Volume 1, Number 2
Research Triangle Park, N.C. 27711
   Second Quarter, 1978




    The Process Measurements Review (PMR), the
new  publication  of the  Process  Measurements
Branch (PMB) of EPA's Industrial  Environmental
Research  Laboratory (IERL-RTP), has received
widespread attention among those interested in en-
vironmental assessment  and  control  technology
measurement programs. The first issue, published
last quarter, enjoyed a circulation of well over 1,800
copies. But for those of you receiving the PMR for
the first time, it may be appropriate to review its
basic objectives.
    The Process Measurements Review reports on
items of interest in the development,  assessment,
and application of measurement  techniques  ap-
plicable to IERL-RTP energy and industrial process
research  and  development  programs. Articles
describing advances in sampling, analysis, quality
assurance, and on-line process control are featured
regularly.  The first few issues are primarily  based
on PMB-sponsored work.  However, it is intended
that future issues feature articles submitted by
other organizations. In this context, comments and
suggestions for future topics are actively solicited
by the IERL-RTP Task Officer and the Editor.
    The Process Measurements Review is available
to anyone involved or interested in measurement
techniques  applicable  to the characterization and
evaluation of energy and  industrial processes and
control  equipment. If you are  not currently re-
ceiving the Process Measurements Review and
would like to be on the mailing list, complete and
return the request form contained in this issue.
             SULFUR OXIDE



                The "Workshop on Measurement Technology
             and  Characterization of Primary  Sulfur Oxides
             Emissions from Combustion Sources" was held at
             Southern Pines, N.C., April 24-26, 1978. It was spon-
             sored by EPA's Environmental  Sciences Research
             Laboratory  (ESRL).  Twenty-eight  papers were
             presented that dealt with the sampling and analysis
             of particulate sulfate, sulfuric acid mist, and sulfur
             dioxide.  Also discussed were the effects of process
             operating parameters on the emission levels and on
             the measurement of these sulfur oxide species. Ac-
             curate discrimination between particulate sulfates
             and sulfuric  acid was identified as a major problem
             in the characterization of the emissions. The con-
             trolled condensation technique is the most accurate
             method presently available for this differentiation.
             However, even this technique may suffer losses of
             20 percent of the sulfur trioxide. A series of recom-
             mendations  for  research programs  in sulfur oxide
             measurements was  developed by the workshop at-
             tendees. Proceedings  of the  workshop will  be
             available soon.  Information is available from  the
             ESRL Project Officer, John Nader (919-541-3085).
                The views expressed in  the Process Meas-
            urements Review  do not necessarily reflect  the
            views and policies of the Environmental Protection
            Agency. Mention of trade names or commercial
            products does not constitute endorsement or recom-
            mendation for use by EPA.

Process Measurements Review
                  Volume 1, Number 2, Second Quarter, 1978
       For Level 1  environmental  assessment pro-
   cedures to be effective, the precision and accuracy
   of both the sample collection and sample analysis
   schemes  must satisfy  Level  1  data  quality re-
   quirements. The primary procedure for characteriz-
   ing process streams containing particulate matter
   and vapors is the Source Assessment Sampling
   System (SASS) for sample collection and specified
   analytical methods for subsequent sample analysis.
   An experimental program designed to evaluate the
   SASS and the associated  Level  1 analytical pro-
   cedures has been completed. The experimental pro-
   gram  was coordinated  by Research Triangle In-
   stitute (RTI) in conjunction with Arthur D. Little,
   Inc. (ADD, Southern Research  Institute (SoRI),
   TRW Systems, and Radian Corporation.
       The project  was conducted in two  phases.
   Phase I consisted of a field evaluation of the SASS
   on a preselected,  stable source characterized by
   high  organics and high particulate  loadings. Si-
   multaneous samples were collected with two SASS
   trains and a Method-5 train. Three complete sample
   runs were made. The relative positions of the trains
   were fixed with the probes of the  two SASS trains
   positioned at a point of average duct velocity and
   within a few inches of  each other. The Method-5
   train was downstream from the SASS  trains and
   operated according to the Federal Register method;
   i.e., the duct was traversed, and isokinetic sampling
   conditions were maintained. To ensure consistency,
   all analytical work for Phase I was  done  by one
   organization.  Results  from Phase I  were used to
   estimate within- and  between-train precisions for
   particulate and to estimate the biases of the SASS
   trains with respect to Method 5 for total particulate
   determinations. In  addition, the results were used
   for comparisons between SASS trains for organic
   and inorganic sampling.
   «   Phase  II  of  the  program  consisted of in-
   terlaboratory evaluation of the analytical methods
   involving the  analysis of split samples by par-
   ticipating laboratories. Three aliquots of each of
   three sample types were supplied to each of the
   three participating  organizations  for analysis by
   current Level 1 procedures. The three sample types

   •   A known, artificial, liquid sample containing 16
   •  A real particulate  sample obtained from a
      source significantly different from the one
      selected for Phase I sampling.
  •  The combined XAD-2 extracts from the SASS
     runs in Phase I.
 A full Level 1 analysis was performed on one aliquot
 of each of three sample  types; the remaining ali-
 quots  were analyzed  using  a reduced  Level  1


 Particulate Loading and Sizing
     Results of the particulate loading and sizing
 comparisons showed the following:
  •  Particle size distributions compared very well
     between  SASS trains  for all  three  runs.
     Typical results are shown in Figure 1.
  •  Particulate matter concentrations determined
     by the SASS  trains  compared very well with
     Method 5. The largest difference was within 20
     percent (Table 1).
  •   The estimated precision between trains, given
     as a standard deviation, is 36 mg/m3 (10 percent
     on a relative basis).

 Collected Organics
     A complete Level 1 organics analysis  was car-
 ried out on one set of SASS runs. For this set, the
 organic material  collected by the SASS  trains
 agreed well in quantity and composition (i.e., volatile
 (TCO), nonvolatile  (Grav), and organic compound
 categories) and was  collected proportionally in
 corresponding SASS components.  The results of
 volatile and nonvolatile analyses are given  in Table

 Collected Inorganics
    For one set of SASS runs, mercury, arsenic, and
antimony were determined by atomic absorption on
the combined second and  third impinger solutions.
For these limited  analyses, the data for each ele-
ment agreed within a factor of 2.
 Table 1. Particulate Matter Concentration,  mg/m3
SASS-1     SASS-2    Method 5
     1         408         337        342
     2         399         349        322
     3         353         315        371
a m 28 mg/m3 (8%) within train precision, including
source variation
(o2 +  o*)I/a = 36 mg/m3 (10%) between train preci-

Process Measurements Review
                                                Volume 1. Number 2. Second Quarter, 1978


            | 30

            3 25
            ° 20
            g  10

                              Figure 1. Comparison of particle size fractionation
                                            of two SASS trains.
         Table 2. Organic Extractables, mg/m3
        SASS-1 SASS-2 SASS-1 SASS-2 SASS-1 SASS-2

   TOO   0.03    0.01    3.41    3.58     (Rinse)

   Grav   1.65    1.58    10.2    8.99    69      81

   Total   1.7     1.6     13.6    12.6     69      81

        Certain methods  employed  in the  organic
   analysis scheme are  still being refined, and inter-
   pretation of the organic data from complex sources
   can be an involved process requiring great attention
to detail. However, from this preliminary analysis of
Phase II data, it appears that the organic analysis
scheme can yield results  of  adequate quality  to
satisfy Level 1 requirements.
    Results of the inorganic sample  preparation
and  Spark Source  Mass  Spectrometer  (SSMS)
analysis  scheme  indicate  that  variability in the
values for some  elements may be exceeding the
allowable factor of 2 to 3 in the Level 1 procedures.
The cause of the variability cannot be isolated with
the data available. Further studies will be initiated
to examine potential solutions to the problem.
    A report on the evaluation, in draft form, is be-
ing reviewed by EPA  with publication expected
shortly. Also, a paper describing the evaluation was
presented at the EPA process measurements sym-
posium in Atlanta in February. The proceedings  of
the symposium, including this paper, are scheduled
to be available soon. The IERL-RTP Project Officer
for the   SASS  evaluation  is  Bill  Kuykendal
                     (See page 6 for articles on ion chromatography and analysis of sulfur In coal.)

Process Measurements Review                                                Volume 1, Number 2. Second Quarter, 1978
                  LEVEL 1 ENVIRONMENTAL ASSESSMENT," EPA-600/2-76-160a

                  (Changes 1-5 were reported in the Volume 1, Number 1 issue of the PMR.)
          Change 6 -  "Cleaning XAD-2 with Methylene Chloride, Drying"
                      Appendix D, Page 130
                      Date Accepted: April 6, 1978

              To remove contaminants from manufacturer-supplied XAD-2 resin, the original procedure
          required cleaning of the resin by extraction with water, methanol, diethyl ether, and pentane.
          Ether and pentane are hazardous to store, difficult to contain in the extraction equipment, and
          present greater flammability and explosion hazards than other acceptable solvents. The new
          cleaning procedure substitutes methylene chloride for the ether and pentane. The old pro-
          cedure remains acceptable, but is no longer recommended for Level 1. In addition, the original
          procedure fails to specify a drying procedure for the cleaned resin. The new procedure
          specifies a fluidized-bed technique using pure nitrogen for drying.

          Change 7-   "Total Chromatographable Organic Analysis ITCOI"
                      Chapter VIII, Pages 82, 90, 93, and 102
                      Date Accepted: April 14, 1978

              The original procedures specified  analysis of Cj-Cg hydrocarbon compounds by gas
          chromatography  in the field. C 7-C12 compounds were analyzed in  the laboratory from solvent
          extraction  solutions.  Higher  molecular weight hydrocarbons  were classified by  liquid
          chromatography  from dried extract.  Data have shown that significant amounts of the more
          volatile compounds are lost in this analytical scheme. Therefore, the field analysis is expanded
          to include the C7 compounds and the laboratory solvent extraction analyses are expanded to
          include C8-C16 compounds. The nonvolatile compounds are characterized in the original man-
          ner after exchange to cyclopentane solvent.

          Change 8-   "Use of SASS Cyclones Without Vortex Breakers"
                      Chapter III, Page 29
                      Date Accepted: April 13,1978

              Originally, vortex breakers were specified for use in the three SASS cyclones. However,
          rigorous calibrations  of the cyclone set  have shown that the cut points for the two larger
          cyclones (10 and 3 micrometers) are more  nearly achieved without vortex breakers. According-
          ly, the procedure has been changed to specify that the 10- and 3-micrometer cyclones are to be
          operated without the vortex breakers.

          Change 9-   "IR  Sample Preparation and Analysis"
                      Chapter  VIII,  Page 102
                      Date Accepted: May 22, 1978

              The original  procedure for preparation of samples for infrared analysis specified the use
          of a single NaCl plate. However, single plate preparations are subject to sample evaporation
          and other adverse thermal effects. Therefore,  the procedure has been modified to require
          analysis of the sample between two NaCl plates or mixture of the sample material with KBr
          and formation of  a pellet.

          NOTE: Revisions appear in condensed form. For complete change notices, contact Ann Turner
          at RTI (919-541-6893).

Process Measurements Review
                  Volume 1, Number 2, Second Quarter, 1978
   D. E. Blake.

   Source Assessment Sampling System: Design and
   Development,  EPA-600/7-78-018,  PB  279757/AS

       This document chronologically describes the design
   and  development of the Source Assessment Sampling
   System (SASS). The SASS train is the principal sampling
   element for ducted sources when performing EPA's Level
   1 environmental assessment studies. As such, it  samples
   process streams and separates the samples into filterable
   particulate (four  size fractions), organic vapors,  and in-
   organic vapors. The design concept and philosophy are
   discussed, as well as the evolutionary development of the
   system. Developmental testing, problem areas, and subse-
   quent system changes are described in detail.  The docu-
   ment also includes a complete description of the calibra-
   tion  procedures used to determine the size cut points  of
   the particulate fractionating cyclones.

   J. C. Harris and P. L. Levins.

   EPA/IERL-RTP Interim Procedures for Level  2
   Sampling  and   Analysis  of  Organic Materials,
   EPA-600/7-78-016, PB 279212/AS (2/78).

       This document is an interim report representing con-
   cepts and guidelines to be utilized in considering pro-
   cedures for sampling and analysis of organic compounds
   during Level  2  environmental  assessments.  The
   guidelines are general  in nature, but suggestions for
   specific procedures are also presented. Please note that
   this is an interim document that will be replaced eventual-
   ly by a Level 2 Organics Procedure Manual That manual
   will  contain more developed concepts and procedures
   specified for a wide range of conditions.
       This document is intended for use by experienced
   research chemists who are thoroughly familiar  with en-
   vironmental sampling and analysis, Level 1 procedures,
   and the objectives of the phased approach. It does not at-
   tempt to teach details of EPA's Environmental Assess-
   ment Program.  Rather, it  relies  heavily on  reports
   previously published by IERL-RTP and its contractors.

   J. W. Adams, T. E. Doerfler, and C. H. Summers.

   Effect of Handling Procedures on Sample Quality,
   EPA-600/7-78-017, PB 279910/AS (2/78).

       This report presents results of an evaluation of the ef-
   fects of typical shipping and storage procedures on
   organic materials  collected  in Level  1 • environmental
   assessment studies. Parameters reviewed included sam-
   ple  container composition,  head  space composition,
   temperature,  lighting,   and  catalytic  species  content.
   Three sample sets representing fractions obtained during
   a Level 1 environmental assessment were used for the
   evaluation. Each contained six model organic compounds.
   A  simulated 3-week  shipping and storage  cycle
   represented elapsed time between sample collection and
   analysis. All three experiments,were conducted in accord-
   ance with statistical principles appropriate for  factorial
   experiments. Experimental results "were analyzed using
   analysis of variance to assess the relative effect of each
   shipping/storage condition studied.
L. N. Davidson, W. J. Lyman, D. Shooter, and J. R.

Technical  Manual  for  the  Analysis  of  Fuels,
EPA-600/7-77-143, PB 279196/AS (12/77).

    This manual is intended as a guide in research proj-
jects concerned with fuel combustion. It discusses stand-
ard methods of sampling and  analysis for a variety of
hydrocarbon fuels. The analyses  covered are  those of
prime concern to the combustion engineer. For each fuel
covered, the manual indicates the analyses that are likely
to be required,  the preferred method of analysis, and
available sampling procedures.  For each  method of
analysis listed,  the manual summarizes the  method,
discusses its applicability,  and describes its precision.
Gaseous fuels, liquid petroleum fuels, waste lubricating
oil, shale oil, coal liquids, methyl fuel, coal, coke, refuse-
derived solid fuels, and peat are included. The appendixes
give the availability of Standard Reference Materials for
fuel-related analyses, laboratory directories, typical values
(or ranges) of parameters specified for each fuel, and
results of fuel analyses conducted by the contractor.

P. P. Leo  and J. Rossoff.

Controlling S02 Emissions From Coal-Fired, Steam-
Electric Generators: Solid Waste Impact (Volumes 1
and 2), EPA-600/7-78-044a and -044b,  PB 281099/AS
and 281100/AS  (3/78).

R. L. Sugarek and T. G. Sipes.

Controlling S02 Emissions From Coal-Fired, Steam-
Electric  Generators:  Water  Pollution  Impact
(Volumes  1 and 2), EPA-600/7-78-045a and -045b, PB
279635/AS and 279636/AS (3/78).

J.  R.  Koscianowski,   L.  Koscianowska, and M.

Tests  of Fabric  Filtration  Materials,  EPA-
600/7-78-056, PB 279637/AS (3/78).

J. A.  Cavallaro, G. A. Gibbon, and  A. W.  Deur-
brouck.      ,

A Washability  and Analytical Evaluation of Poten-
tial Pollution   From  Trace  Elements in  Coal,
EPA-600/7-78-038, PB 28Q759/AS (3/78).
 Copies of these publications are available at cost
       National Technical Information Service
       U.S. Department of Commerce
       5285 Port Royal Road
       Springfield, Virginia 22151.

Process Measurements Review
                 Volume 1, Number 2, Second Quarter, 1978
       Ion exchange chromatography has long been
   known as a powerful tool for the separation of ions
   in solution. Until recently  though, its applicability
   has been somewhat limited  by the lack of a universal
   ion detection technique. One technique responsive
   to all ions, conductimetric detection, was considered
   impractical because of the presence of the high con-
   centration of electrolytic eluent normally  used  in
   the separation. A novel technique, developed by
   H. Small, T.  S. Stevens, and H. G. Bauman, and
   reported in a 1975 issue of Analytical Chemistry,
   reduces this background to a minimum and makes
   possible the use of a conductimetric detector. The
   key to the technique is a second eluent neutraliza-
   tion column in series with the separator column. The
   combination of these two  columns and a  conduc-
   timetric detector has resulted in a new analytical
   methodology known  as ion  chromatography.
       Ion chromatography allows  the separation and
   detection of several anions as low  as  10 ppb in a
   single analysis. Analysis time is less than 30 minutes
   and precision (replicability) is better than ± 3 per-
   cent. Numerous applications  of the  technique have
   begun  to appear  in the  literature. Mulik, et al.
   reported in a 1976 issue of Analytical Letters the
   use of ion chromatography to determine sulfate and
   nitrate in ambient aerosols. Recently,  Steiber and
   Statnick demonstrated  the  applicability  of  this
   technique in the measurement of sulfite and sulfate
   in flue gas desulfurization systems. The paper has
   been published by Ann Arbor Science Publishers,
   Inc.  in  a   book  entitled  "Ion  Chromatographic
   Analyses of Environmental Pollutants." Applicabili-
   ty of the technique in the study of wet limestone and
   dual alkali scrubbers has also been demonstrated in
   work conducted at TRW Systems, Redondo Beach,
   California, for EPA. Finally, S. A. Bouyoucos stated
   in an article in Analytical Chemistry that ion  chro-
   matography has been used for the determination of
   certain organic compounds.
       Because ion chromatography is a rapid,  sen-
   sitive, and selective method for the analysis of a
   large variety of ions, it is now being considered as a
   technique for the laboratory-based  analyses of all
   simple and complex  anions and select cations (e.g.,
NH4 "*") in  the  Level  1  environmental  assessment
program. The anions to be analyzed would include
NOg-, N03-, SOg^, S04 = ,  P04S, F-,  and
Cl   .From  an  analytical  point  of  view,  ion
chromatography is much more efficient than using a
variety of individual analysis techniques, including
classical colorimetric techniques and ion selective
electrodes. Indeed, one  can safely predict that ion
chromatography will  replace  such techniques in
many other  laboratories  in addition  to those  in-
volved in the Level 1 program.
    For further information  on  how ion  chro-
matography is being utilized in the environmental
assessment  program,  contact Ray Merrill, IERL-
RTP (919-541-2557).
    An improved technique for the analysis of
sulfur forms (pyritic, organic, and inorganic) in coal
has been developed by TRW Systems and Energy,
Redondo Beach, California, under an EPA program.
The procedure uses low temperature plasma ashing
to remove organic sulfur from the  sample, leaving
the pyritic and inorganic sulfur free of interferences
from the organic matrix. To evaluate the procedure,
sulfate sulfur and pyritic sulfur were determined on
a series of nine plasma ashed coals in triplicate and
the results compared to analyses of the same coals
using standard  ASTM procedures. Three  of  the
samples were Eastern interior coals expected to
contain  significant amounts  of sulfur occurring as
finely divided, homogenous particles. Six were Ap-
palachian coals expected to have the sulfur occurr-
ing in large particle nodes.
    The sulfate sulfur values  determined  for
Eastern interior  coal by plasma ashing were 40 per-
cent  higher  than those  determined  by ASTM
methods. They  were 14 percent  higher for Ap-
palachian coals.  Pyritic sulfur  values  by plasma
ashing were 8 percent higher for Eastern interior
coals and 8 percent lower for Appalachian coals than
the ASTM values. The plasma ashing procedure
gave total inorganic  sulfur results which were 24
percent higher than ASTM procedures for Eastern

Process Measurements Review
                                                                      Volume 1, Number 2, Second Quarter, 1978
   interior coals and 1.4 percent lower for Appalachian
   coals. Results from a single sample of coal tailings
   showed differences  in  the total inorganic sulfur
   values that  were  similar to those for Eastern in-
   terior coals;  i.e., the ashing results were 22 percent
   higher than the ASTM procedure values. These
   results indicate that the plasma ashing procedure is
   more effective for analyzing coals containing finely
   divided sulfur than  the  ASTM procedures and is
   equally as effective  as the ASTM procedures for
   other coals.
        The TRW program will also investigate exten-
   sion of the plasma ashing technique to the direct
   measurement of organic sulfur. This will be accom-
   plished by trapping the sulfur dioxide liberated dur-
   ing the ashing process. Successful completion of this
   project will provide a  technique which  directly.
   analyzes all three sulfur forms in a single sample of
   coal. The IERL-RTP Project Officer is Frank Briden
                                                       FUGITIVE EMISSIONS SYMPOSIUM
                                                         The "Third Symposium on Fugitive Emissions:
                                                     Measurement and Control," sponsored by EPA's In-
                                                     dustrial Environmental Research Laboratory-RTP,
                                                     will be held October 23-25 at the Jack Tar Hotel, San
                                                     Francisco, California. The symposium will provide a
                                                     forum for the exchange of information on the  im-
                                                     pact,  measurement, and control of airborne and
                                                     waterborne  fugitive   emissions from  industrial
                                                     sources.  Twenty-five  speakers from  industrial,
                                                     academic, and  governmental  organizations  will
                                                     discuss the current status of research, development,
                                                     and applications studies. If you are interested in at-
                                                     tending the Symposium, contact Hank Kolnsberg or
                                                     Joanne  King,  TRC,  Wethersfield,  Connecticut
                          Request for the Process Measurements Review
I Address.
                                             Position or Title.
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                       Return to:
                                       Ann Turner
                                       Research Triangle Institute
                                       P.O. Box 12194, Building 6
                                       Research Triangle Park, N.C. 27709
     Check if applicable:
                                   I	j Incorrect address

 Process Measurements Review
                                            Volume 1, Number 2, Second Quarter, 1978
          The Process Measurements Review is prepared by the Research Triangle Institute, P. 0. Box 12194,
       Research Triangle Park, N.C. 27709, for the U.S. Environmental Protection Agency, Industrial En-
       vironmental Research Laboratory, Process Measurements  Branch, Research Triangle Park,  N.C.
       27711, under EPA Contract No. 68-02-2156. The EPA Task Officer is James A. Dorsey (919-541-2557)
       and the RTI Editor is Raymond M. Michie, Jr. (919-541-6492). Comments on this issue and suggestions
       for future topics are welcome  and may be addressed to either the Task Officer or the Editor.
United States
Environmental Protection
Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, N.C. 27711
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