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                              United States
                              Environmental Protection
                              Agency
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                              Environmental Monitoring Systemsjk^M^N
                              Laboratory               ^M.**Wt \x
                              Research Triangle Park NC 27711
                              Research and Development
                              EPA-600/S4-81 -080  Dec. 1981
Project  Summary
                              Analysis  of  Commercial
                              Cylinder  Gases of Nitric Oxide,
                              Sulfur  Dioxide,  and  Carbon
                              Monoxide  at  Source
                              Concentrations—Results  of
                              Audit 5

                              C. E. Decker, W. C. Eaton, R. C. Shores, C. V. Wall
                               The U.S. Environmental Protection
                              Agency  (EPA)  has  established a
                              national performance audit program
                              to determine the accuracy of analyses
                              of cylinder  gases supplied by com-
                              mercial gas manufacturers. As of June
                              1981, five  audits have been per-
                              formed on  14  individual suppliers.
                              Audit 1 was performed in June 1978,
                              Audits  2 and  3  in January and
                              September  1979.  Audit 4 in April
                              1980, and  Audit 5 in  March-June
                              1981. To ensure that manufacturers
                              would not give preferential treatment
                              to EPA in providing the gases, EPA
                              obtained cylinder gases for all audits
                              through an anonymous third party.
                               Audits 1 through 5 include cylinders
                              of sulfur  dioxide (90 and 500 ppm),
                              nitric oxide  (50  and 300 ppm), and
                              carbon monoxide (50 and 500 ppm).
                              Cylinder  gases  were analyzed  by
                              Research Triangle  Institute  (RTI)
                              according to  EPA's "Traceability
                              Protocol for Establishing True Con-
                              centrations of Gases Used for Calibra-
                              tion  and Audits  of  Continuous
                              Emission Monitors" (Protocol 1, June
                              15, 1978).  Internal quality control
                              procedures by RTI and external quality
                              assurance performance audits by EPA
                              prior to each audit are important
                              elements of the Quality Assurance
                              Plan.  Results of Audit 5 and a
                              summary of results for all five per-
                              formance audits are presented for
                              each manufacturer included in the
                              audit program.
                               This Project Summary was develop-
                              ed by EPA's Environmental Sciences
                              Research Laboratory, Research Tri-
                              angle  Park, NC,  to announce  key
                              findings of the research project that is
                              fully documented in a separate report
                              of the same title (see Project Report
                              ordering information at back).


                              Introduction
                               High quality gas standards must be
                              used for calibration and auditing of
                              ambient  air  and  source emissions
                              monitors. Manufacturers of commercial
                              cylinder gas supply gas standards with a
                              certified analysis and statement of
                              accuracy. Generally, the level of accur-
                              acy is specified as a percentage of the
                              component value.  To  ascertain  the
                              accuracy of analyses of commercially
                              available cylinder  gases,  the  U.S.
                              Environmental Protection Agency (EPA)
                              has initiated a national performance

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audit program of commercial gas manu-
facturers. In June 1981, Audit 5 of this
program was completed. Audit 1 was
performed in June 1978, Audits 2 and 3
in January and September 1979, and
Audit 4 in April 1980. Results of these
audits  are documented  in  separate
reports that are available from the EPA
Project Officer.
  Audit 5 was conducted from March to
June 1981 to analyze the concentration
of cylinder gases purchased from  a
representative sample of manufacturers
and to determine the accuracy of the
manufacturers' certified concentrations
Audit 5  included  cylinders  of  sulfur
dioxide at 90 and  500 ppm, nitric oxide
at 50 and  300  ppm,  and  carbon
monoxide at 50 and 500 ppm obtained
from  14 different  manufacturers.  In
order to ensure that suppliers would not
give  preferential treatment to EPA in
providing  the  gases,  EPA  obtained
cylinder gases for Audit 5 through  an
anonymous third  party. Specifications
of the  type of analysis or the type of
cylinder (steel or  aluminum) were not
included on the purchase request. The
only specifications given to the manu-
facturers were   cylinder  size,
components,   nominal  concentration
levels,  and a request for a  certified
analysis.  The  request for a  certified
analysis did not specify that manufac-
turers  should analyze cylinder  gases
according  to  the  EPA's  Traceability
Protocol No. 1.

Procedure
  Cylinders of gas procured for Audit 5
were  analyzed  by  RTI  using  source
emission analyzers,  according to EPA's
Traceability Protocol No. 1.  National
Bureau of  Standards-Standard Refer-
ence Materials (NBS-SRM's) were used
to generate gas concentrations for cali-
bration  of  the   source  emission
analyzers, as specified in Protocol No. 1.
Each cylinder gas was analyzed three
times with an NBS-SRM (gas standard)
or  Gas   Manufacturers  Primary
Standard  (GMPS)  being  introduced
between analyses as a control check on
the analyzer. A strict internal quality
control program was maintained during
Audit 5. Prior to the audit, an external
quality assurance  performance  audit
was conducted by EPA on the organiza-
tion  performing the audit (RTI). Agree-
ment to within ±3 percent was required
between RTI  and  EPA before the audit
could begin. In addition, EPA provided a
confirmatory  analysis of any cylinder
gas  where  the  percent  accuracy
between  the manufacturers' analysis
and the mean-of the auditor's analysis
varied by more than 4 percent.

Summary of Results
  The results of Audit  5 are given in
Tables 5  through 7 of  the full report.
Each table includes the  manufacturer's
name, cylinder  type,  manufacturer's
analysis,  mean of theauditor'sanalysis,
EPA confirmatory analysis (if required),
parts-per-million  difference, and
percent  accuracy.  The audit  results
show that  for  26  cylinders of sulfur
dioxide, 9 cylinders had inaccuracies of
>10 percent; 5 of the 9 cylinders had
inaccuracies of >30 percent, and 1 of
the 5 cylinders  had  an inaccuracy of
>100 percent. Results  for nitric oxide
and carbon monoxide were substantial-
ly better than those for sulfur dioxide: of
28  nitric oxide cylinder gases, 2 had
inaccuracies  between  10 and  20
percent; of 28 carbon monoxide cylinder
gases, 4  had inaccuracies between 10
and 20 percent; the remaining  nitric
oxide  and  carbon  monoxide cylinder
gases had inaccuracies  of <10 percent.

Conclusion
  High quality gas standards must  be
used   by  organizations  performing
ambient  air monitoring, source emis-
sion monitoring, and research studies.
The results of Audit 5 show the need for
improvement in the quality of cylinder
gases available from commercial manu-
facturers.

Recommendations
  Based  on the results of Audit 5, it is
recommended  that  audits  of
commercial cylinder gas manufacturers
be continued on a routine basis. Future
monitoring programs should define the
need to include additional gases besides
sulfur dioxide, nitric oxide, and carbon
monoxide in the national performance
audit.

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  C. E. Decker, W. C. Eaton, R. C. Shores, andC. V. Wall are with Research Triangle
    Institute, Research Triangle Park, NC 27709.
  D. J.  von Lehmden is the EPA Project Officer (see below).
  The complete report, entitled "Analysis of Commercial Cylinder Gases of NO,
    SO2 and CO at Source Concentrations: Results of Audit 5," (Order No.
    PB 82-118 654; Cost: $6.00, subject to change)  will be available only from:
          National Technical Information Service
          5285 Port Royal Road
          Springfield, VA 22161
          Telephone: 703-487-4650
  The EPA Project Officer can be contacted at:
          Environmental Monitoring Systems Laboratory
          U.S. Environmental Protection Agency
          Research Triangle Park, NC 27711

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