United States National Risk Management

Environmental Protection Research Laboratory

Agency Cincinnati OH 45268

Research and Development EPA/600/SR-97/024 July 1997

Testing the Performance of

Real-Time Incinerator Emission

Monitors

S.B. Ghorishi, W.E. Whitworth, Jr., C.G. Goldman, and L.R. Waterland

Project Summary

In a recently completed test program

at the U.S. Environmental Protection

Agency (EPA) Incineration Research Facility (IRF), ten prototype or developing

continuous emission monitors (CEMs)

for measuring trace metal or trace organic species concentrations were

tested. Of the ten CEMs tested, four

measured concentrations of several

specific volatile organic compounds

(VOCs), one measured total particulatebound polynuclear aromatic hydrocarbon concentrations, two measured

concentrations of up to 14 trace metals, and three measured mercury concentrations. While the testing consisted

of obtaining quantitative measurement

data on the four measures of CEM performance checked in a relative accuracy test audit as described in 40 CFR

60 Appendix F—relative accuracy (RA),

calibration drift (CD), zero drift (ZD),

and response time—the primary project

objective focused on the RA measurement. The RA measurement was

achieved by comparing the monitored

analyte concentration reported by the

CEM to the concentration determined

by the EPA reference method (RM) for

the analyte. Four series of tests were

performed, each simultaneously testing up to three monitors measuring the

same or similar analyte type. Each test

series consisted of performing triplicate RM measurements at each of three

target flue gas monitored analyte concentrations while the tested CEMs were

in operation. All measurements were

taken in the wet scrubber exit flue gas

from the pilot-scale rotary kiln incineration system at the IRF.

The test program results clearly

showed the prototype nature of most

approaches tested, and the clear need

for further development. Mercury CEMs

will require the least development and

are nearly commercial offerings. However, the approaches tested for multimetals and VOC determinations require

further development. Given this need,

the importance of continuing test programs of the scope and scale of this

one cannot be overemphasized.

This Project Summary was developed

by EPA’s National Risk Management

Research Laboratory, Cincinnati, OH,

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).

Introduction

EPA is currently developing more stringent emission standards and considering

changes in the way that permits for waste

combustion facilities are handled. More

public involvement in the process has been

proposed. Because the public’s apparent

perception of incinerators is that high concentrations of hazardous compounds are

continually being released from the stacks

of the thermal treatment devices, a means

by which the “real-time” (defined as ranging from instantaneous to within several

hours) organic and metals emissions can

be monitored would be of great benefit to

both regulators and the regulated commu-
2

nity. The ability to have “immediate” knowledge of stack emissions would provide

assurances that the thermal treatment device is operating correctly or indicate the

change of operating conditions needed to

adjust stack emissions. Thus, having this

monitoring capability would constitute one

means of responding to and allaying the

public’s fears by showing that good, safe,

and clean combustion practices can be

demonstrated.

Several developers have designed monitoring units that they claim will measure

various regulated hazardous compounds

using a number of different innovative concepts and technologies. The development

of these CEM approaches for both trace

metal and trace organic analyte classes

has advanced to the state that several

candidate approaches are now in the prototype instrument stage. Given this, the

general objective of the project reported

herein was to test several prototype instruments and establish or estimate for

each unit the effectiveness, reliability, accuracy, and detection limit.

For this test program, ten developing

CEM approaches were tested. These are

listed in Table 1 by monitored analyte

class. As shown, included in the list of

CEMs tested in this program are one

semivolatile organic constituent (SVOC),

four VOC, two multi-metal, and three mercury CEMs.

Test Program

The selected approaches evaluated in

this test program were performed in the

pilot-scale rotary kiln incineration system

(RKS) at EPA’s IRF, located in Jefferson,

AR. The testing consisted of obtaining

quantitative measurement data on four

measures of CEM performance checked

in a relative accuracy test audit of a CEM

as described in 40 CFR 60 Appendix F.

These measures are RA, CD, ZD, and

response time.

Measuring a CEM’s RA requires comparing the monitored analyte concentration reported by the CEM to the

concentration determined by the RM for

the analyte. In this program, the RM for

trace metal (including mercury) monitors

was draft Method 29, the EPA multiple

metals method documented in the boiler

and industrial furnace rules. The RM for

VOCs was Method 0030 with analysis using thermal desorption, purge and trap by

Method 5040, and quantitation by Method

8015A. The RM for SVOCs was Method

0010 with analysis by Method 8270B.

Test Facility

Figure 1 is a process schematic of the

RKS as configured for these tests. The

RKS consists of a primary combustion

chamber, a transition section, and a fired

afterburner chamber. After exiting the afterburner extension, flue gas flows through

a quench section that is followed by a

primary air pollution control system

(APCS). The initial element of the primary

APCS for these tests was the venturi

scrubber/packed-column scrubber combination shown in Figure 1. This scrubber

system removes from the flue gas most of

the coarse particles and any acid gas,

such as HCl. Following the scrubber system, the flue gas is reheated to about

120°C (250°F) by a 100-kW electric duct

heater, then passed through a fabric filter

(baghouse). The baghouse removes most

of the remaining flue gas particles. Downstream of the baghouse, a backup, secondary APCS, comprised of an

activated-carbon adsorber and a high-efficiency particulate air filter is in place. The

CEMs tested in this program sampled flue

gas at the scrubber exit location.

Testing Procedures

The test program consisted of four series of tests; each series tested one set of

CEMs, generally monitoring the same analyte set. Up to three CEMs were tested at

the same time during each of the four test

series. The major portion of the test program consisted of performing three sequential RM measurements, while the

tested CEMs were in operation, at each of

three flue gas concentrations of monitored

analytes. Thus, each test series was designed to supply nine sets of parallel RM

and CEM reading data, three at each of

three analyte concentrations. These nine

sets of parallel RM and CEM data supported the calculation of each CEM’s RA.

Thus, up to three RAs were calculated for

each CEM, one at each of the three flue

gas concentrations tested. Other test efforts supported the measurements of CD,

ZD, and response time.

Test Waste Feed

The incinerator feed material was a synthetic hazardous waste comprised of an

attapulgite clay solid sorbent combined

with a mixture of 14 trace metals and

VOCs. The mixture of VOCs added to the

sorbent base contained 76% toluene by

weight, with 12% each of chlorobenzene

and tetrachloroethene. This mixture was

combined with the clay sorbent in the ratio of 1.0 kg of organic constituent mixture

to 2.4 kg of clay. The mixture was a freeflowing solid with no freestanding liquid

and was continuously fed to the RKS via

a screw feeder system. For all tests, the

target clay/organic mixture feedrate was

68 kg/hr (150 lb/hr). The target kiln exit

gas temperature was 870°C (1,600°F), and

the target afterburner exit gas temperature was 1,065°C (1,950°F).

Table 1. Participants in the CEM Test Program

Monitored

Analyte Developer Approach

SVOCs EcoChem Photoionization of aerosol-bound polycyclic

aromatic hydrocarbons

VOCs EcoLogic Continuous chemical ionization mass

spectrometry

Marine Shale Processors (MSP) Continuous online mass spectrometry

Oak Ridge National Laboratory (ORNL) Direct sampling ion trap mass spectrometry

EPA, Air Pollution Prevention and Online gas chromatography with dual flame

Control Division (APPCD) ionization, electron capture detection

Multi-metals Sandia National Laboratories (SNL) Laser induced plasma spectroscopy

Metorex Extractive beta gauge particulate monitor

with x-ray fluorescence metals analysis

Mercury Perkin-Elmer Gold trap amalgamation collection, cold

vapor atomic absorption spectroscopy

analysis

Senova Noble metal film solid state chemical

microsensor

EcoChem Cold vapor atomic absorption spectroscopy
3

Multi-Metal and Mercury CEM

Tests

The trace metals of interest to the test

program are listed in Table 2, which also

notes the program target scrubber exit

flue gas concentrations of each metal for

the tests of multi-metals CEMs. For the

mercury CEMs tests in Test Series 3, the

low concentration targets were at half the

levels noted in the low concentration column in Table 2. The intermediate concentration targets were those noted in the low

concentration column in Table 2. The high

concentration targets were those noted in

the intermediate concentration column in

Table 2. This change was incorporated at

the request of the mercury CEM developers.

Trace metals were added to the RKS,

to result in scrubber exit flue gas levels,

via two routes. Both routes used an aqueous spike solution of the metals. A concentrated solution was added for the

multi-metal CEM test days at the high

target flue gas metals concentration. This

concentrated solution was diluted for the

multi-metal CEM test days at the intermediate and low target concentrations and

Table 2. Test Trace Metals and Target Flue

Gas Concentrations

Target Flue Gas Concentration,

μg/dscm

Metal Low Intermediate High

Antimony (Sb) 10 40 400

Arsenic (As) 5 20 200

Barium (Ba) 50 200 2,000

Beryllium (Be) 0.5 2 20

Cadmium (Cd) 5 20 200

Chromium (Cr) 20 80 560

Cobalt (Co) 10 40 400

Lead (Pb) 50 200 2,000

Manganese (Mn) 5 20 200

Mercury (Hg) 20 80 800

Nickel (Ni) 10 40 400

Selenium (Se) 40 200 2,000

Silver (Ag) 5 20 200

Thallium (Tl) 5 20 200

for the mercury CEM tests. The two routes

of metals addition were incorporated into

the clay/organic mixture and atomized into

the kiln main burner flame.

VOC and SVOC CEM Tests

The VOCs present in the scrubber

exit flue gas for all tests included benzene, carbon tetrachloride, chlorobenzene, chloroform, 1,2-dichloroethane,

1,1-dichloroethene, tetrachloroethene,

toluene, 1,1,1-trichloroethane, and trichloroethene. The target flue gas concentrations of the compounds were in the

2, 20, and 200 μg/dscm ranges (low, intermediate, and high concentrations).

Naphthalene, phenanthrene, and pyrene

were the SVOCs introduced into the flue

gas for all tests, at the same target flue

gas concentrations noted above.

The VOCs and SVOCs were introduced

into the flue gas by metering a solution of

the spiking compounds in methanol

through a length of fine bore stainless

steel tubing into the afterburner extension

at its centerline. The afterburner exit flue

gas was partially quenched to a temperature of between 360° to 427°C (680° and

800°F) by a water spray introduced at the

Quench

Secondary

burner

Air

Natural

gas,

liquid

feed

Transfer

duct

Ash

bin

Afterburner Solids

feeder

Main

burner

Afterburner

extension

Rotary

kiln Natural

gas

liquid feed

Venturi

scrubber

Scrubber

liquor

recirculation

Flue gas

reheater

Ash hopper

Air

Baghouse

Carbon bed

adsorber

HEPA

filter ID fan

Stack

Atmosphere

ID fan

Rotary Kiln Incinerator Primary Air Pollution Control System

Redundant Air Pollution

Control System

Packed

Column

Scrubber

Figure 1. Schematic of the IRF rotary kiln incineration system.

▼

Packed

column

scrubber
4

beginning of the afterburner extension. A

concentrated organic spiking solution was

prepared and used for the high target flue

gas VOC and SVOC CEM tests. The concentrated solution was diluted appropriately for the intermediate and low target

flue gas concentration tests.

Test Results

VOC CEM Tests

Tables 3 through 5 present the results

of the three sequential RM measurements,

along with the Oak Ridge National LaboTable 3. Measured Flue Gas Concentrations for the Test of the ORNL and EcoLogic CEMs at the Low VOC Concentration

Concentration, μg/dscm

1st Daily RM 2nd Daily RM 3rd Daily RM

Eco- Eco- EcoCompound RM ORNL Logic RM ORNL Logic RM ORNL Logic

Benzene 32.4 1.3 NOa 41.9 1.6 NO 59.6 1.6 NO

Carbon 31.2 <0.4 NO 34.2 <0.4 NO 38.0 0.92 NO

tetrachloride

Chlorobenzene 55.6 0.76 NO 49.2 1.2 NO 86.7 5.6 NO

Chloroform 40.8 0.56 NO 47.3 0.4 NO 41.6 3.6 NO

1,2-Dichloroethane 2.4 2.5 NO 3.3 1.5 NO 2.6 6.8 NO

1,1-Dichloroethene 86.4 3.2 NO 35.6 <0.4 NO 16.9 11.0 NO

Tetrachloroethene 89.9 1.7 NO 73.9 1.3 NO 126 4.3 NO

Toluene 352 9.2 NO 316 9.2 NO 462 16 NO

1,1,1- 2.5 <0.4 NO 4.6 <0.4 NO 6.4 <0.4 NO

Trichloroethane

Trichloroethene 6.9 <0.4 NO 5.9 <0.4 NO 3.9 <0.4 NO

aNO=CEM not operational.

Table 4. Measured Flue Gas Concentrations for the Test of the ORNL and EcoLogic CEMs at the Intermediate VOC Concentration

Concentration, μg/dscm

1st Daily RM 2nd Daily RM 3rd Daily RM

Eco- Eco- EcoCompound RM ORNL Logic RM ORNL Logic RM ORNL Logic

Benzene 32.7 12.0 97 28.7 <2.3 820 36.4 5.5 870

Carbon 46.9 10.1 7.9 41.7 3.8 24 58.5 6.4 16

tetrachloride

Chlorobenzene 59.8 25.8 81 46.3 7.2 81 74.3 27.6 98

Chloroform 57.1 23.9 140 56.7 9.6 230 66.3 18.4 170

1,2-Dichloroethane 17.4 43.3 210 12.3 16.6 340 15.3 29.5 290

1,1-Dichloroethene 24.0 55.3 320 20.5 26.7 430 14.3 40.5 370

Tetrachloroethene 81.4 11.1 120 64.1 2.5 770 101 7.4 710

Toluene 342 147 210 218 71.8 120 413 103 250

1,1,1- 13.8 <2.3 800 13.3 <2.3 910 12.9 <2.3 840

Trichloroethane

Trichloroethene 19.4 4.6 420 18.6 0.9 770 20.4 1.8 510

ratory (ORNL) and EcoLogic CEM results,

for each of the three VOC concentrations

tested in Test Series 1. The EcoLogic

CEM data for the first day of testing at the

low VOC concentration were not reported

in EcoLogic’s test report because of operator error that resulted in CEM readings

that were inflated and incorrect. RAs calculated using the RM and CEM data in

Tables 3 through 5 are summarized in

Table 6. The data in Table 6 show that

the calculated RAs for the ORNL CEM

ranged from 123% to 305% at the low test

concentration, with an average of 196%

over the seven compounds reported.

ORNL CEM RAs were improved at the

intermediate test concentration, at 113%

to 278%, with an average of 154% over

the nine compounds reported. Further improvement is seen at the high test concentration, with an RA range of 84% to

144%, and an average of 105% over all

ten compounds reported. In fact, the RA

for all VOCs reported uniformly improved

as the test concentration increased.
5

Table 5. Measured Flue Gas Concentrations for the Test of the ORNL and EcoLogic CEMs at the High VOC Concentration

Concentration, μg/dscm

1st Daily RM 2nd Daily RM 3rd Daily RM

Eco- Eco- EcoCompound RM ORNL Logic RM ORNL Logic RM ORNL Logic

Benzene 102 36.8 140 89.1 50.7 160 91.3 28.6 190

Carbon 423 101 380 409 119 350 446 76.4 360

tetrachloride

Chlorobenzene 337 138 250 299 170 270 269 97.6 280

Chloroform 417 101 330 411 168 350 413 91.2 390

1,2-Dichloroethane 184 88.4 450 174 114 500 183 6.3 540

1,1-Dichloroethene 116 38.7 350 140 44.2 440 162 35.9 480

Tetrachloroethene 429 62.6 690 374 61.7 740 324 37.8 690

Toluene 1,760 847 1,300 1,393 921 1,200 1,024 460 760

1,1,1- 175 24.9 170 164 37.8 190 182 20.3 210

Trichloroethane

Trichloroethene 189 15.7 340 176 19.3 300 185 14.7 360

Table 6. Relative Accuracies of the ORNL and EcoLogic CEMs

RA,%

ORNL EcoLogic

Test Concentration Test Concentration

Compound Low Intermediate High Low Intermediate High

Benzene 173 119 98 NC 5,020 154

Carbon tetrachloride NCa 129 100 NC 135 27

Chlorobenzene 164 93 84 NC 74 52

Chloroform 123 105 97 NC 396 33

1,2-Dichloroethane 305 278 144 NC 2,890 239

1,1-Dichloroethene 299 277 115 NC 2,520 283

Tetrachloroethene 162 142 113 NC 1,640 128

Toluene 145 131 88 NC 65 47

1,1,1-Trichloroethane NC NC 110 NC 7,320 36

Trichloroethene NC 113 103 NC 5,140 116

Averageb 196 154 105 NC 2,520 121

Medianb 164 129 100, NC 1,640, 52,

103 2,520 116

a NC=Not calculated.

b Average and median excludes NC entries.

For the intermediate test concentration, the RAs of the EcoLogic CEM

ranged from 65% to 7,320%, with an

average of 2,520%. Improved performance was seen at the high test concentration, for which the RA ranged from

27% to 283% and averaged 121%. As

seen for the ORNL CEM, the RAs for

nine of the ten VOCs reported were improved at the high test concentration

compared to the intermediate concentration.

Tables 7 through 9 present the results

of the three sequential RM measurements, along with the EPA/APPCD and

MSP CEM results, for each of the three

VOC concentrations tested in Test Series 4. The tables indicate that, out of

the nine sampling periods, MSP obtained

data for only two periods. RAs corresponding to the RM/CEM concentration

data given in Tables 7 through 9 are

summarized in Table 10. The data in

Table 10 show that the RAs for the EPA

CEM ranged from 71% to 3,190% and

averaged 638% for the low test concentrations. The relatively high average RA

was driven by the two very high RAs for

1,2-dichloroethane and 1,1-dichloroethene. These two compounds were found

in EPA/APPCD system blanks. EPA/

APPCD’s decision not to blank-correct

their data led to the corresponding high

RAs. The median RA for the low concentration test at a much improved 113%
6

Table 7. Measured Flue Gas Concentrations for the Test of the EPA/APPCD and MSP CEMs at the Low VOC Concentration

Concentration, μg/dscm

1st Daily RM 2nd Daily RM 3rd Daily RM

EPA/ EPA/ EPA/

Compound RM APPCD MSP RM APPCD MSP RM APPCD MSP

Benzene 8.2 21.31 NOa 5.9 29.93 795 8.4 22.21 707

Carbon 13.9 9.68 NO 11.9 5.99 118 13.3 4.99 126

tetrachloride

Chlorobenzene 21.6 18.56 NO 20.8 29.16 143 16.0 18.8 60.2

Chloroform 15.8 16.95 NO 18.4 14.89 3,439 15.8 9.25 1,515

1,2-Dichloroethane 1.8 43.21 NO 1.5 39.18 73.7 1.6 30.33 78.5

1,1-Dichloroethene 2.0 76.34 NO 6.3 90.23 322 5.1 84.49 271

Tetrachloroethene 32.7 15.65 NO 26.9 31.7 124 20.6 8.56 107

Toluene 160.9 131.92 NO 149.4 221.38 1,308 97.1 57.85 814

1,1,1- 2.1 2.21 NO 1.9 2.22 3.6 1.8 3.53 4.1

Trichloroethane

Trichloroethene 2.6 2.18 NO 2.9 2.71 3,022 3.0 1.74 1,602

aNO=Not operational.

Table 8. Measured Flue Gas Concentrations for the Test of the EPA/APPCD and MSP CEMs at the Intermediate VOC Concentration

Concentration, μg/dscm

1st Daily RM 2nd Daily RM 3rd Daily RM

EPA/ EPA/ EPA/

Compound RM APPCD MSP RM APPCD MSP RM APPCD MSP

Benzene 33.9 35.8 NOa 32.9 42.41 NO 33.6 50.34 NO

Carbon 53.5 31.45 NO 57.8 37.58 NO 64.1 40.55 NO

tetrachloride

Chlorobenzene 29.5 24.86 NO 64.6 54.15 NO 75.0 40.73 NO

Chloroform 43.2 26.33 NO 62.1 31.61 NO 63.5 43.31 NO

1,2-Dichloroethane 20.7 27.97 NO 18.1 34.9 NO 16.6 55.71 NO

1,1-Dichloroethene 14.2 47.14 NO 11.3 54.48 NO 9.9 101.19 NO

Tetrachloroethene 39.3 22.87 NO 92.7 58.32 NO 96.8 30.3 NO

Toluene 143 90.22 NO 498.5 306.1 NO 551.8 163.48 NO

1,1,1- 17.3 13.68 NO 16.2 14.33 NO 17.4 14.54 NO

Trichloroethane

Trichloroethene 22.9 16.04 NO 20.6 16.63 NO 19.1 15.74 NO

aNO=Not operational.

to 137%, removes the dominant influence

of the two compounds for which the CEM

did poorly. The RAs for the EPA CEM

were improved at the intermediate test

concentration, ranging from 29% to 1,130%

and averaging 213%. Poor performance

in quantitating 1,2-dichloroethane and 1,1-

dichloroethene again accounts largely for

the high average RA. Again, the median

RA at 83% to 98% better reflects the

mean performance of the CEM by removing the dominant influence of the RAs for

the two VOCs poorly quantitated. Further

improved performance of the EPA CEM

was seen at the high test concentration,

with an RA range from 34% to 133% and

an average RA of 73%. In fact, at the high

test concentration, the RAs for two compounds poorly quantitated at the low and

intermediate test concentrations are more

in line with those calculated for the other
7

Table 9. Measured Flue Gas Concentrations for the Test of the EPA/APPCD and MSP CEMs at the High VOC Concentration

Concentration, μg/dscm

1st Daily RM 2nd Daily RM 3rd Daily RM

EPA/ EPA/ EPA/

Compound RM APPCD MSP RM APPCD MSP RM APPCD MSP

Benzene 102.6 96.33 NOa 129.5 98.73 NO 117.7 88.66 NO

Carbon 222.5 209.55 NO 266.2 205.53 NO 283.7 135.72 NO

tetrachloride

Chlorobenzene 104.8 119.78 NO 146.5 113.78 NO 127.2 126.99 NO

Chloroform 229.4 190.9 NO 243.8 199.06 NO 241.1 178.42 NO

1,2-Dichloroethane 93.7 95.44 NO 121.2 107.96 NO 114.9 90.81 NO

1,1-Dichloroethene 65.9 113.67 NO 65.5 124.81 NO 71.9 144.06 NO

Tetrachloroethene 112.8 150.65 NO 162.6 161.66 NO 132.2 131.62 NO

Toluene 176.6 191.23 NO 445.4 213.8 NO 261.5 217.23 NO

1,1,1- 97.8 92.89 NO 106.8 87.31 NO 103.5 57.93 NO

Trichloroethane

Trichloroethene 98.2 98.46 NO 114.3 91.81 NO 113.1 70.04 NO

aNO=Not operational.

Table 10. Relative Accuracies of the EPA/APPCD and MSP CEMs

RA,%

EPA/APPCD MSP

Test Concentration Test Concentration

Compound Low Intermediate High Low

Benzene 429 83 48 18,300

Carbon tetrachloride 86 45 95 1,200

Chlorobenzene 87 98 53 3,150

Chloroform 76 71 34 85,800

1,2-Dichloroethane 3,190 334 40 6,740

1,1-Dichloroethene 2,040 1,130 133 10,700

Tetrachloroethene 137 134 50 673

Toluene 113 158 138 3,040

1,1,1-Trichloroethane 150 29 73 315

Trichloroethene 71 45 70 384,000

Average 638 213 73 51,400

Median 113, 137 83, 98 53,70 3,150, 6,740

eight compounds. For this reason, the

median RA at 53% to 70% is comparable

to the average RA.

The calculated RAs based on the two

available CEM/RM measurement pairs for

the MSP CEM were quite large, ranging

from 315% to 412,000% and averaging

54,600%. Even the median RAs for the

MSP CEM, at 2,840% to 6,480%, are

quite high.

SVOC CEM Tests

The SVOC CEM tests were performed

at the same time as the second set of

VOC CEM tests. Table 11 presents the

results of the three sequential RM measurements performed each test day, and

compares these to the EcoChem CEM

results for the test days at the low and

intermediate SVOC concentrations. Due

to problems in the flue gas conditioning

(moisture removal) system, the EcoChem

CEM could not be brought into operation

on the last day of testing at the high

SVOC concentration. In addition, no CEM

data were obtained during the first RM

period on the intermediate concentration

test day because the EcoChem CEM was

not in operation, again due to problems

with the flue gas moisture removal system.

Table 11 also notes the RA of the

EcoChem PAH CEM for the two test days

the CEM was in operation. The

table indicates that the RAs for the
8

Table 11. Measured Flue Gas Concentrations for the Tests of the EcoChem PAH CEMs

Concentration, μg/dscm

Test 1st Daily RM 2nd Daily RM 3rd Daily RM RA,%

Low Concentration Test

Naphthalene 1.7 1.8 1.7

Phenanthrene 1.3 1.2 1.3

Pyrene 1.0 0.8 0.9

Total PAH 4.0 3.8 3.9

EcoChem CEM 6.9 14.8 15.5 527

Intermediate Concentration Test

Naphthalene 17.5 10.9 15.8

Phenanthrene 15.7 10.1 15.3

Pyrene 9.1 19.6 9.7

Total PAH 42.3 40.6 40.8

EcoChem CEM NOa 33.2 39.0 99

High Concentration Test

Naphthalene 97.0 NPb NP

Phenanthrene 91.4 NP NP

Pyrene 68.2 NP NP

Total PAH 256.6 NP NP

EcoChem CEM NO NO NO NCc

aNO=Not operational.

bNP=Not performed.

cNC=Not calculated.

Table 12. Measured Flue Gas Concentrations for the Test of the SNL and Metorex CEMs at the Low Metals Concentrations

Concentration, μg/dscm

1st Daily RM 2nd Daily RM 3rd Daily RM

Metal RM SNL Metorex RM SNL Metorex RM SNL Metorex

Antimony (Sb) 4.5 NDa ND 5.1 ND ND 4.5 ND 5.13

Arsenic (As) 4.4 ND 3.65 3.8 ND 0.83 3.6 ND 1.19

Barium (Ba) 11.7 ND ND 15.8 ND ND 18.6 ND 6.23

Cadmium (Cd) 9.7 ND 2.63 12.1 ND ND 13.2 ND 10.02

Chromium (Cr) 22.3 ND 2.49 23.5 ND 0.56 28.0 ND 22.29

Cobalt (Co) 7.8 ND 12.11 7.1 ND ND 7.1 ND 14.68

Lead (Pb) 101 ND 11.51 85.6 ND 9.06 110 ND 12.36

Manganese (Mn) 21.8 ND 5.89 29.2 ND ND 31.6 ND 19.43

Nickel (Ni) 39.6 ND 27.52 29.1 ND 6.15 42.4 ND 21.87

Selenium (Se) 11.4 ND 1.51 12.3 ND 1.47 12.3 ND 3.62

Thallium (Tl) 1.1 ND ND 1.5 ND ND 1.7 ND ND

aND=Not detected.

EcoChem CEM were 527% and 99%. As

was seen in the VOC CEM tests, the RA

at the higher test flue gas concentration

was improved in comparison to the lower

test concentration.

Multi-Metal CEM Tests

Tables 12 through 14 summarize the

results of the three sequential RM measurements performed each test day and

compares these to the Sandia National

Laboratories (SNL) and Metorex CEM

measurements. Neither CEM measured

beryllium or mercury, so these metals are

not included in the three tables. In addition, results for silver are not included in

the tables. Spike recovery from QA

samples was poor, so silver concentra-
9

Table 13. Measured Flue Gas Concentrations for the Test of the SNL and Metorex CEMs at the Intermediate Metals Concentrations

Concentration, μg/dscm

Reference Method 1 Reference Method 2 Reference Method 3

Metal RM SNL Metorex RM SNL Metorex RM SNL Metorex

Antimony (Sb) 11.0 NDa 39.73 11.6 ND 22.00 9.5 ND 8.49

Arsenic (As) 11.1 63 11.92 10.8 42 0.74 8.7 115 6.61

Barium (Ba) 78.0 251 44.37 80.0 199 11.87 49.2 463 9.92

Cadmium (Cd) 14.0 ND 7.22 15.0 ND 26.93 14.2 ND 10.09

Chromium (Cr) 54.7 ND 56.48 59.5 ND 72.51 50.3 ND 25.68

Cobalt (Co) 32.3 ND 14.72 33.9 ND 20.79 27.4 ND 9.79

Lead (Pb) 141 144 107.07 141 93 51.80 136 106 40.86

Manganese (Mn) 24.2 ND 61.4 24.6 ND 55.58 18.2 ND 31.25

Nickel (Ni) 59.9 ND 26.48 61.2 ND 21.26 52.6 ND 15.76

Selenium (Se) 43.2 ND 29.34 54.5 ND 21.27 53.2 ND 18.12

Thallium (Tl) 11.1 ND 12.96 11.2 ND 4.49 12.4 ND 2.72

aND=Not detected.

Table 14. Measured Flue Gas Concentrations for the Test of the SNL and Metorex CEMs at the High Metals Concentrations

Concentration, μg/dscm

Reference Method 1 Reference Method 2 Reference Method 3

Metal RM SNL Metorex RM SNL Metorex RM SNL Metorex

Antimony (Sb) 114 233 27.32 75.7 186 18.35 43.5 131 6.59

Arsenic (As) 82.2 75 21.82 64.8 86 13.28 54.8 65 4.68

Barium (Ba) 331 650 207.37 484.3 NDa 111.07 285 ND 27.29

Cadmium (Cd) 88.0 ND 33.58 60.9 ND 31.73 88.7 ND 22.18

Chromium (Cr) 425 ND 129.33 299 ND 91.85 241 ND 34.70

Cobalt (Co) 357 ND 100.16 229 ND 67.47 248 ND 37.62

Lead (Pb) 1,650 ND 297.20 1,082 ND 282.71 2,176 54 167.04

Manganese (Mn) 179 ND 52.89 89.9 ND 35.25 95.6 ND 16.56

Nickel (Ni) 550 ND 160.10 347 ND 111.42 429 ND 67.89

Selenium (Se) 421 ND 102.52 399 ND 96.70 383 ND 39.92

Thallium (Tl) 114 ND 32.29 94.3 ND 28.10 113 ND 16.84

aND=Not detected.

tions as measured by the RM are highly

suspect. The SNL CEM did not detect any

of the test trace metals on the low concentration test day, only arsenic, barium,

and lead were reported on the intermediate concentration test day, and only antimony, arsenic, barium, and lead for one

or more RM periods were reported on the

high concentration test day.

The RAs corresponding to the measurement pair data in Tables 12 through

14 are summarized in Table 15. The data

in Table 15 show that the RAs for the

SNL CEM ranged from 64% to 1,560% for

the three metals reported on the intermediate concentration test day, and from 65%

to 188% for the two metals reported on

the high concentration test day. RAs for

the Metorex CEM ranged from 88% to

236%, with an average of 129% and a

median of 116% for the low concentration

test. Corresponding RAs for the intermediate concentration test were 72% to

467%, with an average of 168% and a

median of 135%, and, for the high concentration test, 93% to 177%, with an

average of 129% and a median of 121%.

The RAs for the Metorex CEM were comparable for each test concentration. No

marked improvement as flue gas concentration increased, as observed for the VOC

CEMs, is seen in the Metorex CEM data.
10

Table 15. Relative Accuracies of the SNL and Metorex CEMs

RA,%

SNL Metorex

Test Concentration Test Concentration

Metal Low Intermediate High Low Intermediate High

Antimony (Sb) NCa NC 188 NC 467 158

Arsenic (As) NC 1,560 65 125 174 101

Barium (Ba) NC 905 NC NC 135 153

Cadmium (Cd) NC NC NC 89 177 123

Chromium (Cr) NC NC NC 158 94 113

Cobalt (Co) NC NC NC 236 72 118

Lead (Pb) NC 64 NC 115 112 177

Manganese (Mn) NC NC NC 116 261 146

Nickel (Ni) NC NC NC 88 77 121

Selenium (Se) NC NC NC 104 113 93

Thallium (Tl) NC NC NC NC 171 111

Averageb — 843 127 129 168 129

Medianb — 905 65, 116 135 121

188

aNC=Not calculated.

bAverage and median exclude RAs NC.

Table 16. Measured Flue Gas Concentrations and RAs for the Mercury CEM Tests

Mercury Concentration, μg/dscm

EcoChem Perkin-Elmer Senova

Test RM CEM CEM CEM

Low Mercury Concentration

RM 1 21 22 78 NOa

RM 2 16 20 42 NO

RM 3 13 19 11 NO

RA,% 60 602 NCb

Intermediate Mercury Concentration

RM 1 56 83 61 NO

RM 2 34 43 NO NO

RM 3 40 56 125 NO

RA,% 92 1,150 NC

High Mercury Concentration

RM 1 119 137 NO 232

RM 2 94 81 NO 116

RM 3 86 62 405 165

RA,% 61 NC 186

aNO=Not operational.

bNC=Not calculated.

Mercury CEM Tests

Table 16 summarizes the results of three

sequential RM measurements performed

each mercury CEM test day and compares these to the corresponding three

mercury CEM measurements. Calculated

RAs for each CEM are also given in the

table for the three test days, each representing a different flue gas mercury concentration. The table indicates several

periods during which the Perkin-Elmer and

the Senova CEMs were not in operation.

The data in Table 16 show that the

EcoChem CEM had an RA of about 60%

for both the low and the high concentration tests. The RA at the intermediate

concentration was increased, at 92%. The

RA of the Perkin-Elmer CEM was 602%

at the low mercury concentration and

1,150% (based on two measurement pairs)

at the intermediate mercury concentration.

The RA of the Senova CEM was 186% at

the one test concentration having data.

The full report was submitted in fulfillment of Contract No. 68-C4-0044, Work

Assignments 0-4 and 1-1, by Acurex Environmental Corporation under the sponsorship of the U.S. Environmental

Protection Agency.
11

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/SR-97/024

S. B. Ghorishi, W. E. Whitworth, Jr., C. G. Goldman, and L. R. Waterland are with

Acurex Environmental Corporation, Jefferson, AR 72079.

R. C. Thurnau is the EPA Project Officer, and M. K. Richards is the Work

Assignment Manager (see below).

The complete report, entitled “Testing the Performance of Real-Time Incinerator

Emission Monitors,” (Order No. PB97-142871; Cost: $38.00, 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 and Work Assignment Manager can be contacted at

National Risk Management Research Laboratory

U.S. Environmental Protection Agency

Cincinnati, OH 45268