PROCESS
MEASUREMENTS
REVIEW
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INDUSTRIAL
ENVIRONMENTAL
RESEARCH
LABORATORY
Volume 1, Number 2
Research Triangle Park, N.C. 27711
Second Quarter, 1978
WHAT IS THE
PROCESS
MEASUREMENTS
REVIEW?
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
MEASUREMENT
WORKSHOP
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.
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Process Measurements Review
Volume 1, Number 2, Second Quarter, 1978
FIELD EVALUATION OF THE SOURCE ASSESSMENT
SAMPLING SYSTEM AND LEVEL 1 PROCEDURES
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
were:
A known, artificial, liquid sample containing 16
components.
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
scheme.
PHASE I RESULTS
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
2.
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
Run
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-
sion
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Process Measurements Review
Volume 1. Number 2. Second Quarter, 1978
40
35
| 30
3 25
<
° 20
u.
15
g 10
SASS2
SASS1
it-
Cyclone
Cyclone
Cyclone
Filter
Figure 1. Comparison of particle size fractionation
of two SASS trains.
Table 2. Organic Extractables, mg/m3
Cyclone
XAD-2
(Extract)
XAD-2
(Module)
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
PHASE II RESULTS
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
(919-541-2557).
(See page 6 for articles on ion chromatography and analysis of sulfur In coal.)
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Process Measurements Review Volume 1, Number 2. Second Quarter, 1978
REVISIONS TO "1ERL-RTP PROCEDURES MANUAL:
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).
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Process Measurements Review
Volume 1, Number 2, Second Quarter, 1978
RECENT EPA PUBLICATIONS OF INTEREST
D. E. Blake.
Source Assessment Sampling System: Design and
Development, EPA-600/7-78-018, PB 279757/AS
(2/78).
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.
Valentine.
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.
Szablewicz.
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
from:...-,-..
National Technical Information Service
U.S. Department of Commerce
5285 Port Royal Road
Springfield, Virginia 22151.
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Process Measurements Review
Volume 1, Number 2, Second Quarter, 1978
ION CHROMATOGRAPHY
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).
ANALYSIS OF SULFUR IN COAL
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
6
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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
(919-541-2557).
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
(203-563-1431).
Request for the Process Measurements Review
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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
Agency
Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, N.C. 27711
Official Business
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