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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