United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
Research and Development
EPA-600/S9-81 -018 June 1982
Project Summary
Proceedings:
Symposium on
Process Measurements for
Environmental Assessment
February 25-27, 1980
Philip L. Levins, Judith C. Harris, and Karen D. Drewitz
This report is a summary of the
proceedings of the Second Symposi-
um on Process Measurements for
Environmental Assessment held in
Atlanta, GA, February 25-27. 1980.
The symposium focused on the
state-of-the-art of sampling and anal-
ysis techniques that are appropriate
for process measurements in the
context of an environmental assess-
ment program. It included methods
for qualitative and quantitative chemi-
cal characterization of organic and
inorganic species in process and dis-
charge streams and biologi9al assays
of environmental samples. The sym-
posium represents a continuing effort
on the part of the Process Measure-
ments Branch of the EPA's Industrial
Environmental Research Laboratory
at Research Triangle Park, NC, to
share recently developed methodology
and encourage the interchange of
ideas among researchers in govern-
ment, industry and academia. Topics
included:
• Use of sorbents for sampling.
• Sampling of reactive species.
• Sampling and analysis methodol-
ogy for coal conversion processes.
• Advanced inorganic analysis tech-
niques.
• Advanced organic analysis tech-
niques.
• Application of bioassay methods
to complex samples.
The interchange of information was
accomplished through the presenta-
tion of 22 papers and through a poster
session. The poster session was an
experiment at this symposium that
proved very successful. Twelve re-
search groups were provided space
during one evening session to display
posters outlining their research pro-
grams. Leaders involved in the 12
programs manned the exhibits and
responded to questions by attendees
on an informal basis.
This Project Summary was develop-
ed by EPA's Industrial Environmental
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).
Summaries of the speakers'
remarks follow:
M. R. Guerin, Analytical Chemistry
Division, Oak Ridge National
Laboratory
Guerin discussed disciplinary ap-
proaches to program objectives, empha-
sizing the integrated approach to chem-
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ical/biological analysis. He stated that,
while environmental and health assess-
ments are increasingly dependent on
the results of biological testing, biologi-
cal testing, in turn, is becoming increas-
ingly dependent on physical and chemi-
cal assistance to achieve reliable and
interpretable results. Examples of on-
going programs related to environmen-
tal assessments were presented by
Guerin to indicate the nature of the
products generated at various levels of
interaction. He identified the three
approaches to program objectives as the
independent, the interactive, and the
integrated approaches. Guerin explained
that the most effective approach to an
integrated chemical/biological program
requires that each level of interaction be
present and that the collaborating
groups give the programmatic objective
as much attention as is given to discipli-
nary concerns.
A. R. Kolber, Research Triangle
Institute
Kolber described results of a study of
the toxic potential of coal gasification
byproducts and effluents. He also rec-
ommended future bioassay study needs
in support of a major synfuels industry.
Kolber explained that the study indicates
that simple bioassay of crude complex
mixtures, such as effluent tar and oils,
may not provide an accurate estimation
of potential health risk when these
mixtures contain highly bioactive minor
substituents, or when antagonistic
reactions within the mixture mask
actual mutagenicity and/or toxicity.
Kolber summarized recent progress
in sampling, chemical analysis, and
bioassay methodology development for
synthetic fuel process effluents (com-
plex mixtures). He characterized the
various streams and effluents of envi-
ronmental significance regarding po-
tentially hazardous substances, and he
specified bioassay tests for various
types of samples.
J. C. Harris, Arthur D. Little, Inc.
Harris gave results of a systematic
laboratory investigation of the applica-
bility of macroreticular resins for general
and compound-specific sampling of
organics from water, based on small-
scale chromatographic experiments.
She explained that the objective was to
develop screening procedures and a
data base that would allow selection of
the resin(s) best suited to a particular
sampling application and selection of a
sampling module size/configuration
that gives quantitative collection of
contaminants) from the aqueous stream
of interest. Harris described the experi-
mental approach which involved quan-
titative characterization of sorbent/sor-
bate systems by frontal chromatographic
analysis of breakthrough and measure-
ment of recovery. Effects of sample flow
rate, sorbent type, organic compound
type, and (to a limited extent) sample
matrix have been considered and were
also described.
Harris concluded by reporting that a
mixed resin cartridge, incorporating
XAD-2 for collection of non-polar or-
ganics and XE-347 for collection of
polar organics, has been tested and
appears promising for full-scale sam-
pling applications.
W. F. Gutknecht, Systems and
Measurements Division, Research
Triangle Institute
Gutknecht detailed the approaches to
measurement and interpretation of
infrared (IR) and low resolution mass
spectra (LRMS) taken by four EPA
contractors following the guidelines of
the Level 1 Environmental Assessment
Program. He also discussed the mecha-
nism of evaluation which involved
supplying each contractor with test
spectra and samples for analysis and
interpretation. Using IR, the contractors
identified 55 to 85 percent of the struc-
tural moieties present in the various
samples, and, using LRMS, the contrac-
tors identified 50 to 90 percent of the
compound classes represented.
The sources of error in IR and LRMS
measurement and interpretation were
identified, and Gutknecht suggested
methods to improve data quality and
interpretation. He stressed that thor-
oughness of interpretation is most
important for accuracy of the IR anal-
yses. Recommendations to improve
LRMS data quality include using the
reference series Eight Peak Index of
Mass Spectra, setting intensity and
mass/charge range criteria to simplify
spectra, using the LC fraction data with
caution, and analyzing IR and LRMS
data independently to avoid bias.
K. W. Lee, Radian Corporation
Lee described characterization of coal
gasification by-products and ambient
air samples taken from a Lurgi gasifica-
tion facility in the Kosovo Region of
Yugoslavia. Primary by-products, or-
ganic vapors, and particulate-borne
organics were analyzed for sulfur- and
nitrogen-containing organic compounds
using selective-detector gas chromato
graphy. The main problem was correla-
ting the emissions from the gasificatior
plant with the components found in the
ambient air samples.
Lee discussed the phased analytica
approach that was developed to solve
the correlation problem. The methods
verifications, and quality controls were
discussed and the application of these
methods to the Lurgi gasification facility
was outlined. According to Lee, selective
detection revealed a positive correlatior
between sulfur- and nitrogen-containing
compounds in the primary by-products
and the ambient air samples. Relative
quantification and tentative identifies
tion of the major sulfur- and nitrogen-
containing compounds was establishec
by comparison with standards and b\
peak enrichment techniques. These
identifications were confirmed by GC/
MS.
Bruce W. Farnum, Grand Forks
Energy Technology Center, U.S.
Department of Energy
Farnum discussed the characteriza
tion of process streams from the lique
faction of low-rank coal with synthesis
gas (1:1 CO:H2>. He identified the process
streams obtained and described the
methods of analysis chosen for eac\
stream. Reaction conditions were als<
specified. The characterizations of th<
water effluent, the light oils, and thi
heavy oils were described in detail b<
Farnum.
J. M. Giddings, Environmental
Sciences Division, Oak Ridge
National Laboratory
Giddings described the 4-hour photo
synthesis test which is a rapid bioassa
to measure the effects of coal-derive^
materials on algal photosynthesis
Researchers at Oak Ridge Nations
Laboratory developed the test as part c
an overall program to assess the poten
tial environmental hazards of coa
conversion technologies.
Giddings explained that algal culture
or natural algal communities are ex
posed to the test materials for 4 hours
Photosynthesis is determined by th
14C-bicarbonate method during the fine
2 hours of exposure and compared wit
controls for a measure to toxicity. I
bioassays with individual aromati
compounds, quinones and aromati
amines were found to be particular)
toxic to algae; azaarenes and thiophene
were the least toxic classes testec
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Experiments with the water soluble
fractions (WSFs) of more than 20 natural
and synthetic oils showed that coal
liquefaction products are considerably
more toxic than petroleum products;
shale oils are intermediate in toxicity.
Further studies with particular subtrac-
tions of several WSFs have identified
ether-soluble bases as the major contri-
butors to the toxicity of coal-derived oils.
Giddings also reported on and ex-
plained the advantages that the 4-hour
photosynthesis test has over the Algal
Assay Bottle Test for measuring the
toxicity of complex materials.
V. A. Fassel, Ames Laboratory (U.S.
Department of Energy) and the
Department of Chemistry (Iowa State
University)
Fassel described the direct determi-
nation of benz(a)pyrene and other poly-
nuclear aromatic hydrocarbons (PAHs)
in SRC II, a coal liquid and a sample of
shale oil by the utilization of laser-
excited Shpol'skii effect spectroscopy
(LESS). This is a simple and less elabor-
ate approach than the existing method-
ologies which require that individual
compounds or a small group of com-
pounds be isolated by utilizing high
performance liquid chromatography,
capillary column gas chromatography,
or thin layer chromatography. Detection
and quantitation of the isolated PAH
compounds is usually performed by
mass spectrometry or luminescence
spectrometry. In contrast, LESS allows
the determinations to be accomplished
without prior isolation of the compounds.
Fassel explained that less of PAHs in
n-octane, frozen to a solid at 15 K, has
been utilized to achieve: (1) site selected
luminescence of a PAH compound, (2)
selectively excited luminescence of any
individual alkylated benz(a)anthracene
present in a mixture of multialkylated
benz(a)anthracenes, and (3) quantitate
selected PAHs including benz(a)pyrene
in diluted samples of SRC II and shale
oil.
T. Vo-Dinh, Health and Safety Research
Division, Oak Ridge National Labora-
tory
Vo-Dinh reported on a study to gauge
how well certain rapid, easy-to-use, and
cost-effective luminescence techniques
can be employed for the analysis of
polynuclear aromatic (PNA) compounds.
Two luminescence techniques were
considered; synchronous luminescence
(SL) spectroscopy of solutions at room
temperature and room temperature
phosphorimetry (RTP).
Vo-Dinh described the analysis carried
out on 13 polynuclear components in a
liquid chromatography fractionated
XAD-2 extract from Source Assessment
Sampling System runs. This same
sample was used, in an interlaboratory
evaluation of current Environmental
Protection Agency Level 1 organic
analysis procedures. Comparative re-
sults show that SL and RTP provide data
that are of more than adequate quality
for Level 1. These techniques should
also be seriously considered in the
development of Level 2 organic analysis
procedures.
Vo-Dinh also gave an example of the
use of luminescence for rapid screening
of an unfractionated coal liquefaction
product for a major PNA component.
D.L. Stalling, Columbia National
Fisheries Research Laboratory, U.S.
Fish and Wildlife Service
Stalling summarized the application
of a series of modular chromatographic
enrichment procedures designed to be
integrated into an automated sequential
system, controlled by a microprocessor,
for fractionation of complex residues
extracted from environmental samples.
Stalling reported that complex multiclass
residues are usually encountered in the
analysis of environmental samples for
organic contaminants. Analyses of this
type can be facilitated by a comprehen-
sive approach, including fractionation of
contaminants by class. He described the
three modular chromatographic proce-
dures developed and tested in an effort
to provide such a procedure: gel perme-
ation chromatography (GPC), cesium
silicate chromatography (CsSC), and
dispersed-carbon chromatography.
These procedures have enabled detec-
tion of chlorinated dibenzofurans,
terpenes, naphthalenes, and phenolics
in addiiton to the common organochlorine
pollutants in fish samples by electron
capture gas chromatography (EC-GC),
negative ion mass spectrometry (Nl-
MS), and conventional GC/MS.
D.C. Tigwell, Illinois Environmental
Protection Agency
Tigwell described the design and
construction of a multichannel, remote-
controlled, Teflon-and-glass positive-
displacement apparatus and its use for
the simultaneous sampling of trace
organic compounds on XAD and granular
activated carbon. He explained the
sampling theory which led to the con-
clusion that the type of information
which will be most useful for assessing
the environmental impact of trace levels
or organic compounds is loading data
obtained from constant-volume (time-
proportioned) composite samples. The
theoretical results define the sampling
requirements of the composite which
consequently specify the operational
requirements of the composite sampling
device. Tigwell showed how the sam-
pling and operational requirements are
met by the new composite sampler.
Tigwell also cited several applications
of this apparatus. It has been used to
collect samples of raw and finished
drinking water, samples from the Illinois
River, and from municipal and industrial
effluents, including an untreated coal
conversion process wastewater. Four
radio-controlled units are being used in
a nationwide EPA-funded study of the
movement of organics through munici-
pal treatment plants.
K.T. Menzies, Arthur D. Little, Inc.
Menzies discussed two ion chroma-
tographic techniques developed to
quantify formic and acetic acid in both
diesel engine exhaust and mine air
subjected to diesel emissions. A com-
monly reported anion separation system
(utilizing a weak borate eluent) ade-
quately separated the acids of interest
in diesel exhaust. It was, however,
affected by the presence of strong acids
during subsequent consecutive analyses.
Menzies explained that, in order to
preclude this problem and the necessary
frequent regeneration of the anion
system's suppressor column, an ion
chromatography exclusion scheme was
utilized. Samples collected in a mine
environment were reliably concentrated
by freeze-drying and then analyzed on
an ICE system with dilute hydrochloric
acid eluent. The precision of the ICE
method was experimentally determined
to be ± 2.5%. The accuracy was not
independently determined but good
precision and recovery yield confidence
that measured values are within ±5% of
the true value. No interferences were
observed in the ICE system due to strong
acids, carbonic acid, or other water
soluble species present in mine air
subject to diesel emissions.
R.P. Baldwin, Department of Chem-
istry, University of Louisville
Baldwin described and tentatively
evaluated a new electroanalytica! ap-
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proach using chemically modified elec-
trodes for the determination of specific
classes of organic compounds. In par-
ticular, Baldwin considered a model
analytical system applicable specifically
for the determination of dissolved alde-
hydes and ketones.
The method detailed by Baldwin
proposes the use of recently developed
chemically modified electrodes (CMEs):
first to pre-concentrate a specific organic
analyte at the electrode surface via a
selective chemical reaction; and then to
quantitate the subsequent surface-
bound reaction product via conventional
voltammetric techniques. Baldwin ex-
amined the chemical reactivity of the
surface-modifying functional groups
toward specific classes of organics with
respect to the sensitivity enhancement
and the gross chemical selectivity that
can be imparted by means of the pre-
concentration step.
In the example described by Baldwin,
for the model analyte ferrocene carbox-
aldehyde, a detection limit of lO^M was
observed using a pre-concentration
time of only 5 minutes. No major inter-
ference was observed when the analysis
was carried out in the presence of a
hundredfold excess of ferrocene.
J. Cairns, Jr., University Center for
Environmental Studies and Biology
Department, Virginia Polytechnic
Institute and State University.
Cairns discussed a computer-inter-
faced toxicity testing system for simu-
lating variable effluent loading. Minl-
and microcomputer interfacing with a
toxicity testing system provides a means
of systematically varying the concentra-
tion of a test chemical or chemicals in a
continuous-flow system. The same
computer can also be used for the data
acquisition system to store the volumi-
nous time-series biological response
data necessary for cross correlations
with variable chemical concentrations.
Cairns described the instrumentation
making such tests feasible and gave an
example of a toxicity test on fish using
this method. According to Cairns, the
apparatus and the results of the test
provide compelling evidence that suf-
ficient promise exists for resolving some
or all of the problems encountered in
simulating "real world" conditions in
toxicity testing and for justifying con-
tinued research and development of the
apparatus.
M. Auyong, Lawrence Livermore
Laboratory
Auyong discussed the design and
operational experience of the on-line
wastewater monitoring system at the
Lawrence Livermore Laboratory. This
system was developed to monitor the
sewage effluent on a continuous basis
as a check on control procedures. The
monitoring system is designed to detect
elevated radiation, metal concentration,
and pH levels.
The detection assembly was described
by Auyong as consisting of an x-ray
fluorescence unit which detects high
levels of metals, sodium iodide crystal
detectors that scan the sewage for the
presence of elevated levels of radiation,
and an industrial probe for pH monitor-
ing. With the aid of a microprocessor,
the data collected are reduced and anal-
yzed to determine whether levels are
approaching established environmental
limits. If these levels are exceeded, a
sample of the suspect sewage is auto-
matically collected for further analysis,
and an alarm is sounded to alert per-
sonnel.
Auyong gave examples of instances
when the monitoring system has helped
to avert treatment plant problems when
a spill has occurred.
D.E. Bause, GCA/Technology Division
Bause gave results of an evaluation of
four leachate procedures, ASTM Method
A, ASTM Method B, EPA/OSW Extrac-
tion (EP), and Carbonic Acid Extraction
(CAE). They were examined for their
general applicability, reproducibility,
Environmental Assessment methods
compatibility, and leaching power.
Bause explained that the leachates
generated by these methods were anal-
yzed for nine metals by atomic absorp-
tion methods and for F", Cl~, and SCu2" by
ion chromatography. Seven energy
process wastes (including oil shale, FBC
waste, fly ash, boiler slag, scrubber
sludge, and hopper ash) were extracted
to evaluate the general applicability of
the leachate tests.
Results described by Bause indicated
that the ASTM methods had the best
reproducibility, while the EP had the
poorest precision. The EP and CAE
procedures leached the largest quanti-
ties of trace metals from the wastes.
However, based on the total metal
concentration in the sample, the leachate
methods generally extracted < 1 %. The
EP and ASTM-B methods caused some
difficulty with flameless AA analyses.
Based on the Resource Conservation
and Recovery Act (RCRA) criteria, five of
the energy wastes would be classified
as hazardous by at least one of the
leachate procedures. Selenium usually
exceeded the threshold value for the
leachate.
Bause concluded by recommending
improvements to the leachate test.
D.J. Brusick, Director of the Depart-
ment of Genetics and Cell Biology,
Litton Bionetics, Inc.
Brusick reviewed sample collection,
storage, and pretest handling proce-
dures, and illustrated how the applica-
tion of these techniques to the specific
health effects and ecological tests
proposed for Level 1 biological assess-
ment will affect the test responses and
ultimately the goals of this program.
Level 1 Environmental Assessment
Bioassays should permit an accurate
ranking of emissions from stationary
site sources with respect to their poten-
tial hazard. Moreover, the ranking must
ensure that the potential hazard is likely
to be derived from the emissions as
released into the environment and that
pretest processing should be kept to a
minimum and applied uniformly across
all Level 1 bioassays if performed.
Brusick stressed the importance of
the sample history in the final inter-
pretations of the test results. He also
stressed that Level 1 assessment should
include the environmental fate and rate
of release of the emission along with the
chemical and bioassay toxicity determi-
nations.
D.F.A. Natusch, Colorado State
University
Manuscript not available.
G.L. Fisher, Battelle Columbus Labo-
ratories
Fisher described the application of
bioassays including bacterial mutagen-
esis, mammalian lung cell function, and
mammalian hematopoietic cell matura-
tion to the study of the biological signifi-
cant physical and chemical properties of
coal fly ash. He discussed the effects of
sample collection, particle size, solvent
extraction, temperature treatment, and
irradiation.
He reported that the results of the
study demonstrate the extreme com-
plexity of coal fly ash in terms of matrix
composition, morphological appearance,
surface trace element, and organic
chemical composition. Acute inhalation
studies have demonstrated that coal fly
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ash may be equally as toxic as alpha-
quartz to the pulmonary alveolar macro-
phage. The feasibility of application of
sophisticated cloning techniques for the
evaluation of potential lympohemato-
poetic effects from complex mixtures
has been demonstrated. Mutagens in
coal fly ash appear to be absorbed to fly
ash surfaces and hence may exist in the
environment for relatively long periods
of time. Fisher also described new tech-
niques which are being developed to
evaluate the carcinogenic potential of
coal fly ash and to measure the potential
immunotoxicity of fly ash.
K.T. McGregor, GCA/Technology
Division
McGregor summarized part of a recent
series of studies to evaluate several
areas of the Level 1 elemental analysis
scheme. The effects of organic matter
on elemental determinations by spark
source mass spectrography (SSMS), the
primary Level 1 elemental analysis
technique, were investigated. In addi-
tion, several sample preparation tech-
niques were evaluated in terms of
efficacious elimination of organic matter
without resultant elemental losses or
contamination. The utility of the methods
as preparation techniques for atomic
absorption spectrometry (AAS) mea-
surements (principally Hg) was also
assessed.
McGregor reported the Level 1 ele-
mental analysis scheme to be reliable
and to provide the kind of information
desired from the Level 1 study. Prob-
lems were noted with some SSMS
determinations and additional work in
this area is recommended. The prepara-
tion of paniculate filter samples for
SSMS analysis by the Level 1 Acid
Extraction procedure may bias the
resulting data. The Modified Hydrofluoric
Acid Digestion Bomb method shows
great promise as a Level 2 preparation
procedure for analytical techniques
requiring solution samples.
R.F. Maddalone, TRW DSSG
Maddalone described the application
of several inorganic sampling and anal-
ysis methods to paniculate samples
from oil- and coal-fired boilers equipped
with FGD systems. As a result of these
analyses, data was obtained on such
topics as SMSS accuracy, trace element
enrichment across an FGD, particle size
and elemental distribution, surface
composition, and compound identifica-
tion using Fourier Transform Infrared
(FTIR) instruments.
Maddalone discussed the results that
showed that certain elements (As, Cr,
Mn, Ni, Sb, Se, V, and Zn) exhibit a
concentration increase in the paniculate
matter emitted from one examined FGD
system compared to the material enter-
ing a FGD under both oil- and coal-
firings. This enrichment is due to the
preferential emission of small particles
(<3 yum) which contain increased con-
centrations of these trace elements.
Surface analysis using Electron Spec-
troscopy for Chemical Analysis (ESCA)
showed that particles emitted from the
La Cygne FaD system were coated with
sulfur and carbon. The materials emitted
from an FGD can be identified using
FTIR. Sensitivities on the order of 0.1
/ug/cm2 can be expected for FTIR.
R.L. Barbour, Battelle Columbus
Laboratories
Barbour discussed the application of
Fourier Transform Infrared Spectros-
copy (FTIR) to environmental assess-
ment programs and various sample
handling methods. Also discussed, in
relation to their potential contributions
to the field of environmental assess-
ment, were inorganic compound spe-
ciation and on-the-fly GC/FTIR.
Barbour explained that FTIR is a
versatile tool in the field of environ-
mental assessment because it is the
only method by which both organic and
inorganic compounds can be analyzed.
Information concerning both inorganics
and organics can range from simple
class determination to compound-by-
compound characterization of the
sample. Methods currently being devel-
oped such as the computer-assisted
spectral interpretation program and
GC/FTIR, promise rapid expansion of
application of FTIR to the field of envi-
ronmental assessment.
Philip L. Levins, Judith C. Harris, and Karen D. Drewitz are with Arthur D.
Little, Inc.. Cambridge. MA 02140.
Larry D. Johnson is the EPA Project Officer (see below}.
The complete report, entitled "Proceedings: Second Symposium on Process
Measurements for Environmental Assessment, February 25-27,1980, "(Order
No. PB 82-211 574; Cost: $27.00, 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:
Industrial Environmental Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
: 1982—559-092/3426
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