit Program  -  1980.   EPA-600/4-81-077,
     U.S. Environmental Protection  Agency,  Research  Triangle  Park,  North
     Carolina 27711, December 1981.

3.   Streib, E.W., R.G. Fuerst,  and M.R.  Midgett.   A Summary  of  the  1981
     EPA National Performance Audit  Program on Source Measurements.   EPA-
     600/4-83-026, U.S. Environmental Protection Agency,  Research Triangle
     Park, North Carolina 27711, June 1983.

4.   Streib, E.W. and M.R. Midgett.  A Summary of  the  1982 EPA National Per-
     formance Audit Program on Source Measurements.  EPA-600/4-83-049, U.S.
     Environmental Protection Agency,  Research  Triangle  Park,  North  Caro-
     lina 27711, April 1984.

5.   Chauvenet, W.  Manual of Spherical and Practical Astronomy:   Volume
     II -  Theory and  Use  of Astronomical  Instruments   (Method  of  Least
     Squares).  J.P. Lippincott  and Co.,  Philadelphia, Pennsylvania,
     1863 (?).

6.   American Society for Testing and Materials.  Annual  Book of  ASTM Stan-
     dards - 1979.  Part  26.   01-026079-13, American  Society  for  Testing
     and Materials, Philadelphia, Pennsylvania.
                                       22

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       APPENDIX A




FREQUENCY DISTRIBUTIONS
           23

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                            DGM FREQUENCY DISTRIBUTION  OF ABSOLUTE PERCENT DIFFERENCE - 0383
1 Samp.
763
757
754
743
739
737
Mln.
.0
.0
.0
.0
.0
.0
10%
.4
.4
.4
.4
.4
.4
20%
.8
.8
.8
.8
.8
.8
30%
1.2
1.2
1.2
1.2
1.2
1.2
40*
1.6
1.6
1.6
1.5
1.5
1.5
50%
2.2
2.2
2.2
2.2
2.2
2.2
60%
2.9
2.9
2.8
2.7
2.7
2.7
70%
3.7
3.7
3.6
3.6
3.6
3.5
80%
4.4
4.4
4.4
4.2
4.2
4.2
90%
5.9
5.8
5.7
5.6
5.6
5.6
Max.
466.7
60.9
14.7
10.1
9.3
8.2
Mean
5.7
3.0
2.8
2.6
2.6
2.6
Std.
dev.
32.7
4.3
2.3
2.0
2.0
1.9
Skewness
12.39
.00
-.01
-.02
-.04
-.05
Median
2.2
2.2
2.2
2.2
2.2
2.2
10
.£•
                            DGM  FREQUENCY DISTRIBUTION  OF ABSOLUTE PERCENT DIFFERENCE - 0983
1 Samp.
614
611
609
597
590
589
Min.
.0
.0
.0
.0
.0
.0
10%
.3
.3
.3
.3
.3
.3
20%
.7
.7
.7
.7
.7
.7
30%
1.1
1.1
1.0
1.0
1.0
1.0
40%
1.5
1.5
1.5
1.5
1.5
1.5
50%
1.9
1.9
1.9
1.9
1.9
1.9
60%
2.4
2.3
2.3
2.3
2.2
2.2
70%
2.9
2.9
2.9
2.8
2.8
2.8
80%
3.5
3.4
3.4
3.3
3.3
3.3
90%
5.1
5.0
5.0
4.8
4.7
4.7
Max.
303.4
69.2
14.4
10.0
8.0
7.2
Mean
4.1
2.6
2.4
2.2
2.2
2.1
Std.
dev.
21.3
3.7
2.3
1.8
1.6
1.6
Skewness
13.57
.02
-.02
-.03
-.05
-.08
Median
1.9
1.9
1.9
1.9
1.9
1.9

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S02 FREQUENCY DISTRIBUTION OF PERCENT DIFFERENCE - NO OUTLIERS REMOVED




                              AUDIT 0283
Sample
No.
1
2
3
4
5
No.
Obs.
113
113
113
112
113
Min.
.06
.00
.01
.03
.00
10%
.35
.24
.30
.19
.27
20%
.82
.50
.36
.52
.55
30*
1.34
.84
.69
.80
.98
40%
1.75
1.39
1.21
1.20
1.40
50%
2.39
1.99
1.56
1.91
1.69
60%
3.21
2.53
2.08
2.19
2.46
70%
4.28
3.49
3.14
2.73
3.38
80%
5.89
4.35
3.86
3.83
4.07
90%
9.97
8.03
6.65
5.79
6.48
Max.
296.27
292.08
296.01
294.96
303.47
Mean
8.76
7.45
6.89
6.62
7.23
Std.
Dev.
31.02
29.94
30.02
29.93
30.85
S02 FREQUENCY DISTRIBUTION OF PERCENT DIFFERENCE - NO OUTLIERS REMOVED




                              AUDIT 0883
Sample
No.
1
3
4
6
8
No.
Obs.
90
90
90
90
90
Min.
.10
.00
.00
.01
.02
10%
.35
.11
.16
.33
.20
20%
.71
.43
.52
.54
.39
30%
.86
.59
.79
.81
.72
40%
1.03
1.13
1.14
1.27
1.04
50%
1.66
1.49
1.33
1.47
1.28
60%
2.17
1.98
1.60
1.91
1.48
70%
3.43
2.53
2.13
2.91
2.03
80%
4.94
3.70
4.52
3.66
3.51
90%
12.03
8.38
8.25
5.94
8.71
Max.
97.00
96.98
96.97
96.97
96.97
Mean
4.96
4.74
4.91
4.29
3.77
Std.
Dev.
11.86
12.95
13.30
12.03
10.69

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NOX FREQUENCY DISTRIBUTION OF PERCENT DIFFERENCE - NO OUTLIERS  REMOVED




                              AUDIT 0483
Sanple
No.
1
2
3
4
5
No.
Obs.
59
62
63
62
63
Min.
.17
.33
.00
.12
.04
10%
.84
.77
.40
.42
.77
20*
2.51
1.37
.59
1.23
1.99
30*
4.02
2.01
1.63
2.01
2.34
40%
6.20
3.45
3.39
3.40
3.08
50%
9.38
4.45
5.69
4.45
4.53
60%
11.39
5.79
7.28
7.84
5.83
70*
14.07
8.54
8.83
11.10
10.88
807.
22.95
13.46
15.66
16.18
15.71
90%
66.16
39.57
31.41
66.48
67.13
Max.
772.70
638.70
887.23
669.47
663.16
Mean
36.91
28.64
32.70
30.91
32.64
Std.
Dev.
110.70
90.85
118.83
95.03
102.22
NOX FREQUENCY DISTRIBUTION OF PERCENT DIFFERENCE - NO OUTLIERS REMOVED




                              AUDIT 1083
Saaple
No.
2
3
5
7
9
No.
Obs.
53
53
54
54
52
Mln.
.34
.09
.02
.17
.11
10%
.59
.23
.20
.71
.75
20%
1.60
1.56
.93
1.08
1.36
30%
2.96
2.29
1.57
2.12
2.51
40%
3.72
3.39
2.21
3.20
3.19
50*
5.15
4.35
2.85
4.04
5.80
60%
7.09
4.90
4.10
4.74
7.08
70%
11.49
8.01
5.94
5.29
8.71
80%
15.63
11.72
8.40
8.61
11.65
90%
39.78
53.16
21.76
16.77
21.94
Max.
98.14
111.03
155.40
120.89
142.66
Mean
15.32
14.92
13.95
13.69
15.27
Std.
Dev.
24.39
26.90
31.62
28.76
30.32

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NATIONAL COAL AUDIT FREQUENCY DISTRIBUTION OF ABSOLUTE PERCENT DIFFERENCES OF EXPECTED AND REPORTED VALUES




                                               STUDY:  0383
Sanple

1000
6000

1000
6000

1000
6000

1000
6000
No.

245
247

245
247

241
243

241
243
Min.

.00
.00

.00
.00

.00
.00

.01
.00
10%

.00
.67

1.46
.82

.14
.09

.04
.08
20%

1.35
1.01

2.44
1.47

.27
.26

.09
.13
30%

1.35
1.68

3.90
2.28

.54
.44

.13
.19
40%

2.70
2.35

5.37
2.94

.81
.61

.17
.28
50% 60%
SULFUR
2.70 4.05 5
3.02 3.36 4
MOISTURE
6.83 8.29 10
3.59 4.40 5
ASH
1.08 1.35 1
.70 .96 1
GROSS CALORIFIC
.24 .31
.37 .50
70%

.41
.36

.24
.22

.62
.23

.48
.72
80%

8.11
6.04

14.63
6.85

2.03
1.49

.73
1.03
90%

10.81
10.74

24.39
12.40

3.11
2.71

1.57
2.46
Max.

24.32
35.23

347.80
38.01

57.97
8.49

7.36
12.66
Mean

5.01
4.37

12.76
5.71

1.88
1.31

.59
1.01
Std.
Dev.

5.30
4.82

32.22
6.86

5.32
1.72

.99
1.84

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NATIONAL COAL AUDIT FREQUENCY DISTRIBUTION OF ABSOLUTE PERCENT DIFFERENCES OF EXPECTED AND REPORTED VALUES




                                               STUDY:  0983
Sample

2000
9000

2000
to 9000
oo

2000
9000

2000
9000
No.

223
221

225
223

223
221

221
219
Min.

.00
.00

.17
.00

.00
.00

.01
.01
10%

.68
.00

1.57
1.85

.26
.27

.30
.14
20*

1.36
1.35

3.30
3.70.

.44
.41

.59
.22
30%

1.69
2.70

5.04
5.56

.62
.55

.80
.28
40%

2.71
2.70

6.61
7.41

.88
.68

.96
.36
50% 60%
SULFUR
3.05 4.07
4.05 5.41
MOISTURE
7.30 8.52
9.88 12.96
ASH
1.06 1.32
.82 1.09
GROSS CALORIFIC
1.09 1.24
.43 .52
70%

5.42
8.11

9.57
16.05

1.59
1.23

1.49
.62
80%

6.44
13.51

10.78
21.60

1.94
1.78

1.87
.75
90%

10.51
16.22

12.70
29.63

2.82
2.60

2.45
1.10
Max.

44.41
277.03

87.83
91.98

242.54
484.40

9.59
9.17
Mean

4.90
9.31

8.40
15.12

3.54
5.49

1.39
.63
Std.
Dev.

6.00
26.92

9.07
16.83

22.11
45.38

1.26
.87

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      NATIONAL ORSAT AUDIT FREQUENCY DISTRIBUTION OF ABSOLUTE PERCENT DIFFERENCES OF EXPECTED AND REPORTED VALUES


                                                     STUDY:  0583



                                                                                                            Std.

  Sample   No.    Min.    101    20%    30%    40Z    50%    60Z    70%    80%    90%     Max.     Mean     Dev.


                                                          C02


  2000     127    .00     .00   2.00    4.00   4.00   6.00   8.00   8.00  14.00  24.00   98.00     11.15   16.00


                                                          <>2
ro

^2000     127    .00     .66    .66     .66    .66   1.99   1.99   2.65   3.31  10.60   35.10      3.98    6.98


                                                          CO


  2000     106    .00     .00    .00   10.00  10.00  20.00  20.00  40.00  50.00  80.00   80.00     26.13   26.57

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      NATIONAL ORSAT AUDIT  FREQUENCY  DISTRIBUTION OF  ABSOLUTE PERCENT DIFFERENCES OF EXPECTED AND REPORTED VALUES




                                                      STUDY:   1183





                                                                                                             Std.

  Sample   No.    Min.    10Z     20Z     30%     40%     50Z    60Z    70Z    802    90%     Max.     Mean     Dev.




                                                           C02




   3000    103    1.41    1.41    1.41     2.82    4.23    4.23   4.23    7.04   7.04   9.86    43.66     5.87    5.88




                                                           02



w  3000    103      .00    .00     .00      .89    1.79    1.79   2.63    3.57   4.46   8.93    73.21     4.43   10.01
o



                                                           CO




   3000     80      .00    .00     .00    20.00   20.00   20.00 20.00   40.00  60.00  60.00   300.00    32.25   43.57

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             APPENDIX B




INSTRUCTIONS FOR EPA AUDIT MATERIALS
                 31

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            INSTRUCTIONS FOR USE OF ENVIRONMENTAL PROTECTION AGENCY
                 METHOD 5 DRY GAS METER PERFORMANCE TEST DEVICE


NOTE:  All procedures referred to are from revised Method 5 published in the
       Federal Register, Volume 12, Number 160, Part II, Thursday, August 18,
       1977, pp. 41776-41782 and references contained therein.  This revised
       method should be adhered to in all details in the use of this quality
       assurance performance device.

EQUIPMENT:  The participant in this study should possess the following
            equipment, including the performance test device supplied by EPA.

Quantity	Item	

    1     Method 5/Source Sampling Meter Box
    1     Stopwatch, preferably calibrated in decimal minutes
    1     Thermometer, ambient range
    1     Barometer.  If unavailable, call nearest National Weather Service and
          request the ABSOLUTE barometric pressure.  (Corrected for temperature
          and acceleration due to gravity, but not corrected for altitude.)
    1     Performance Test Device.  A calibrated flow orifice housed in a quick-
          connect coupling and identified with an engraved three-digit serial
          number.
            WARNING:  THE DEVICE MUST NOT BE DISASSEMBLED UNDER ANY CIRCUMSTANCES.
            Use these devices at room temperature.
PROCEDURE:
          Calibration of Vacuum Gauge — The vacuum pressure gauge on the
          meter box must be calibrated in the range of use (11-22" Hg) against
          a standard (Hg Manometer) to ensure accurate results.

          Remove the performance test device from its case and insert it into
          the gas inlet quick-connect coupling on the source sampling meter box,

          Turn the power to the meter box on and start the pump.

          Adjust the coarse flow rate control valve and the fine flow rate
          control valve to give a reading of 19" Hg (vacuum reading).
            CAUTION:  The vacuum reading must be accurate and stable for the
            test period.

          Allow the orifice and source sampling meter box to warm up for 45
          minutes with flow controls adjusted as described in Step 3 before
          starting quality assurance runs.
                                        32

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PROCEDURE:   (continued)
          Make triplicate quality assurance runs.  For each run, record
          initial and final dry gas neter volumes, dry gas meter inlet and
          outlet temperatures,  internal orifice pressure drop (AH), ambient
          temperature,  and barometric pressure.  Run duration should be
          •lightly greater than 15 minutes.  The following procedure is
          recommended.   Fifteen minutes after a run is started,  the partici-
          pant watches  the dry gas meter needle closely.  As the needle reaches
          the zero (12  o'clock) position, the pump and stopwatch are stopped
          simultaneously.  The dry gas meter volume and time are recorded.

          This complete run procedure is performed three times to provide the
          required triplicate quality assurance runs.

          Calculate the corrected dry gas volume for each run using equation 5.1
          of the above-referenced Method 5.  For each replicate, record the
          corrected dry gas volume in dry standard cubic meters, the sampling
          time in decimal minutes, the barometric pressure in mm Hg, and the
          ambient temperature in degrees Celcius on the enclosed data card.  Be
          sure to record the performance test device serial number on the data
          card in the column headed "Orifice Number."

            NOTE 1:  If you calculate dry gas volume in English  Units, use the
                     conversion factor of 0.02832 m^ft^ to obtain the volume in
                     •etric units.

            NOTE 2:  If your stopwatch is not in decimal minutes, be sure to
                     convert (e.g. 15 minutes 20 seconds is reported as 15.33
                     minutes).

          After recording the requested data on the enclosed data form, return
          the data form and the performance test device to:

          Quality Assurance Division (MD-77A)
          Environmental Monitoring Systems Laboratory
          U.S. Environmental Protection Agency
          Research Triangle Park, NC  27711
          ATTN:  Ellen  W. Streib

          A postpaid return envelope and label are enclosed for  this purpose.
                                       33

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     INSTRUCTIONS FOR  USE  OF  ENVIRONMENTAL PROTECTION  AGENCY  STATIONARY
               SOURCE QUALITY ASSURANCE SOg REFERENCE SAMPLES


HOTE:  All Method 6 procedures referred to are  from the amended method pub-
       lished in the Federal Register  Vol.  1*2.  No.  160, Part II, Thursday,
       August 16,  1977,  pp  1»1782-U1781*.   This  amended method  should  be
       adhered to in all details in the analysis of these  reference stand-
       ards.

1.   Prepare 3 percent hydrogen peroxide according to Section 3.1.3 of the
     method (30 ml is required for each sample  and each blank).

2.   Prepare each reference sample for analysis as follows:  Wrap a paper
     towel around the ampoule  and  with the ampoule in an  upright  position
     break off the top at the prescored mark by exerting pressure sideways.
     From the ampoule pipette  exactly  5  ml of the reference sample into a
     100 ml volumetric  flask.   Add 30 ml of  3 percent hydrogen  peroxide
     solution.  Dilute exactly to the mark with deionized,  distilled water.
     Analyze the sample in accordance with the procedure detailed in Section
     1».3 of the  method,  beginning with  "Pipette a 20  ml  aliquot  of this
     solution..."  (Note:   If more than 50 ml of barium perchlorate titrant
     is required  for  any  sample  analysis,  a  smaller aliquot  should  be
     selected to allow titration with less than 50 ml titrant.)

3.   Calculate the concentration, CsQ2 (concentration of sulfur dioxide,
     dry basis, corrected to standard  conditions, mg/dscm),  using Equation
     6-2.  A value  of 21 x  10"^  dscm should be used for Vm(std),  in the
     equation.  A value of 100 ml  should  be used for Vsoinin the equation.

1*.   Record the reference standard sample numbers and their corresponding
     S02 concentrations in mg/dscm on the enclosed data form.   Return the
     form to:

               Quality Assurance Division (MD-77A)
               Environmental Monitoring Systems Laboratory
               U.S. Environmental Protection Agency
               Research Triangle Park, NC 27711
               ATTN:  Ellen W. Streib

If other than  EPA Method 6  is used  for  your  analyses, please  explain  in
detail your analytical  procedure on the  back  of the enclosed  data  form.

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   INSTRUCTIONS FOR USE OF ENVIRONMENTAL PROTECTION AGENCY STATIONARY
             SOURCE QUALITY ASSURANCE NOX REFERENCE SAMPLES


Note:  All Method 7 procedures referred to are from the amended method
       published in the Federal Register Vol. 42, No. 160, Part 11,
       Thursday, August 18, 1977,  pp 41784-41786.  This amended method
       should be adhered to in all details in the analysis of these
       reference standards.

1.  Prepare absorbing solution according to Section 3.1 of the method.

2.  Prepare each reference sample for analysis as follows:  Wrap a paper
    towel around the ampule and with the ampule in an upright position
    break off the top at the prescored mark by exerting pressure sideways.
    From the ampule pipette exactly 5 ml of the reference sample into a
    100-ml beaker.  Add 25 ml absorbing solution to the beaker; adjust
    the pH to 9-12 (using pH paper as indicated in Section 4.2 of the
    method) by dropwise addition of sodium hydroxide (1N). Quantitatively
    transfer the contents of the beaker to a 50-ml volumetric flask and
    dilute exactly to the mark with deionized, distilled water.  Mix
    thoroughly and pipette a 25-ml aliquot of the diluted sample into
    a porcelain evaporating dish.  Beginning with the evaporation step
    in Section 4.3, complete the sample analysis.

3.  Calculate total pg NO2 per sample using Equation 7-3.  Calculate
    the sample concentration,  C (concentration of NOX as NO2, dry basis,
    corrected to standard conditions, mg/dscm), using Equation 7-4.
    A value of 2000 ml should be used for V8C in Equation 7-4.

4.  Record the reference sample numbers and their corresponding concentrations,
    C, in mg/dscm on the enclosed data form.  Return the form to:

                       Quality Assurance Division (MD-77A)
                       Environmental Monitoring Systems Laboratory
                       Environmental Protection Agency
                       Research Triangle Park, NC 27711
                       ATTN:   Ellen W. Streib

If other than EPA Method 7 is  used for your analyses,  please  explain in detail
your analytical procedure on the back of the enclosed data form.
                                       35

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                    COAL AUDIT PROGRAM INFORMATION
1.   There 1s approximately 50 grains of 60 mesh coal  per bottle.

2.   Analyze the coal samples for moisture and on a dry basis for ash,
     sulfur and gross calorific value.  Report moisture, ash, and sulfur
     In weight percent with gross calorific value reported as BTU/lb.

3.   All methods used 1n the analysis of these coal samples should follow
     American Society for Testing and Materials (ASTM) recommended procedures
     or an accepted automatic analytical device.

f.   Suggested procedures are:

                    Holsture 	 D-3173
                    Ash	 D-3174
                    Sulfur 	 D-3177
                    Gross Calorific Value ... D-2015

     Please note on the data card (columns 17-32) the ASTM method number.
     If an ASTM method was not used for analysis note that on the back of
     the data card.  Be parameter specific.

5.   If you cannot analyze the coal sample for all four parameters, analyze
     for what you can.  Analysis of moisture 1s necessary to calculate on
     a dry basis any of the other three parameters.  Analysis of sulfur 1s
     also necessary for the calculation of gross calorific value.

6.   Analyze each sample 1n duplicate (if possible) and record results as
     analysis 1 and analysis 2 for each parameter.

7.   Most laboratories will use site number 001.  Multiple site numbers
     are used by laboratories that receive more than one set of samples.
     These central laboratories have requested auditing of their satellite
     laboratories.

8.   After recording the requested data on the enclosed data card, return the
     data card  to:

                    Ms. Ellen W. Streib
                    Quality Assurance Division  (MD-77)
                    Environmental Monitoring Systems Laboratory
                    U.S. Environmental  Protection Agency
                    Research Triangle Park, NC  27711

     A postpaid return envelope  1s enclosed for this purpose.

9.   If you  have any questions concerning this or any source method audit,
     please  call  (919/541-7834).
                                          36

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              INSTRUCTIONS FOR USING EPA METHOD 3 AUDIT MATERIALS

Equipment Supplied with Audit Kit
    (1)   Small gas cylinder containing four liters of gas
    (2)   Nozzle for cylinder (taped on cylinder)
    (3)   Tygon tubing
Equipment to be Supplied by Participant
    (1)   Orsat analyzer
    (2)   Clamp
    (3)   Extra Tygon or surgical tubing

Procedure
    (1)   Leak-check apparatus by clamping off tubing.
          SEE DIAGRAM.
    (2)   Fill up burette with gas by using positive pressure.  Vent this sample
          through the manifold to the atmosphere.
    (3)   Repeat Step 2.
    (4)   Fill up burette past fill mark with the gas and carefully vent out
          excess to the atmosphere, until the fill mark is reached.
    (5)   Analyze for C0?, 09 and CO as described in Sections 4.2.5, 4.2.6
          and 4.2.7 of EPA Method 3.
    (6)   Record the results on the data card enclosed with the sample.
    (7)   Repeat Steps 4 through 6.
    CAUTION:  If the tubing is punctured excess times, leakage can occur.
              Replace if necessary.
    Send the data card to the address below. (The cylinder gas can should
not be returned.)
                    Ms. Ellen Streib
                    Quality Assurance Division (MD-77A)
                    Environmental Monitoring Systems Laboratory
                    U.S. Environmental Protection Agency
                    Research Triangle Park,  NC  27711
                                       37

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Note:  Site number will always  be 001 except when  other Orsat apparatus
       or  participants are using the same gas  sample.   The extra
       apparatus or participants should be labeled 002, 003, etc.
APPARATUS  SET-UP
                                     38
                                                  U.S. GOVERNMENT PRINTING OFFICE' 1985-559-111/10763

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