U.S. Environmental Protection Agency
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Dioxin Emission Monitoring Systems
The U.S. EPA Environmental Technology Verification (ETV)
Program's Advanced Monitoring Systems (AMS) Center, operated
by Battelle under a cooperative agreement with EPA, has verified
the performance of four dioxin emission monitoring systems.1
The verification test was conducted in collaboration with EPA's
Office of Research and Development, Office of Solid Waste and
Emergency Response, and Office of Air Quality Planning and
Standards; the Chlorine Chemistry Council, and Battelle. The
dioxin emission monitoring systems are designed to replace
manual stack sampling techniques used to quantify dioxins in flue
gas which are labor intensive and expensive. The verification
reports and statements can be found at: http://www.epa.gov/nrmrl/
std/etv/vt-ams.html under dioxin emission monitoring systems.
Technology Description and Verification Testing
ETV verified the technologies using a 2.94 million British thermal
unit (860 kilowatts) per hour, 3-Pass Wetback Scotch Marine
Package Boiler, manufactured by Superior Boiler Works, Inc., and
located at the EPA Research Triangle Park (NC) facility. The four
verified technologies (Table 1) fall under one of two categories:
automated isokinetic sampling systems of flue gas with laboratory
analysis, or semi-continuous laser-based systems that produce ions
which are typically
detected using a
time-of-flight mass
spectrometer
(TOFMS). Long-
term continuous
samplers collect
samples over time
periods up to
several weeks to
obtain a cumulative
record of source
emissions and
provide evidence of
emission levels.
Verification test site for dioxin Real or semi-real -
Dioxin at a Glance
Dioxins refers to a group of chemical
compounds that are members of three
closely related families: the
polychlorinated dibenzo-p-dioxins
(PCDDs), polychlorinated
dibenzofurans (PCDFs) and certain
polychlorinated biphenyls (PCBs).
Health Effects
Short-term exposure of humans to high
levels of dioxins may result in skin
lesions, such as chloracne and patchy
darkening of the skin, and altered liver
function. Long-term exposure is linked
to impairment of the immune system,
the developing nervous system, the
endocrine system, and reproductive
functions. Chronic exposure of
animals to dioxins has resulted in
several types of cancer.
Sources
Dioxins are mostly formed as a result
of combustion processes such as
commercial or municipal waste
incineration and from burning fuels
(like wood, coal or oil). EPA's Draft
Dioxin Reassessment Report1 makes
the finding that anthropogenic
emissions dominate current releases in
the United States, but acknowledges
the need for more data on natural
sources.
1 Draft has been provided to Hie National Academy of
Sciences for review.
emission monitoring systems
(Continued on page 2)
Table 1. Verified Dioxin Emission Monitors
Technology Name
BM Becker Messtechnik Gmbh
AMESA (Adsorption Method for Sampling Dioxins
and Furans)
Monitoring Systems GmbH
Dioxin Monitoring System
IDX Technologies, LTD.
RIMMPA-TOFMS (Resonance lonization with
Multi-Mirror System Photon Accumulation Time-of-
Flight Mass Spectrometer)
SRI International
Jet-REMPI (Resonance Enhanced Multi-photon
lonization)
Description
A long-term sampling apparatus which is based on the isokinetic sampling of flue gas and the adsorp-
tion of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and other
persistent organic pollutants on an exchangeable adsorption-resin-filled cartridge.
A long-term sampling device using an automatic isokinetic sampler for measurement of PCDDs, PCDFs,
and other persistent organic pollutants. Samples are collected using a filter cartridge.
A laser-based mass spectrometry system that has been developed for the real-time detection and quan-
tification of PCDD and PCDFs.
A laser-based system that produces ions which are typically detected using a TOFMS that takes advan-
tage of the pulsed nature and well-defined temporal character of laser ionization.
The ETV Program operates largely as a public-private partnership through competitive cooperative agreements with non-profit research institutes. The
program provides objective quality-assured data on the performance of commercial-ready technologies. Verification does not imply product approval or
effectiveness. ETV does not endorse the purchase or sale of any products and services mentioned in this document.
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(Continued from page 1)
time continuous monitors, with a
frequency of measurement at real time or
up to an hour, provide quick feed back to
the plant operator by measuring dioxin
emission levels on-site.
ETV evaluated the performance of the
dioxin monitoring systems in terms of
relative accuracy (RA), range, data
completeness, and operational factors
(ease of use, maintenance, and
consumables/waste generated). RA and
range were determined by comparing the
dioxin monitoring systems results to those
from EPA Method 23 reference samples
collected simultaneously. Range was
determined from measurements of a
variety of defined operating conditions
that produced different levels of dioxins.
Table 2 contains some of the test
parameter results. Because the ETV
Program does not compare technologies,
the performance results shown in Table 2
do not identify the vendor associated with
each result and are not in the same order
as the list of technologies in Table 1.
Potential Outcomes of Dioxin
Emission Monitoring Systems
Demonstrated effectiveness of dioxin
emission monitoring systems promotes:
• More continuous monitoring of
dioxin emissions
• Improved emission inventories
• Better estimates of human expo-
sures
• Opportunities for process control
^1 to reduce dioxin emissions.
Table 2. Selected Performance Results for Verified Dioxin Monitoring Systems
Measurement Systems
RA"(%)
RSD».°(%)
A
22.6
9.7
B
48.2
21.9
C
78.2
61.5
D
Analysis of the
collected samples
could not positively
quantify
PCDD/PCDFs
No quantifiable
results
Operational Factors
Instrument
Installation
Time
Time for
Operation
Training
Down Time
<48 hrs
1 - 2 hrs in
basic operation
<1%
<48 hrs
2 hrs in
basic operation
3%
N/A«
Extensive
training/
experience for
operation of
system
7%
Could not be
evaluated
Extensive training/
experience for
operation
of system
Could not be
evaluated
a Relative Accuracy for PCDDs and PCDFs. A 0% value means perfect accuracy.
b Relative Standard Deviation: The intermethod relative standard deviation (RSD) was
calculated using the standard deviation of the paired dioxin monitor and reference
method results for the test run.
c Relative Standard Deviation of Reference Method 23 was found to be 8.4
d Installation time was not part of the verification test for this monitor. Instrument was
installed before verification testing.
Verified dioxin
monitoring systems
References
U.S. EPA, ETV, http://www.epa.gov/etv/.
Lee, Chun Wai, Dennis Tabor and Kenneth
Cowen. 2006. ETV Test of PCDD/F Emissions
Monitoring Systems. Presentation given at the
4th International Conference on Combustion,
Incineration/Pyrolysis and Emission Control,
September 26-29 in Kyoto, Japan.
Battelle, 2005. The Monitor, Vol. 8, Number 5.
August/September.
National Center for Environmental Assessment.
Dioxin and Related Compounds, U.S. EPA.
http ://cfpub .epa.gov/ncea/cfm/recordisplay .cfm?
deid=55264.
ETV Advanced Monitoring
Systems Center
Robert Fuerst, EPA
fuerst.robert@epa.gov
Tel: (919) 541-2220
Amy Dindal, Battelle
dindala@battelle.org
Tel: (561) 422-0113
EPA/600/S-07/002
February 2007
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