United States
Environmental Protection
Agency
Research and Development
Atmospheric Research and
Exposure Assessment Laboratory
Research Triangle Park NC 27711
EPA/600/S3-91/071 Jan. 1992
w EPA Project Summary
Superfund Innovative Technology
Evaluation, The Delaware SITE
Study, 1989
W.A. McClenny, G.M. Russwurm, M.W. Holdren, A.J. Pollack, J.D. Pleil,
J.L. Yarns, J.D. Mulik, K.D. Oliver, R.E. Berkley, D.D. Williams
K.J. Krost, and W.T. McLeod
The Delaware SITE (Superfund Inno-
vative Technology Evaluation) Study
was carried out by personnel from the
Atmospheric Research and Exposure
Assessment Laboratory (AREAL), U.S.
EPA, and AREAL contractors, Battelle
Columbus Laboratory, ManTech Envi-
ronmental Technology, Incorporated
(formerly NSI Environmental Sciences),
and Tecan Remote, Incorporated. Per-
sonnel of the Delaware Department of
Natural Resources and Environmental
Control (DNREC) hosted the operation
and obtained permission to use local
sites for monitoring. The objective of
the study was to field test several moni-
toring methods that have progressed
through a feasibility testing stage and
appear ready for predemonstration test-
ing at Superfund sites. Monitoring oc-
curred near four Superfund sites in the
vicinity of New Castle, Delaware, and at
the Delaware Reclamation Plant located
just north of the Delaware Memorial
Bridge. Several different types of new
monitoring equipment were deployed
including: (1) automated gas chromato-
graphs, (2) canister-based sequential
samplers, (3) personal sampling de-
vices, (4) canister-based sector sam-
plers, (5) long path infrared transmission
monitors, and (6) solid sorbent-based
phenolic compound samplers.
This Project Summary was devel-
oped by EPA's Atmospheric Research
and Exposure Assessment Laboratory,
Research Triangle Park, NC, to an-
nounce key findings of the research
project that Is fully documented in a
separate report of the same title. (See
Project Report ordering Information at
back.)
Introduction
The Superfund Innovative Technology
Evaluation (SITE) Program promotes the
development, acceptance, and use of prom-
ising innovative technologies capable of
meeting the objectives of the overall Su-
perfund program. One objective of the pro-
gram is to provide the means for developers
of technology to demonstrate innovative
technologies at Superfund sites as alter-
natives to the systems currently in use. A
second objective is to provide support to
stimulate the development of promising
concepts and technologies to the point
that they are suitable for demonstration at
Superfund sites. In the case of the Dela-
ware SITE program, a proposal was made
by AREAL to the SITE program coordina-
tor to carry out predemonstration testing of
new monitoring techniques. After accep-
tance, a schedule was established for the
testing in the summer of 1989. (
The schedule of the SITE project con-
sisted of the following items:
Selection of a field site
Predemonstration plan preparation
a. Planning/coordination meeting
with participants, and
b. Preparation of plans for
predemonstration testing.
1. Documentation of experimen-
tal design, and
2. Preparation and clearance of
a quality assurance plan.
Preliminary field screening study
Preparation of a target compounds
list for each test site
Printed on Recycled Paper
-------
• Performance of the field testing
• Review of data and preparation of a
highlight report
• Presentation of preliminary data at
the 1990 EPA/AWMA Symposium on
Measurement of Toxic and Related
Air Pollutants
Development of information products
for the SITE program
The site proposed by J.J. Kliment of
the Delaware Department of Natural Re-
sources and Environmental Control
(DNREC) was selected. The site was near
New Castle, Delaware, and included four
Superfund sites and one site near the Dela-
ware Reclamation Plant. A map of all the
sites is shown in Figure 1. Figure 1 shows
the Superfund sites: Army Creek, Dela-
ware Sand and Gravel, Halby, and Stan-
dard Chlorine along with the Pigeon Point
site which is nearthe Delaware Solid Waste
Authority. The location of a monitoring site
in the residential area referred to as
Llangollen Estates and the P4 monitoring
site maintained by the state of Delaware
are also shown. The Standard Chlorine
plant site was part of a large industrial
complex.
Experimental Plan
The experimental plan called for five
methods of monitoring to be tested in the
field. An automated gas chromatograph
(GC) using a solid sorbent to preconcen-
trate volatile organic compounds (VOCs)
from the ambient air was placed in the P4
station. The unit cycled through an auto-
mated sample and analysis sequence ev-
ery hour. The objective of this monitoring
method was to evaluate the use of a solid
sorbent as a VOC preconcentrator and
further to demonstrate the use of auto-
mated GCs as a means to establish the
variability of VOC concentrations in time.
The P4 site was also used for place-
ment of sector samplers. These units were
placed at the P4 and S20 sites to charac-
terize the industrial complex near Stan-
dard Chlorine. Data was also taken near
the Army Creek and Delaware Sand and
Gravel site using the sector samplers.
Personal sampling devices (PSDs) were
used as fenceline dosimeters at several of
the sites. These units sample by diffusion
and are small and convenient to use. Since
the units are less than two inches in diam-
eter, they can be attached to any conve-
nient structure and used to obtain a
time-integrated ambient air sample. To es-
tablish the validity of the fenceline moni-
tors for screening of VOCs, they were
used in side-by-side tests with canisters.
Long path monitors based on selective
absorption of infrared radiation by target
gases were used at four of the sites. The
objective was to define the field capabili-
ties of FTIR-based long path monitors.
These monitors use source and receiver at
one end of a monitoring path and a retro-
reflector at the other end. The pathlength
is typically 300 m long, giving a total
pathlength of 600 m.
New solid sorbents specifically chosen
for retention of phenolic compounds were
also used at the Superfund sites. How-
ever, the field study was intended as a
scoping study in this case since only labo-
ratory studies had been done up to this
point.
Results and Discussion
The main field study was carried out
during the period 24 July through 9 August
1990 at the Superfund sites as planned.
Individual experiments and experimental
results are summarized below.
Automated Gas Chromatograph
AREAL's new automated GC using a
multisorbent bed for preconcentration
operated successfully when cycled
on an hourly basis over two weeks.
The automated GC was calibrated
daily for 12 consecutive days with a
relative standard deviation (RSD) of
response that was less than 10% for
all but dichlorodifluoromethane.
Use of the automated GC data in the
Temporal Profile Analysis (TPA) ap-
proach resulted in the identification
of groups of compounds originating
from nearby sources.
Fourier Transform Infrared Long Path
System
An independent calibration of the Fou-
rier transform infrared (FTIR) sys-
tem, in which a mixture of seven
gases was presented to the system,
demonstrated that the results are
compound-dependent and differ by 2
to 35% from the nominal calibration
standards.
• The precision of the FTIR was deter-
mined by presenting the same mix-
ture of gases to the FTIR on 16
occasions. The results again show a
compound dependency, with RSD
values from 4 to 41%.
The detection limits of this instru-
ment are compound-specific but can
generally range from 20 to 100 ppb.
The comparison of the FTIR data
with the results from the canister tech-
nique was complicated by the rapidly
changing concentrations caused by
the movement of a small plume of
industrial emissions that touched
down intermittently along the moni-
toring path. The comparison for p-
dichlorobenzene was good, the xe-
sults of point sampling and long path
monitoring being statistically the
same. For chlorobenzene, the FTIR
was operating very close to the theo-
retical detection limit, and the aver-
age difference between results was
34%. The error bars on the FTIR
data for this compound are large
enough to conclude that no statisti-
cal difference really exists.
Canister samples taken simulta-
neously but transported in opposite
directions along the path show differ-
ences of up to a factor of 2. Canister
samples taken simultaneously and
side by side in the traversal of the
path show variabilities of about 15%.
Sector Sampling
.Sector sampling was used to identify
the major compounds emitted from
an industrial complex.
Sequential Sampler
A set of 25 compounds was ana-
lyzed by using the TPA technique,
and a subset of these compounds
showed strong correlation (>0.85).
The air mass carrying these com-
pounds was seen to have passed
over the industrial complex prior to
its arrival at the sampler.
Personal Sampling Devices
Eleven sampling events were moni-
tored at three sites, and data were
analyzed for six volatile compounds.
The analysis shows good agreement
with the canister data. The PSDs can
be used as fenceline dosimeters
around landfills.
Anion Exchange Resin
This was the first field test of sorbent
sampling with anion exchange res-
ins. The technique was the least de-
veloped technique to be tested in the
Delaware field study. Interpretation
of results is limited and complicated
""by the lower-than-expected sample
concentrations.
One of the most interesting observa-
tions was that the dominant concentra-
tions noted in monitoring near "old"
Superfund sites were due to local (within 5
km) industrial emissions.
The Delaware SITE Study of 1989 has
shown the feasibility for field monitoring for
five of the six monitoring techniques that
were tested for organic compounds. Auto-
mated gas chromatographs, canister-based
sequential samplers, personal sampling
devices for VOCs, canister-based sector
samplers, and long path infrared transmis-
sion monitors were successfully used to
monitor target compounds at ambient air
concentrations. Comparisons between per-
-------
sonal sampling devices and canisters, and
between long path infrared transmission
monitors, were effective in providing for a
strong quality assurance program. Based
on results of the study, four articles for
submission to peer-reviewed journals have
been prepared. Information from the Dela-
ware study is already being used in EPA
Region I (sector samplers), in EPA Region
VII (long path infrared transmission moni-
tors), and in EPA Region IV (automated
gas chromatographs).
Conclusions and
Recommendations
Automated Gas Chromatograph
This system should be redesigned
so that liquid nitrogen is no longer
required.
A single supplier of an integrated
system including both the GC and
the preconcentrator should be identi-
fied.
• Different sorbents such as the
Supelco triple bed sorbent should be
evaluated as a preconcentrator of
VOCs.
Figure 1. Monitoring sites for the 1989 Delaware SITE study.
Fourier Transform Infrared Long Path Sys-
tem
Several changes to the instrument de-
sign need to be addressed to improve the
detection capability of this technique. These
include
Recoat the retro-reflector with a coat-
ing that is nonabsorbing across the
spectral region of interest.
Direct the beam through the inter-
ferometer before it traverses the path
in order to eliminate the background
emission.
Identify and install a smaller light
source.
Develop a procedure for determining
the precision and accuracy of the
FTIR data.
Sector Sampling
The design of this instrument should
be altered to include sector limits
that can be reset rather than being
fixed at 90°.
The instrument should be provided
with a threshold for wind speed.
Technology transfer to the regional
offices should be initiated.
Sequential Sampler
The difficulty with the accumulation
of water vapor in the instrument's
valve system must be solved.
A portable, battery-operated wind
speed/wind direction sensor must be
identified for use with the sampler at
monitoring sites.
Technology transfer of this technique
to the EPA regional offices should be
initiated.
Personal Sampling Devices
• The use of sorbents other than Tenax
GC should be evaluated. This re-
quires both laboratory and field test-
ing.
An investigation should be made into
the use of supercritical fluid extrac-
tion of VOCs from solid sorbents.
The use of these devices as a screen-
ing technique for a wider range of
volatile compounds at Superfund sites
should be investigated.
Anion Exchange Resin
A sealable field sampling cartridge
should be developed that is capable
of sustaining sample flow rates up to
1 L/min.
The sampling technique should be
retested at a site with known high
concentrations of phenolic com-
pounds.
A series of both laboratory and field
tests should be conducted in which
the impinger method (EPA Method
TO-8), given in the Compendium of
Methods for the Determination of
•&U.S. GOVERNMENT PRINTING OFFICE: 1992 - 648-080/40143
-------
Toxic Organic Compounds in Ambi-
ent Air, is used as a comparison.
The information in this document has
been funded in part by the U.S. Environ-
mental Protection Agency. It has been sub-
jected to Agency review and approved for
publication. Mention of trade names and
commercial products does not constitute
endorsement or recommendation for use.
The EPA authors, W.A. McClenny (also the Project Officer; see below), J.D. Pleil, J.L.
Vams, J.D. Mullk, RE. Berkley, K.J. Krost, arid W.T. McLeod, are with the Atmo-
spheric Research and Exposure Assessment Laboratory, Research Triangle Park, NC
27711. G.M. Russwurm, K.D. Oliver, andD.D. Williams are with ManTech Environ-
mental Technology, Inc., Research Triangle Park, NC27709. M.W. Holdren andAJ.
Pollack are with Battelle Columbus Laboratories, Columbus, OH 43201.
The complete report, entitled "Superfund Innovative Technology Evaluation, The
Delaware SITE Study, 1989," (Order No. PB92-125749/AS; Cost: $26.00, 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:
Atmospheric Research and Exposure Assessment Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati. OH 45268
BULK RATE
POSTAGE & FEES PAID
EPA PERMIT NO. G-35
Official Business
Penalty for Private Use $300
EPA/600/S3-91/071
------- |